CN103255467A - Novel material surface modification method and apparatus - Google Patents

Novel material surface modification method and apparatus Download PDF

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Publication number
CN103255467A
CN103255467A CN2012104108641A CN201210410864A CN103255467A CN 103255467 A CN103255467 A CN 103255467A CN 2012104108641 A CN2012104108641 A CN 2012104108641A CN 201210410864 A CN201210410864 A CN 201210410864A CN 103255467 A CN103255467 A CN 103255467A
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workpiece
anode
negative electrode
liquid
foam
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李锋
林均品
郝国建
王开阳
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University of Science and Technology Beijing USTB
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Taiyu (beijing) Materials Sci & Tech Co Ltd
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Abstract

The invention provides a novel material surface modification method and apparatus. The method comprises the following steps: introducing liquid electrode as an anode, using a workpiece as a cathode, adjusting electric parameter and producing glow effect on the workpiece surface. The method is characterized in that the processing gap between anode and cathode is full of a conductive medium which is composed of conductive liquid. Glow effect can be generated on the surface of the workpiece by adjusting voltage, current, electrolyte concentration and other technological parameters, thereby the surface properties of the workpiece are improved and changed. On the other hand, the invention provides an apparatus for changing and improving the conductive surface, and the apparatus comprises (1) an automatic control interface of power supply and corresponding computer; (2) an electrolytic plasma reaction generation chamber, and an apparatus for adding corresponding electrolyte and discharging from the processing zone; (3) a temperature controlling means of electrolyte; (4) and a mechanical apparatus for moving the processed workpiece. By the effects of the liquid glow effect, various physical and chemical changes can be generated on the material surface, thereby improving the antioxidation performance, the stress state or the like of the material surface.

Description

A kind of method and apparatus of type material surface modification
Technical field
The present invention relates to a kind ofly in liquid, produce the aura effect, and use the method and apparatus that this technology is carried out material surface modifying.
Background technology
The steel of metal, particularly many forms before finally coming into operation, needs to clean usually.After steel is produced, usually has one deck expanded skin (black oxide) film in its surface, or other dirt form, comprising iron rust, oil or lubricating grease, the drawing compound, chip and the cutting fluid that contain pigment, polishing and polishing compound.All these all must be removed usually, in order to guarantee coating, the enough sticking power of filming of product surface, prevent or reduce that taking off of coating and matrix split and the reduction of product subsequent technique performance.
The method that the metallic surface is cleaned has a lot, at different objects and requirement different sorting techniques is arranged.By the difference of cleaning principle, traditional metallic surface purging method mainly is divided into: mechanical cleaning, matting and spraywashing etc.
Yet there is various deficiencies in traditional method: metallic surface machinery cleans, and as technologies such as shot-peening, sandblasts, only is applicable to the equipment that profile is simple, regular, be not suitable for baroque workpiece, in addition, damage matrix surface easily, cause unrelieved stress, the surface treatment quality can not get guaranteeing; Matting, indispensable pickling and alkali washing process process when for example Iron and Steel Production and steel surface are handled is because the caused cost of liquid waste disposal and environmental problem more and more can not be accepted; In the spraywashing process, the solution of injection is short in the time that the cleaning object surface stops, and the cleansing power of washing lotion can not play one's part to the full, and has the problem of liquid waste disposal simultaneously.
The electrolysis process on clean metal surface is usually included in for example zinc-plated and electroplate in the processing of steel band and steel plate etc.Conventional electrolytic cleaning and electro-plating method are to operate in low voltage range, and these class methods are generally operated under the current density of low voltage (general 3-12V) and 1-15A/dm2.In this low voltage range, electric current is with the unidirectional increase of the voltage that applies.Under certain conditions, along with the increase of voltage, reach the instable point of appearance, and electric current begins to reduce with the increase of voltage.Unstable situation indicates on the surface of certain electrode discharges.These discharges (" little electric arc " or " microplasma ") occur between any suitable non-conductive layer that exists from the teeth outwards, for example gas or vapor film.This is because the some potential gradient in these zones is very high.
Fast development along with machinery manufacturing industry, the output of mechanical component is increasing, traditional method for cleaning surface and equipment can not adapt to the demand for development of this scale operation, press for seek at a high speed, cleaning technique efficiently, to improve the ability of producing and cleaning; In addition, searching is more cleaned, the cleaning way of more environmental protection also more and more causes people's attention.Since occurring 20th century such as new cleaning technique such as ultrasonic cleaning, Dry ice cleaning, laser cleaning and the plasma clean etc. that improve cleaning quality, reduce or avoid environmental pollution that have successively.
Prior art
GB-A-1399710 mentions, can adopt the surface of electrolysis process clean metal, if this method is to operate in the scope that just exceeds unstable region, then can superheated and do not have excessive energy expenditure, " unstable region " is defined as the zone that electric current descends with the increase of voltage.Increase voltage slightly, increase with the increase of voltage again at electric current, and when the continuous film of processed surface formation gas, can obtain effectively to clean.Yet, compare the energy expenditure height (10-30kWh/m2) of this method with the energy expenditure (0.4-1.8kWh/m2) of acid pickling.
SU-A-1599446 narrates a kind of high-voltage spark erosion purging method to welding rod, and this method is used high current density, about 1000A/dm2 in phosphoric acid solution.
SU-A-1244216 narrates a kind of little electric arc clean method to machine parts, and this method adopts anodizing, operates under 100-350V.Do not mention the concrete grammar of handling electrolytic solution.
Narrated other electrolytic cleaning methods in GB-A-1306337, in these methods, spark erosion combines with independent chemistry or electrochemistry cleaning step, with except descaling; In US-A-5232563, under the low voltage of 1.5-2V, by generate the bubble except crude removal in wafer surface, remove crude removal from semiconductor wafer; Talk about in EP-A-0657564, common low voltage electrolytic cleaning is inoperative to removing lubricating grease, but under high-voltage (little electric arc) condition, utilizes the anodizing effect of acid, can remove lubricating grease by the successful metal to energy electrolytic oxidations such as aluminium.
For example, in JP-A-08003797 and DE-A-4031234, mention, in electrolytic cleaning is bathed, adopt near the method for jet electrolytic liquid electrode, can in cleaning area, produce high-speed turbulent flow.
Mention in EP-A-0037190, under the situation of the incomplete submergence of object, adopt the method electrolytic cleaning of independent jet electrolytic liquid to be subjected to alpha-contamination object, the object that is cleaned is anode.The voltage that uses is 30-50V.Recommend the short period of time to handle about 1 second, avoiding the corrosion on surface, and think that it is unnecessary removing oxide compound fully.Also mention non-immersion in CA-A-1165271, this method is by the box anode in some holes was set the end of at, pumping or water pouring electrolytic solution.The purpose of this configuration is only to electroplate in a side of metal strip, particularly avoids using sacrificial anode.
DE-A-3715454 has narrated the employing bieletrolysis and has handled the clean metal silk, and this method comprises makes wire pass through first Room, and wire is negative electrode in this chamber, makes wire pass through second Room again, and wire is anode in this chamber.In second Room, utilize the ionizing event of oxygen-containing gas layer, form plasmasphere on the surface of wire anode.During entire treatment, wire is immersed in the electrolytic solution.
The EP-A-0406417 narration is a kind of for the continuation method from copper rod pull copper wire, and in this method, before wire-drawing operation, using plasma cleans copper rod.The shell of " plasmatron " is anode, the coaxial anode in the canular inside of U-shaped that wire also is porous surrounds, in order to cause the generation of plasma body, voltage is maintained the low but numerical value of concrete regulation not, be reduced in the liquid level of electrolyte above the submergence wire, reduce flow, impel wire surface to discharge.
The low voltage electrolytic cleaning is widely used in the metallic surface of preparing plating or other coating processing, and is not having under the situation of unacceptable high energy, can not handle the attached layer of oxide compound of expanded skin uniform thickness.Therefore, this class electrolytic cleaning method other cleaning processes common and in the multistep operation combine.
WO-A-97/35052 narrates the electrolysis process that a kind of employing electro-plasma (arc-over) cleans conductive surface, in this method, anode remains under the high dc voltage, and liquid electrolyte flows through the one or more holes in the anode, impact is (negative electrode) on workpiece, thereby forms the path of conduction.This system reduces with the increase that is applied to the voltage between anode and the negative electrode or remains unchanged basically at electric current, operates under there is the operating mode of discontinuous bubble of gas and/or steam in workpiece surface in treating processes.
WO-A-97/35051 has narrated the electrolysis process on a kind of cleaning and coated with conductive surface, and this method is to similar in the method described in the WO-A-97/35052, and difference is that anode comprises the metal as the attached layer of workpiece surface metal.
In the process of operation WO-A-97/35051 and WO-A-97/35052 method, form arc-over or electro-plasma at workpiece surface, they form in bubble layer.Plasma body has the effect of removing oxide skin and other dirt from the workpiece surface rapidly, stays the metallic surface of cleaning, and this metallic surface can also be passivated (the further oxidation of ability).
In addition, if anode be by, make as non-inert materials such as non-refractory metals, then some atoms metals will be transferred to negative electrode from anode, form metal cover in clean Surface.
Also can in above-mentioned operation operating mode, adopt inert anode and the electrolytic solution that is included in the metal ion that will apply described in the WO-A-99/15714 to apply.In this case, this method becomes a kind of special plating form, but because this method is to carry out existing under the high-voltage of arc-over, so this plating is faster than common plating, coating has bigger sticking power to matrix metal.
The WO-A-98/32892 narration is a kind of basically with the aforesaid method method of operating, but the mixture of the gas of employing conduction is as conducting medium.This gas/steam mixture is before injecting machining gap by the hole in the anode, generates in the anode of two or more chambers shape.This gas/steam mixture is by the aqueous electrolyte liquid in the anolyte compartment being heated to boiling point or producing more than the boiling point, both can adopt principal current, and also can adopting independently, electric heater heats these anolyte compartments.
WO2001/00941 has narrated a kind of method of cleaning the conductive surface of thread workpiece.Wherein configuration surface is to form electric tank cathode, and in electrolyzer, the dc voltage of anode remains on more than the 30V, suitably regulates operating parameters, sets up arc-over (electro-plasma) on the surface of workpiece.The machining gap of this method between anode and negative electrode has been full of the conducting medium of being made up of foam, and foam comprises gas mutually and liquid phase.
Now, the contriver has developed a kind of improved method, the method and apparatus that wherein adopts electrolysis aura effect (arc-over) can be under normal pressure conductive surface and the nonmetallic non-conductive face of plate workpiece to be carried out surface modification for example cleans the surface of steel.Increase the dimension on surface capable of washing, expanded the range of application of electrolysis aura purging method.Conductive path forms among anode and negative electrode are immersed in electrolytic solution, does not need to add in addition conducting medium.This treatment process equipment, technology are simple, and cost is low, and is suitable for the parts of Any shape complexity.
Summary of the invention
The invention provides a kind of method and apparatus that utilizes liquid aura effect to carry out material surface modifying, this method comprises that introducing liquid electrode is anode, do negative electrode with workpiece, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, surface at workpiece produces the aura effect, the method is characterized in that, machining gap between anode and the negative electrode is full of the conducting medium of being made up of electric drain, and conducting medium comprises gas mutually and liquid phase.By regulating voltage, electric current, concentration of electrolyte, and processing parameter such as treatment time can produce the aura effect on the surface, and the material surface performance is transformed, improved.
On the other hand, the invention provides the device that cleans conductive surface, this device comprises:
(1) power supply and corresponding computer are controlled the interface automatically;
(2) electrolytic reaction generation chamber, and corresponding electrolytic solution adds and discharges the device for the treatment of zone;
(3) temperature-control device of electrolytic solution;
(4) the mobile mechanism of handling workpiece.
Invention description
The present invention is to a kind of improvement of existing cleaning technique, is mainly reflected in the following aspects:
(1) eurytropy: expanded the dimension that can handle workpiece, for thread, plate workpiece is surperficial all can clean; The processing workpiece geometries is unrestricted, can handle the different shape complex surfaces, because aura effect directivity is not strong, can be deep into fine eyelet and the concave interior of object, and cleaning performance is more even.
(2) low cost: equipment is simple, and cleaning reaction is to carry out under normal pressure, does not need vacuum unit; The electrolytic solution cost of material is cheap, only adopts NaHCO 3Solution does not need other conducting medium and corresponding medium generating unit; Reaction requires temperature not high, and it is lower to consume energy.
(3) controllability: parameters such as voltage, electric current and temperature can be carried out processing quality control by computer setting and data logging.
(4) function is strong: can improve the surface property of material itself as being stained with property and wettability when finishing the cleaning decontamination, improve the antioxidant property of material surface, the residual stress that cause because of machining processes on the reduction surface etc.
(5) feature of environmental protection: electrolytic solution adopts NaHCO 3Solution need not to add other chemical agent, and reacted waste liquid need not carry out specific environment-protecting clean and handle environmentally safe.
The cleanup action that electrolysis aura purging method reaches, can explain from two aspects: being the microcell fusion effect of workpiece surface on the one hand, is that plasma body is for the activation of material surface on the other hand.
When negative electrode contacts with electrolytic solution, because having good specific conductivity, surface in contact causes big electric current, local joule heating makes electrolytic solution volatilize, thereby forms the liquid/gas two-phase at contact interface, causes unstable.Noble potential causes forming little hydrogen and steam bubble at negative electrode, when strength of electric field reaches 10 5During V/m, the gas space ionization in the bubble, and electricity can take place and breaks in bubble.When each bubble generation breaks, form of short duration little electric arc, produce plasma body, and of short duration little electric arc improved the temperature of microcell internal surface, cause the partial melting on surface.
In addition, the electrolysis aura can produce the activation of various high energy particles and free radical, the dirts such as organism, oxide compound that are attached to matrix surface progressively can be activated decomposition, finally evaporation or break away from workpiece surface.With regard to reaction mechanism, electrolysis aura effect is cleaned and generally included following process: working gas is activated into plasma state; Gas phase excited state material is attracted to solid surface; Be adsorbed particle group and solid surface pollutant reaction and generate the product molecule; The product molecule is resolved and is formed gas phase; Reaction residue breaks away from the surface.
Clean by electrolysis aura effect, multiple physics, chemical transformation take place in material surface.Cleaning material surface under appropriate processing condition makes its form generation noticeable change, improves the antioxidant property of material surface, stressed condition etc.Can introduce multiple free group, make the surface by nonpolar, difficult viscosity transfer to certain polarity is arranged, easily viscosity and wetting ability, be conducive to bonding, apply and printing.
The processing parameter that needs in the cleaning process to control mainly contains: voltage, electric current, concentration of electrolyte, temperature and treatment time.Voltage and current is often determining whether the processing of electrolysis aura can produce, and the concentration of electrolytic solution and temperature effect the electric conductivity of electrolytic solution-electrode contact interface, and the treatment time affects state and the degree of material surface modifying.
The invention effect
The invention provides the device that cleans conductive surface:
(1) power supply and corresponding computer are controlled the interface automatically:
Power supply can realize exchanging and direct supply between conversion, the voltage and current in the stable control reaction process guarantees security.In addition, the computer interface that links to each other with power supply can conveniently arrange and control automatically the voltage and current parameter of reaction, and record data.
(2) electrolysis aura reaction generation chamber, and corresponding electrolytic solution adds and discharges the device for the treatment of zone:
Electrolysis aura reaction generation chamber mainly comprises electrolyzer, positive plate, and electrode-electric source connection line.NaHCO3 solution adds and the discharge treatment zone by reaction generation chamber pipelines on two sides.
(3) temperature-control device of electrolytic solution:
Electrolytic solution heats by the thermopair of reaction generation chamber bottom, carries out measurement and the demonstration of temperature by thermistor, and the maximum of a rly. control electrolyte temperature, reports to the police and outage when temperature surpasses the setting maximum, stops heating.
(4) the mobile mechanism of handling workpiece:
Can be at the mechanism of the continuous migration workpiece of one dimension direction by this, can straight-lined manufacturing.
Description of drawings
Fig. 1 is a kind of setting drawing reduced graph of type material surface modification
The electric current and voltage on Fig. 2 cleaning process cleaning part surface is monitored figure in real time
Fig. 3 is that liquid aura effect produces principle schematic
Fig. 4 is the SEM surface topography map (front) before the modification of high-Nb Ti-Al plate surface is handled
Fig. 5 is the SEM surface topography map (front) after the modification of high-Nb Ti-Al plate surface is handled
Fig. 6 is the SEM surface topography map (positive high power) after the modification of high-Nb Ti-Al plate surface is handled
Fig. 7 is the SEM surface topography map (cross section) before the modification of high-Nb Ti-Al plate surface is handled
Fig. 8 is the SEM surface topography map (cross section) after the modification of high-Nb Ti-Al plate surface is handled
Fig. 9 is the SEM surface topography map (cross section high power) after the modification of high-Nb Ti-Al plate surface is handled
Embodiment
Further specify the present invention with reference to some embodiment below.
It is the titanium aluminum alloy of 45A18Nb that composition is adopted in experiment, is cut to the fritter plate tensile sample of 12mm*10mm*2mm, and has studied its 12mm*10mm front and the cross section of 12mm*2mm respectively.The electrolysis aura cleans 5min and handles, then by flying-spot microscope, and energy depressive spectroscopy, and nanometer micromechanics probe is probed into the different surface of these two areas in the variation of cleaning front and rear surfaces.
Embodiment 1
Figure 4 shows that the sample front before electrolysis aura surface cleaning, the surface topography picture under flying-spot microscope can be observed tissue and present typical laminar structured feature, and the sheet interlayer is being mingled with some brilliant white particulate state precipitated phases.
After electrolysis aura surface cleaning, under identical magnification, as shown in Figure 5, the lamellar structure that can observe intermetallic compound thickens, and a lot of holes occur at the sheet interlayer.Further amplify, as shown in Figure 6, can see the very intensive aperture that also distributing in lamellar structure inside.
Young's modulus and hardness value correlative value are as shown in table 1 before and after the positive processing of sample, can see that the Young's modulus of specimen surface after processing and hardness value are totally on a declining curve, have only the Young's modulus at center and the hardness on the limit to increase to some extent.Illustrate that aura processing clean has reduced the unrelieved stress of material surface.
Figure BSA00000794309900081
Positive front and back Young's modulus and the hardness value handled of table 1
Embodiment 2
Fig. 7 and Fig. 8 are respectively the sample cross section before and after aura is handled cleaning, the surface topography picture that amplifies under flying-spot microscope.Similar with the front, after the processing, the lamellar structure of titanium aluminum alloy sample thickens, at sheet interlayer and the inner much intensive holes that produce of lamella.
And can observe the tissue topography of similar blister at the edge of sample.By Fig. 9, the picture that section edges is amplified can see clearly that sample is by the transition change of center to the edge surface pattern.Be that the center is the sheet tissue that aperture gathers, then form the blister form of growing up gradually to the edge.
Corresponding therewith, Young's modulus and hardness value were as shown in table 2 before and after handled in the sample cross section.Contrast is positive, can find that the Young's modulus in cross section and hardness value are higher slightly than the front; But with positive, the Young's modulus of sample cross-sections surfaces and hardness value all descend to some extent after processing.
Young's modulus and hardness value before and after handle in table 2 cross section

Claims (18)

1. the method for a type material surface modification, this method comprises introduces liquid electrode as anode, with workpiece as negative electrode, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, the method is characterized in that, machining gap between anode and the negative electrode is full of the conducting medium of being made up of electric drain, and conducting medium comprises gas mutually and liquid phase.
2. one kind is utilized high-voltage, plate the process of other metal or alloy of skim in the metallic surface, be to utilize electrolytic action that thereby the technology of the surface attachment layer of metal film of metal or other material product is played to prevent corrosion, improve wear resistance, electroconductibility, reflective and promote attractive in appearance etc., to reach the method for material surface modifying, this method comprises does anode with institute's coated metal or other insoluble materials, workpiece to be plated is done negative electrode, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, plasma body acts on and workpiece on the one hand, with workpiece surface 1-3 nanometer layer activation.The positively charged ion of coated metal is reduced formation coating at workpiece activating surface to be plated.The method is characterized in that the machining gap between anode and the negative electrode is full of the conducting medium of being made up of electric drain, conducting medium comprises gas mutually and liquid phase.The feature of this method is that also the tension force of active surface discharges under the effect of plasma body, stay nano level male and fomale(M﹠F) on the surface, makes that the positively charged ion of coated metal and the electrolytic coating between the workpiece are finer and close evenly.This method changes substrate surface character or size, strengthen metal erosion resistance (coated metal adopts corrosion resistant metal more), increase hardness, prevent abrasion, improve electroconductibility, oilness, thermotolerance and surface aesthetic.
3. a novel hydronic method produces TRANSIENT HIGH TEMPERATURE in the metallic surface and quenches, and causes surface grain refinement.In the process of oxidation, formed the fine and close anti oxidation layer of one deck, improve the metallic surface antioxidant property, to reach the method for transformation, improvement metallic surface performance.This method comprises that introducing liquid electrode is anode, with the negative electrode of workpiece as the liquid plasma treatment, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, the method is characterized in that, machining gap between anode and the negative electrode is full of the conducting medium of being made up of electric drain, and conducting medium comprises gas mutually and liquid phase.Moment high temperature-cooling-moment moment high temperature appears in workpiece surface ... circulation heat-processed.Showing as, produce violent electrical spark at workpiece surface, electrical spark produces-buries in oblivion-produces ...
4. type material surface-treated method, produce the method for fine and close hole in the metallic surface, this method comprises that introducing liquid electrode is anode, with the negative electrode of workpiece as the liquid plasma treatment, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, the method is characterized in that, machining gap between anode and the negative electrode is full of the conducting medium of being made up of electric drain, and conducting medium comprises gas mutually and liquid phase.The micro-lip-deep projection of workpiece and depression in the process of plasma effect, because strength of discharge is different with discharge time, local micro-melting of metal can occurs and condense, and produce fine and close hole at workpiece surface like this.
5. type material surface-treated method, infiltrate non-metallic element at workpiece surface, trace element, the method of rare earth element etc., this method comprises that introducing liquid electrode is anode, with the negative electrode of workpiece as the liquid plasma treatment, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulate electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, the method is characterized in that, machining gap between anode and the negative electrode is full of conducting medium, this medium comprises the non-metallic element that needs infiltrate, trace element, positive ion or the simple substance of the purpose element of one or more materials such as rare earth element, conducting medium is made up of foam, and foam comprises gas and liquid phase.
6. a novel surface is handled the self-propagating reaction that brings out intermetallic compound, again by further handling, to obtain the method near the closely knit product of theoretical density.This method comprises that introducing liquid electrode is anode, be negative electrode with the powder base that certain intensity will be arranged, in being placed with the electrochemical pond of special electrolytic solution, volts DS between anode and the negative electrode remains on more than the 90V, suitably regulates electrical parameter, produce on the surface of workpiece the aura effect and/the liquid plasma body, the method is characterized in that, after the energising, plasma body can bring out self-propagating reaction, can obtain the constant substantially block materials of shape.Machining gap between anode and the negative electrode is full of conducting medium, and conducting medium is made up of foam, and foam comprises gas and liquid phase.
7. the method for claim 2 wherein at the positive ion of workpiece formation coating, obtains from one or more metal electrodes.Also can by after the positive ion that joins in the electrolytic solution provide.Be not only applicable to the workpiece of wire rod, sheet material is suitable equally.
8. each method of claim 1-7, wherein foam comprises the gas of at least 20 volume %.
9. each method of claim 1-7 wherein by the lip-deep one or more holes of anode working, is introduced machining gap with foam.
10. each method of claim 1-7 wherein is not by anode foam to be introduced machining gap.
11. each method of claim 1-7, wherein Dao Dian foam be will conduction aqueous electrolyte liquid boil generation.
12. each method of claim 1-7, wherein foam is to adopt to make bubble catalytic media net and produce.
13. each method of claim 1-7, the wherein generation of foam, character and stability are made infusion, tensio-active agent, viscosity modifier or the control of other additive by add one or more in conducting medium.
14. the method and apparatus of a type material surface modification, comprising: have the encapsulation process district of one or more anode assemblies, this district be fit to handle pending surface or some are surperficial, and each anode assemblies comprises outermost one deck: the insulating ceramic pipe; The second layer: Graphite Electrodes pipe; The 3rd layer: make bubble catalytic media net; The 4th layer: the heating of metal net.The device that liquid electrolyte is added described pipe: and flowing fluid electrolytic solution in the described pipe is changed into the device of foam;
(1) move the device that pending workpiece passes through treatment zone between the anode assemblies continuously:
(2) device of opening and closing treatment zone; Catalyzer/device with the adding of control foam and discharge treatment zone.
15. the method and apparatus of a type material surface modification, the material classification of processing is not limited to metallic substance, and is suitable equally for non-metallic material.
16. the device of claim 14, the electrolytic solution that flows in the insulating ceramic pipe wherein, through making the interaction of bubble catalytic media net and heating of metal net, produce a large amount of bubbles in the feasible electrolytic solution that flows, the conductive foam between Graphite Electrodes pipe and effect workpiece forms.
17. the device of claim 14 or 15, wherein treatment zone is to adopt the sealing of flexible seal material.
18. the device of claim 14 or 15, wherein treatment zone is installed the outlet that at least two one or two foams inject entrance and at least two one or two foams discharge treatment zone for the treatment of zone.
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