CN1034522C - Plasma-reinforced electrochemical process for surface ceramicification and relevant product - Google Patents
Plasma-reinforced electrochemical process for surface ceramicification and relevant product Download PDFInfo
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- CN1034522C CN1034522C CN95114880A CN95114880A CN1034522C CN 1034522 C CN1034522 C CN 1034522C CN 95114880 A CN95114880 A CN 95114880A CN 95114880 A CN95114880 A CN 95114880A CN 1034522 C CN1034522 C CN 1034522C
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- sodium
- electrolyte solution
- borax
- described method
- arc discharge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The present invention discloses a method of coating the surface of a metallic matrix with ceramics and a product thereof. The present invention utilizes the arc discharging of plasma to sinter electrolyte materials on the surface of a matrix, and thus, a film with a ceramics structure is formed. The film of the present invention has the advantages of good uniformity, compaction with the matrix, good shock resistance, good tarnish resistance, multiple design and color and good decorative effect, and is suitable for the surface treatment of matrix workpieces with any dimension, shape and structure.
Description
The product that the present invention relates to the anodised method of metal material surface and make with this method.
Along with modern industry and science and technology development, stupalith is with its distinctive performance, rich in natural resources advantage and become third generation engineering materials after iron and steel, aluminium.Because the bulk ceramics material fragility is big, workability is poor, is fettering its widespread use always.Implement the potteryization coating at metal and alloy surface, can guarantee to replace expensive metallic substance with cheap metallic substance under the use properties prerequisite, give simultaneously the matrix metal material some with other surface strengthening technology the property that can't obtain, widen its scope of application.On the other hand, carry out surface ceramic deposition as matrix, can improve the moulding and the processing characteristics of stupalith, for the surface ceramic deposition part for preparing complicated shape provides safeguard, for new way has been opened up in the widespread use of pottery with easy work material.
A kind ofly strengthen electrochemical reaction with plasma by SU1812247A is known, prepare the method for potteryization rete as ionogen at metal and alloy surface with Sodium hexametaphosphate 99, wherein current density is 20-500A/dm
2, pulse length is the 0.1-2.5 microsecond, and frequency is 1-150Hz, and voltage is the 140-1000 volt, and the hexa metaphosphoric acid sodium content is 6～12% (about 60-120g/l) in the electrolyte solution.This kind method exists the deficiency of following several respects:
1, the lack of homogeneity of processing back workpiece surface potteryization rete, surface size precision and roughness aspect existing problems, and reformation and reparation difficulty are big.
2, energy consumption is big in the course of processing, the energy that every square metre of need of average processing are 400 kilowatts and the cooling required equipment of electrolytic solution are huge, and investment is expensive, and technique controlling difficulty is big in the production process, manufacturing cost is high, and is extensive, mass industrialized production required electric power resource is big.
3, the color of product, pattern are single, and decorative effect is poor.
The objective of the invention is to overcome the above-mentioned defective of prior art, the method for the electrochemistry metal surface ceramic of a kind of low cost, less energy-consumption is provided.
Another object of the present invention provides a kind of made metal products that is covered with the potteryization rete.
Method of the present invention ties up to and contains with Sodium hexametaphosphate 99 10-50g/l, boric acid and/or borax 5-20g/l are main, also contain at least a oxysalt that is selected from sodium orthophosphate, sodium sulfate, water glass, ammonium meta-vanadate, sodium metavanadate, Sodium chromate, sodium wolframate, rose vitriol, single nickel salt, ferric sulfate, manganous sulfate, chromium sulphate, also can select to add in the electrolyte solution of additive of the acetate that is selected from calcium, zinc, cobalt, nickel, silicofluoric acid, Potassium monofluoride, ethylenediamine tetraacetic acid (EDTA), at 10-50 ℃ down by 100-400V voltage and 0.5-20A/dm
2The electric energy that produces of current density make as the plasma arc light discharge takes place on the anodic metal base surface, carry out electrochemical anodic oxidation, and make the ionogen that participates in reaction carry out sintering at matrix surface, form rete with ceramic structure.
In the methods of the invention, the forming process of potteryization rete is such:
In the electrochemical oxidation electrolyzer, metal works applies volts DS as anode at yin, yang two inter-stages, on the surface of workpiece following anodic oxidation reactions takes place:
Al＝Al
3+＋3e
OH
-＝1/2H
2O＋1/2[O]＋e
2Al+3[O]=Al
2O
3Form the oxide film of one deck densification, its thickness is about 0.01-0.2 μ m.This layer is thinner, has electrical insulating property, is called the blocking layer.Along with negative and positive interpolar voltage increases, it is very high by (about 10 that strength of electric field becomes
7V/cm), can produce electric breakdown phenomena at anode surface, produce the plasma body arc discharge on the anode workpiece surface, this arc discharge is created in the defectiveness of rete, the place that has slit, film to approach, energy density herein high (about 10
4～10
7W/cm
2), excited series of chemical at anode surface and electrolyte interface place, make the ionization of part material, activation in the ionogen.Because the enhancement of plasma body arc discharge except the electrochemical anodic oxidation main reaction takes place, also has some ionogen to participate in electrochemical reaction, carries out sintering at matrix surface, forms the rete with ceramic structure.
Method of the present invention also comprises the cleaning of the metallic matrix before the anodic oxidation and the rinsing after the anodic oxidation, sealing treatment.Therefore, the inventive method comprises the following steps:
1, cleans
Raw material such as light metal aluminium, titanium, niobium, zirconium, in various manufacturings, preservation process, surface coverage has different types of grease, needs thoroughly to remove greasy dirt in the oxidation first being processed.The preferred alkaline cleaning fluid that adopts, as following prescription: sodium phosphate 50-60g/l, water glass 10-15g/l, yellow soda ash 10-20g/l, tensio-active agent 0.1-10ml/l requires scavenging solution to adopt mandatory stirring or be ejected into workpiece surface in cell body, makes it to clean up, 40 °-60 ℃ of temperature, soak time 20-30 minute.Then workpiece is immersed in the rinse tank, require to use clear water, temperature 15-50 ℃, rinsing is clean, the not residual described scavenging solution of workpiece surface.
2, oxidation
It is the different electrolyte solutions of main salt with boric acid and/or borax 5-20g/l that employing contains Sodium hexametaphosphate 99 10-50g/l, control different process current, voltage, solution temperature, stirring intensity and mode, can obtain the product of different colours, different pattern, different pattern, different performance, applicable to the application of different field.The voltage that produces arc discharge is generally 100-400V, and current density is 0.5-20A/dm
2, solution temperature 10-50 ℃.
Narrate the production technique of variant production below respectively, wherein V represents to produce plasma arc sparking voltage, D
AThe expression anodic current density.
＜1〉porcelain whiteware membrane process
The composition of electrolyte solution: Sodium hexametaphosphate 99 (NaPO
3)
610-50g/l, sodium phosphate (Na
3PO
412H
2O) 10-30g/l, borax (Na
2B
4O
77H
2O) 5-20g/l, calcium acetate (Ca (Ac)
2) 01-5g/l, water glass (NaSiO
3) 0.1-10g/l, zinc acetate (Zn (Ac)
2) 0.1-12g/l, sodium sulfate (Na
2SO
4) 5-10g/l, boric acid (H
3BO
3) 5-20g/l.More than each material all adopt chemically pure reagent, or the highly industry product of special purpose are prepared with distilled water, preparation is in proper order, after earlier Sodium hexametaphosphate 99 thoroughly being dissolved, add other each material, can use the phosphorus acid for adjusting pH value, pH is 4.0-10.5, after the solution preparation, require to leave standstill more than 24 hours, solution temperature is controlled at 15-45 ℃, adopt forced action type to spray and stir, make solution stirring even.Process current density D
A=0.5-5A/dm
2, voltage V=100-400V, oxidization time are 7-30min, can make porcelain whiteware rete, thickness is 5-28 μ m.
＜2〉blue look ceramic membrane technology
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, boric acid 5-20g/l, ethylenediamine tetraacetic acid (EDTA) (EDTA) 1-6g/l, sodium sulfate 5-10g/l, sodium phosphate 5-15g/l, rose vitriol (CoSO
4) 5-20g/l, single nickel salt (NiSO
4) 1-10g/l, Cobaltous diacetate (Co (Ac)
2) 10-20g/l, pH is 4.0-6.Compound method is with＜1 〉, require solution left standstill more than 24 hours, solution temperature is 10 ℃-30 ℃, converted products main two big classes, the even blue look film of the first, it two is orchid point films that the different size flowers of band have decorative effect.Processing requirement: control anodic current density D
A=0.5-10A/dm
2, voltage V=150V-300V prepares the requirement of even blue look film and adopts mandatory solution stirring, plating bath is stirred fully, time 5-20min; The method that the different size flower points of preparation have the orchid point film of decorative effect changes the plating bath alr mode for adopting, the discharge centers number of workpiece surface is reduced, the discharge centers current density is increased, cause that colored point not of uniform size is arranged on some material discharge generation surfaces, play beautiful decorative effect.Specific practice mainly is control anodic current density D
A=0.5-7A/dm
2, force homogeneity to stir (technology as described above) 5-10min, leave standstill 3-5min then, stir suddenly or workpiece is moved in bath trough, reach the big purpose of change in concentration, the period is 1-5min, produces the different decoration coating of flower point.Thickness 5-15 μ m obtains blue from shallow to deep look film.Other color product of this processing condition also can adopt.
＜3〉cream-coloured film
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, sodium phosphate 5-10g/l, boric acid 5-10g/l, nickel acetate (Ni (Ac)
2) 2-15g/l, sodium sulfate 5-10g/l, borax 5-10g/l, ferric sulfate (Fe
2(SO
4)
3) 2-10g/l, ethylenediamine tetraacetic acid (EDTA) 1-6g/l, manganous sulfate (MnSO
4H
2O) 2-10g/l; Compound method is with＜1 〉, pH is 4-6, solution temperature is controlled to be 15-45 ℃, process current density D
A=0.5-10A/dm
2, V=125-350V, oxidization time are 5-20min, thicknesses of layers: 5-25 μ m, adopt＜1〉technology alr mode, and obtain oldlace to dark cream-coloured rete.
＜4〉dark pink film
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-20g/l, sodium phosphate 10-30g/l, water glass 0.5-10g/l, zinc acetate 0.1-12g/l, manganous sulfate 5-20g/l; Compound method is with＜1 〉, process current density D
A=0.5-10A/dm
2, V=150-350V, temperature 10-40 ℃.This handicraft product has two big classes, adopts as＜2〉as described in different alr modes, can make evenly dark pink colour film or have the decorative film of different size flowers.Oxidization time is 5-25min, and thickness is 5-25 μ m, obtains dark pink rete from shallow to deep.
＜5〉coffee-like to black film
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-10g/l, ammonium meta-vanadate (NH
4VO
3) 2-10g/l, sodium metavanadate (NaVO
3) 2-10g/l, sodium sulfate 5-10g/l; Compound method is as＜1 〉, pH is 3-6, process current density D
A=0.5-5A/dm
2, V=150-350V, solution temperature 10-35 ℃, oxidization time is 5-20min, adopts as＜2〉described different alr modes and can make flower point rete or the uniform rete of color and luster.Its color by shallow coffee to coffee to black.Thickness 5-15 μ m.
＜6〉yellow fraction is to yellow film
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-10g/l, ammonium meta-vanadate 2-7g/l, sodium metavanadate 2-7g/l, nickel acetate 5-15g/l, manganous sulfate 1-5g/l, boric acid 5-10g/l; Compound method is as＜1 〉, pH=3-7, process current density D
A=0.5-5A/dm
2, V=150-300V, time 5-15min, temperature 10-30 ℃, employing as＜2〉described different alr modes can produce the uniform rete of surface color or there are ornamental retes of spending some difference size on the surface.The rete color is extremely dark yellow to Huang by yellow fraction.Thickness 5-20 μ m.
＜7〉coppery film modelled after an antique
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 10-15g/l, sodium phosphate 10-15g/l, ammonium meta-vanadate 1-10g/l, Sodium chromate (Na
2CrO
4) 2-10g/l; Compound method is with＜1 〉, process current density D
A=0.5-10A/dm
2, V=150-350V, the time is 5-20min, 10 ℃-50 ℃ of temperature, thicknesses of layers is 5-15 μ m, the film color is extremely bronze-colored deeply by pale yellow bronze.
＜8〉grey film
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 10-50g/l, sodium sulfate 5-10g/l, sodium phosphate 10-15g/l, rose vitriol 2-15g/l, chromium sulphate (Cr
2(SO
4)
3) 2-15g/l, Cobaltous diacetate 2-10g/l, nickel acetate 2-10g/l, ammonium meta-vanadate 2-10g/l; Compound method is as＜1 〉, current density D
A=0.5-10A/dm
2, V=125-350V, temperature 20-50 ℃, oxidization time 5-20min adopts as there are the grey film of spending point, thickness 5-20 μ m in＜2〉the described different alr modes rete of grey from shallow to deep or the surfaces that can make color even.
＜9〉hard ceramic rete
The composition of electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, silicofluoric acid (H
2SiF
6) 2-20ml/l, Potassium monofluoride (KF) 1-10g/l, borax 7-20g/l, sodium wolframate (Na
2WO
4) 1-20g/l; Compound method is as＜1 〉, process current density D
A=1-15A/dm
2, V=100-200V, solution temperature 10-30 ℃, oxidization time 5-25min, technology stirs and adopts forced action type evenly to stir, and prepared rete color is a Dark grey, thickness: 10-100 μ m.
Except that the said products kind, wherein any two plating bath collocation are used, and all can produce the rete of different patterns.Such as,＜1〉the porcelain white films for preparing in the plating bath is＜2〉reoxidation and adopt aforementioned alr mode in the plating bath, can generate the assortment of the blue point of white background cover, concrete technology is seen embodiment two.
3, rinsing
Water temperature requires 15 ℃-60 ℃, requires to clean not residual solution composition.
4, sealing treatment
Workpiece after rinsing can adopt coating processs such as dip-coating, showering, spraying, carries out surperficial sealing treatment, mainly is for improving its glossiness.Adopt coating such as water-soluble acrylic or water soluble amino resin, dry processing according to the requirement of coating, the water soluble acrylic acid bake out temperature is 150～250 ℃, time 5～30min.Product is qualified on inspection after the oven dry packs.
Method of the present invention has strengthened electrochemical reaction owing to adopted the plasma body arc discharge, in the rete of generation from the substances content in the ionogen than the height in the conventional anode oxide film, and do not contain the hydrate of substrate metal oxide.
So, the product that method of the present invention makes is made of the pottery rete of metallic matrix and matrix surface, in the wherein said rete, the content of substrate metal oxide is 70.0～95.0% (weights), and the content of other metal oxide, nonmetal oxide, inorganic salt or their mixture is 5.0～30.0%.Described potteryization rete is formed by plasma body arc discharge enhanced anonizing, and described other metal oxide, nonmetal oxide, inorganic salt or their mixture material are from the electrolyte solution.
The rete pattern of product of the present invention is regular inserted stacking, and porosity is extremely low, and less than 0.5%, macroscopic defects is few.Each component uniform distribution in rete.Because the atoms metal of matrix surface is participated in reaction directly,, and there be not obvious the boundary so combine fine and closely between rete and matrix.
The ceramic layer good uniformity of product of the present invention, with the substrate combinating strength height, hole is few, and shock resistance and solidity to corrosion are all good, and bright-colored, and pattern is many, can form pattern, and is ornamental splendid.Method of the present invention is applicable to the surface treatment of the matrix workpiece of virtually any size, shape, structure.
Further specify the present invention below by embodiment.
Embodiment one
Get 1000ml distilled water and put into the oxidation trough that volume is 1.5L, add the 35g Sodium hexametaphosphate 99, make it abundant dissolving, add borax 10.5g, add sodium phosphate 10g, regulating pH with phosphoric acid is 4.5～5.0, adds the 5g calcium acetate, be mixed with plating bath, placed 24 hours, stand-by.Get the LD31 type aluminium sheet of 50 * 100 * 5mm, clean rinsing then with alkaline cleaning fluid, with anchor clamps on the workpiece, be communicated with power supply, stir in the groove, do negative electrode with stainless steel plate, workpiece is an anode, the beginning oxide treatment, keep constant current 1A, voltage is slow to rise to 160～180V, and workpiece surface has plasma body arc discharge phenomenon, when voltage rose 210～240V, electric current descended, and oxidization time is 10min, stop oxidation, electric current is transferred to 0, voltage transfers to 0, powered-down takes out workpiece, obtains the porcelain white films, through cleaning, carry out sealing treatment, dip-coating in water-borne acrylic resin, baking is 5 minutes in 220 ℃ baking oven, take out, promptly can be finished product.After testing, thickness 10 μ m, microhardness (HV) is 310kg/mm
2(5g), wear-resisting evaluation: 300 seconds sandblast time.Block 9 grades of this experiments.
Embodiment two
1000ml distilled water adds in the oxidation trough of 1.5L, adds Sodium hexametaphosphate 99 35g, and the dissolving back adds boric acid 10g, rose vitriol 2g, and ethylenediamine tetraacetic acid (EDTA) 2g, placed 24 hours the dissolving back, stand-by.With the method among the embodiment one, oxidation obtains a porcelain white films workpiece, puts into this oxidation trough after cleaning, and solution keeps leaving standstill at this moment, the oxidation of switching on, electric current 0.7A/dm
2Keep 1.5min, make workpiece move (or carry out plating bath and stir) then, the surface produces the less relatively arc discharge phenomenon of number, and this process keeps 1min, stop oxidation, powered-down takes out workpiece, makes white base and slanders the workpiece of spending point with blue look, workpiece gets product behind the glazing of sealing described in the embodiment one.
Embodiment three
In the industrial production oxidation trough of a long 7.2m, wide 1.6m, dark 2.3m, add 20000kg water, add the 700kg Sodium hexametaphosphate 99, force to stir, after making it fully dissolving, add borax 140g, ammonium meta-vanadate 100kg, sodium sulfate 200kg, fully, placed 24～48 hours, this groove adopts handpiece Water Chilling Units, keep 15 ℃～35 ℃ of groove temperature, with stainless steel plate as negative electrode.Get one and hang aluminium alloy building shape material (6063 type) 15, through measuring every root surface area is 180 square decimeters, and 15 total surface areas are 2700 square decimeters, put in the rinse bath, soak 25min, after mentioning with overhead traveling crane, control water, in the rinse tank that discharges water, put into second rinse tank after mentioning, put into then in the oxidation trough, begin energising and carry out oxidation, electric current 1A/dm
2, voltage is slow to be risen, and solution stirring is cooled off, when voltage rose to 150V, workpiece surface had small arc light to occur, and keeps the said processing condition in front, oxidization time is 10min, and final voltage is 230V, reduces electric current, powered-down is mentioned workpiece, control water, put into rinse tank, and then rinsing, resin storage tank immersed, enter in the baker at last and dry, unload extension then, packing.Through check, color is coffee-like, thickness 8～11 μ m, and outward appearance is even, microhardness (HV) 260～480kg/mm
2(0.049N).Wear-resisting evaluation: sandblast time 300-500S.
Embodiment four
Get 1000ml distilled water and add in the 1.5L oxidation trough, add sodium phosphate 25g, borax 7g, water glass 10g after the dissolving, placed 24 hours fully, with the stainless steel is negative electrode, gets the titanium alloy sheet (TA1 type) of 50 * 100mm * 1mm, after cleaning, put into the oxidation trough oxidation, anodic current is 3A, and voltage begins to rise, when arriving 100V, the surface has small arc light to produce, and the controlled oxidation time is 15min, and voltage is to 150V, reduce electric current, powered-down takes off workpiece and carries out rinsing, after the oven dry, sample film is a grey, after tested, thickness is 15 μ m, and blocking this experiment is 9 grades.
Embodiment five
Get 100kg kilogram distilled water and put into oxidation trough, add the 3.5kg Sodium hexametaphosphate 99, the dissolving back adds the 1000ml silicofluoric acid fully, borax 1.5kg, sodium wolframate 0.5kg, Potassium monofluoride 0.2kg, fully after the dissolving, leave standstill 24 hours stand-by.Get the pure aluminum plate of 150 * 100 * 10mm, carry out clean, last anchor clamps, put into oxidation trough and handle, electric current is 15A, and voltage is slow to be risen, when arriving 100V, the plasma body arc discharge occurs, voltage rises very slow, and the period is 20min, final voltage is 180V, reduce electric current, powered-down takes out workpiece.Rinsing is dried and is finished product.This thicknesses of layers 50～70 μ m after tested, the wear-resisting time of sandblast is 720～800 seconds, microhardness 900～1300HV (0.098N).With substrate combinating strength 25.6～35.0k8/mm
2
Such scheme only provides as an example, and does not limit the present invention in any way, and those skilled in the art can carry out various changes or improvement to the present invention, but does not all break away from the protection domain of essence of the present invention and claim.
Claims (13)
1, a kind of method of metal base surface potteryization, this method is included in the electrolyte solution, make as anodic metal base surface plasma arc light discharge by electric energy, carry out electrochemical anodic oxidation, formation has the rete of ceramic structure, before described oxide treatment, carry out the cleaning of matrix, after oxidation, carry out rinsing and sealing treatment, it is characterized in that: used electrolyte solution is with Sodium hexametaphosphate 99 10-50g/l, boric acid and/or borax 5-20g/l are main, also contain at least a sodium orthophosphate that is selected from, sodium sulfate, water glass, ammonium meta-vanadate, sodium metavanadate, Sodium chromate, sodium wolframate, rose vitriol, single nickel salt, ferric sulfate, manganous sulfate, the oxysalt of chromium sulphate, and can select adding to be selected from calcium, zinc, cobalt, the acetate of nickel, silicofluoric acid, Potassium monofluoride, the additive of ethylenediamine tetraacetic acid (EDTA); Arc discharge voltage is 100-400V, and current density is 0.5-20A/dm
2, the electrolyte solution temperature is 10-50 ℃.
2, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, sodium phosphate 10-30g/l, borax 5-20g/l, calcium acetate 0.1-5g/l, water glass 0.1-10g/l, zinc acetate 0.1-12g/l, sodium sulfate 5-10g/l, boric acid 5-20g/l; PH is 4.0-10.5; Arc discharge voltage is 100-400V.
3, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, boric acid 5-20g/l, ethylenediamine tetraacetic acid (EDTA) 1-6g/l, sodium sulfate 5-10g/l, sodium phosphate 5-15g/l, rose vitriol 5-20g/l, single nickel salt 1-10g/l, Cobaltous diacetate 10-20g/l; PH is 4.0-6; Arc discharge voltage is 150-300V.
4, the described method of claim 1, it is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, sodium phosphate 5-10g/l, boric acid 5-10g/l, nickel acetate 2-15g/l, sodium sulfate 5-10g/l, borax 5-10g/l, ferric sulfate 2-10g/l, ethylenediamine tetraacetic acid (EDTA) 1-6g/l, manganous sulfate 2-10g/l; Arc discharge voltage is 125-350V.
5, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-20g/l, sodium phosphate 10-30g/l, water glass 0.5-10g/l, zinc acetate 0.1-12g/l, manganous sulfate 5-20g/l; Arc discharge voltage is 150-350V.
6, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-10g/l, ammonium meta-vanadate 2-10g/l, sodium metavanadate 2-10g/l, sodium sulfate 5-10g/l; PH is 3-6; Arc discharge voltage is 150-350V.
7, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 5-10g/l, ammonium meta-vanadate 2-7g/l, sodium metavanadate 2-7g/l, nickel acetate 5-15g/l, manganous sulfate 1-5g/l, boric acid 5-10g/l; PH is 3-7; Arc discharge voltage is 150-300V.
8, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 10-15g/l, sodium phosphate 10-15g/l, ammonium meta-vanadate 1-10g/l, Sodium chromate 2-10g/l; Arc discharge voltage is 150-350V.
9, the described method of claim 1, it is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, borax 10-50g/l, sodium sulfate 5-10g/l, sodium phosphate 10-15g/l, rose vitriol 2-15g/l, chromium sulphate 2-15g/l, Cobaltous diacetate 2-10g/l, nickel acetate 2-10g/l, ammonium meta-vanadate 2-10g/l; Arc discharge voltage 125-350V.
10, the described method of claim 1 is characterized in that consisting of of described electrolyte solution: Sodium hexametaphosphate 99 10-50g/l, silicofluoric acid 2-20ml/l, Potassium monofluoride 1-10g/l, borax 7-20g/l, sodium wolframate 1-20g/l; Arc discharge voltage 100-200V.
11, the described method of claim 1-10 is characterized in that, in oxidising process, mandatory stirring electrolyte solution makes solution even.
12, the described method of claim 1-10 is characterized in that, in oxidising process, forces homogeneity to stir electrolyte solution, stops then stirring, and stirs suddenly or matrix is moved in solution.
13, the product that makes with the described method of claim 1 to 12.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95114880A CN1034522C (en) | 1995-04-18 | 1995-04-18 | Plasma-reinforced electrochemical process for surface ceramicification and relevant product |
| EP95930367A EP0823496B1 (en) | 1995-04-18 | 1995-09-11 | Process for producing ceramic layer by plasma enhanced electrolysis and product thereof |
| DE69526256T DE69526256T2 (en) | 1995-04-18 | 1995-09-11 | PRODUCTION OF A CERAMIC LAYER WITH PLASMA SUPPORTED ELECTROLYSIS AND PRODUCT MADE THEREOF |
| PCT/CN1995/000072 WO1996033300A1 (en) | 1995-04-18 | 1995-09-11 | Process for producing ceramic layer by plasma enhanced electrolysis and product thereof |
| JP8531384A JP2937484B2 (en) | 1995-04-18 | 1995-09-11 | Methods and products for plasma enhanced electrochemical surface ceramicization |
| AU33788/95A AU3378895A (en) | 1995-04-18 | 1995-09-11 | Process for producing ceramic layer by plasma enhanced elect rolysis and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95114880A CN1034522C (en) | 1995-04-18 | 1995-04-18 | Plasma-reinforced electrochemical process for surface ceramicification and relevant product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1115793A CN1115793A (en) | 1996-01-31 |
| CN1034522C true CN1034522C (en) | 1997-04-09 |
Family
ID=5080362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95114880A Expired - Fee Related CN1034522C (en) | 1995-04-18 | 1995-04-18 | Plasma-reinforced electrochemical process for surface ceramicification and relevant product |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0823496B1 (en) |
| JP (1) | JP2937484B2 (en) |
| CN (1) | CN1034522C (en) |
| AU (1) | AU3378895A (en) |
| DE (1) | DE69526256T2 (en) |
| WO (1) | WO1996033300A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050389C (en) * | 1997-04-21 | 2000-03-15 | 哈尔滨环亚微弧技术有限公司 | Energy control method for plasma enhanced electrochemical formation of cermet |
| US7452454B2 (en) | 2001-10-02 | 2008-11-18 | Henkel Kgaa | Anodized coating over aluminum and aluminum alloy coated substrates |
| US7578921B2 (en) | 2001-10-02 | 2009-08-25 | Henkel Kgaa | Process for anodically coating aluminum and/or titanium with ceramic oxides |
| US7569132B2 (en) | 2001-10-02 | 2009-08-04 | Henkel Kgaa | Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating |
| US7820300B2 (en) | 2001-10-02 | 2010-10-26 | Henkel Ag & Co. Kgaa | Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating |
| US20060016690A1 (en) * | 2004-07-23 | 2006-01-26 | Ilya Ostrovsky | Method for producing a hard coating with high corrosion resistance on articles made anodizable metals or alloys |
| EP2371996B1 (en) * | 2008-12-26 | 2016-03-09 | Nihon Parkerizing Co., Ltd. | Method of electrolytic ceramic coating for metal, electrolysis solution for electrolytic ceramic coating for metal, and metallic material |
| US9701177B2 (en) | 2009-04-02 | 2017-07-11 | Henkel Ag & Co. Kgaa | Ceramic coated automotive heat exchanger components |
| CN102102217A (en) * | 2009-12-18 | 2011-06-22 | 中国电子科技集团公司第四十九研究所 | Method for manufacturing alumina film by micro-arc oxidation |
| CN103290448A (en) * | 2013-05-07 | 2013-09-11 | 锡山区羊尖泓之盛五金厂 | Metal surface corrosion-resistant treatment method |
| JP2015074825A (en) * | 2013-10-11 | 2015-04-20 | 株式会社栗本鐵工所 | Film formation method by plasma electrolytic oxidation and metal material |
| CN104404601B (en) * | 2014-12-19 | 2017-09-29 | 中北大学 | A kind of microarc oxidation treatment process of Mg Gd Y Zr cast magnesium alloys |
| CN105862131B (en) * | 2016-06-03 | 2018-05-01 | 武汉工程大学 | A kind of introducing method of molybdenum when preparing molybdenum carbide crystal using MPCVD |
| GB201610615D0 (en) | 2016-06-17 | 2016-08-03 | Keronite Int Ltd | Durable white inorganic finish for aluminium articles |
| CN107630185B (en) * | 2017-09-15 | 2020-01-17 | 芜湖通潮精密机械股份有限公司 | Regeneration method of wallboard in dry etching machine |
| CN111876811B (en) * | 2020-07-27 | 2022-02-25 | 上海交通大学 | Aluminum-lithium alloy micro-arc oxidation method and electrolyte adopted by same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3834999A (en) * | 1971-04-15 | 1974-09-10 | Atlas Technology Corp | Electrolytic production of glassy layers on metals |
| US4869798A (en) * | 1987-10-27 | 1989-09-26 | Flachglas Aktiengesellschaft | Apparatus for the galvanic reinforcement of a conductive trace on a glass pane |
| EP0462073A2 (en) * | 1990-06-14 | 1991-12-18 | JENOPTIK GmbH | Electrolyte for producing thin black conversion layers on light metals |
| RU1812247C (en) * | 1990-08-24 | 1993-04-30 | Институт Прикладной Физики | Method of article working |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3328049A1 (en) * | 1983-08-03 | 1985-02-21 | Hoechst Ag, 6230 Frankfurt | METHOD FOR ONE-STAGE ANODIC OXIDATION OF CARRIER MATERIALS MADE OF ALUMINUM FOR OFFSET PRINTING PLATES |
| CN87103694A (en) * | 1985-10-24 | 1988-11-09 | 鲁道夫·何拉德科夫斯基 | The electro-plating method of aluminum products and used electroplate liquid |
| DE3870925D1 (en) * | 1987-02-02 | 1992-06-17 | Friebe & Reininghaus Ahc | METHOD FOR PRODUCING DECORATIVE COATINGS ON METALS. |
| CN2202135Y (en) * | 1994-08-30 | 1995-06-28 | 哈尔滨环亚微弧技术有限公司 | Arc reinforcing electrochemical deposition device for surface of aluminium alloy |
-
1995
- 1995-04-18 CN CN95114880A patent/CN1034522C/en not_active Expired - Fee Related
- 1995-09-11 DE DE69526256T patent/DE69526256T2/en not_active Expired - Fee Related
- 1995-09-11 JP JP8531384A patent/JP2937484B2/en not_active Expired - Fee Related
- 1995-09-11 WO PCT/CN1995/000072 patent/WO1996033300A1/en not_active Application Discontinuation
- 1995-09-11 EP EP95930367A patent/EP0823496B1/en not_active Revoked
- 1995-09-11 AU AU33788/95A patent/AU3378895A/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3834999A (en) * | 1971-04-15 | 1974-09-10 | Atlas Technology Corp | Electrolytic production of glassy layers on metals |
| US4869798A (en) * | 1987-10-27 | 1989-09-26 | Flachglas Aktiengesellschaft | Apparatus for the galvanic reinforcement of a conductive trace on a glass pane |
| EP0462073A2 (en) * | 1990-06-14 | 1991-12-18 | JENOPTIK GmbH | Electrolyte for producing thin black conversion layers on light metals |
| RU1812247C (en) * | 1990-08-24 | 1993-04-30 | Институт Прикладной Физики | Method of article working |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0823496B1 (en) | 2002-04-03 |
| WO1996033300A1 (en) | 1996-10-24 |
| JPH10509772A (en) | 1998-09-22 |
| DE69526256T2 (en) | 2002-11-07 |
| EP0823496A1 (en) | 1998-02-11 |
| CN1115793A (en) | 1996-01-31 |
| AU3378895A (en) | 1996-11-07 |
| DE69526256D1 (en) | 2002-05-08 |
| JP2937484B2 (en) | 1999-08-23 |
| EP0823496A4 (en) | 1998-05-20 |
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