CN104342714B - A kind of method removing stainless steel watch surface oxidized skin - Google Patents
A kind of method removing stainless steel watch surface oxidized skin Download PDFInfo
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- CN104342714B CN104342714B CN201410565105.1A CN201410565105A CN104342714B CN 104342714 B CN104342714 B CN 104342714B CN 201410565105 A CN201410565105 A CN 201410565105A CN 104342714 B CN104342714 B CN 104342714B
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Abstract
The invention discloses a kind of method removing stainless steel watch surface oxidized skin, including: pending workpiece and discharge plate are relatively fixed and to be arranged in insulating vessel by (a), hold composite buffering working solution in described insulating vessel；B the negative pole end of high-voltage pulse power source is connected by () with described discharge plate, the positive terminal of high-voltage pulse power source is connected with described workpiece；C () connects high-voltage pulse power source, make high-voltage pulse power source pass through discharge plate to described workpiece electrical discharge, the workpiece being immersed in described composite buffering working solution is processed 3 10 min, disconnects described high-voltage pulse power source, takes out workpiece, cleans, is dried.The method that the present invention provides is the most simple to operation, and the surface of the work after removing is clean, uniform, and removal efficiency height, good operating stability, reliability height, length electrode life, low cost, practicality is the strongest in the industrial production.
Description
Technical field
The present invention relates to the cleaning method of metal material oxide skin, a kind of method removing stainless steel watch surface oxidized skin.
Background technology
Along with development and the smelting technique of society constantly improve, the reduction of cost, stainless steel material is widely applied to all trades and professions, at the aspect such as industry, building, chemical industry, medical treatment, decoration, food machinery, the art work, household electrical appliance, daily life, all play integral effect.Stainless steel has the plurality of advantages such as intensity is high, corrosion resistance is good, but its color is the most argenteous, either mirror face stainless steel or frosted Asia light stainless steel, all can give people a kind of icy, sensation of shortage affinity.Therefore, in order to adapt to market diversification demand, in industry, stainless steel work-piece can be carried out colouring plated film by businessman in recent years.At present, the method for stainless steel coloring plated film mainly has following several: 1. chemical oxidation colouring；2. electrochemical oxidation colouring；3. ion deposition oxide coloring method；4. high-temperature oxydation colouring；5. vapor-phase thermal cracking colouring.But, no matter to be required to the coated surface of stainless steel work-piece clean, smooth for which kind of film plating process.And stainless steel billet is in cold rolling, hot rolling and annealing process, its surface all can produce that a Rotating fields densification is firmly combined with matrix and have certain thickness oxide scale layer, typically in ten several micron dimensions；This just needed staff to be removed oxide skin before plated film, if this oxide skin is removed clean, plated film is combined the most insecure with stainless steel base, easily cause locally fade, variable color, time serious, plated film comes off.Visible, remove stainless steel watch surface oxidized skin in the processing of plated film stainless steel device, play very important effect.
At present, remove both at home and abroad stainless steel oxidation skin and mainly use following several ways:
1, physical mechanical mode, mainly makes medium produce friction with stainless steel surfaces, such as sandblasting etc. by power；This method operation is simple, but this single physical mechanical processing mode, there is treatment effeciency low, to processing the problem that flatness is poor at the knuckle of workpiece and to thin plate；
2, chemistry and electrochemical means, mainly produces chemical reaction by pickling, electrolysis with stainless steel surfaces；This method is time-consumingly long also produces a large amount of nitrogen oxides, relatively big to environmental hazard, and pickling is insufficient causes oxide skin to remain, and excessive erosion can cause again surface of the work flatness to be lost；Additionally, due to the surface of the work active center distribution uniformity is poor, relies solely on naked eyes and be difficult to detection crudy, thus cause pickling workpiece quality stability bad；
3, laser ablation method, as CN1224644A discloses a kind of method removing oxide from metal surface, including: utilize generation pulse width the shortest, the laser instrument of the electromagnetic radiation that pulse recurrence frequency is the highest and mean power is the highest, produce radiation, make this radiation through at least one optical element so that its be focused into this metal surface contact point at least about 5MW/cm2The incident beam of surface power density, and make the radiation laser beam of focusing in the horizontal completely across covering the oxide of metal surface, so that by the interaction of one or more pulses by evaporating this oxide removal.The method scale removal is uneven, unclean, and needs the laser instrument of costliness can be only achieved, and practicality is relatively poor；
4, physicochemical manner, is mainly combined with chemical mode by physics mode, as steel brush be combined with pickling, ultrasonic wave is combined with pickling, ultrasonic wave, pickling combine with electrolysis；These modes use relatively broad in current industry, as CN100402703C discloses a kind of method removing oxidized skin on hot rolling nickel stainless steel material, including: stainless steel bars or sheet material chemical pickling liquid are soaked 4～180min at 5～95 DEG C by (1), (2) material will be cleaned by and be placed in water with supersonic generator ultrasonically treated 5～120s, the component of described pickle and weight proportion be: sulfuric acid or hydrochloric acid 5%～25%, inorganic sulphide 0.5～15%, remaining is water.CN1900384A discloses a kind of technique using ultrasonic wave and electrolytic combination to remove part surface oxidized skin, be in same electrolyte utilize difference electrolysis with ultrasonic wave combine scale removal, by control electrolysis, ultrasonic technique parameter realize at 20 ± 2 DEG C, 3～the 5min/5 μm time in complete remove metal material surface oxide skin.These methods are higher relative to single one physical method or its effect of chemical Treatment, but as ultrasonic applications is being removed on stainless steel watch surface oxidized skin, itself there is inadequate natural endowment: 1. ultrasonic sound field is propagated in liquid medium, must decay, namely the position sound field near ultrasonic transducer is strong, the most weak further away from sound field；The most ultrasonic cavitation is also uneven, and cavitation bubble can form one layer strong, one layer of weak, one layer of strong, one layer of weak spatial distribution, removes uneven problem so existing when the stainless steel watch surface oxidized skin removed；3. being attended by the Non-Linear Vibration of cavitation bubble during ultrasonic wave cavitation in a liquid to produce the collapse of each harmonic and subharmonic and cavitation bubble and can give off continuing noise, these compositions are overlapped mutually and can form liquid cavitation noise.Noise radiates to working space with Air Interface through water, and about at about 85dB, harm staff is physically and mentally healthy.And electrochemistry removes stainless steel watch surface oxidized skin, there is also some uncertain factors, mainly have: 1. treatment fluid: each state of matter (valence state, activity, acidity, precipitation formation etc.) in treatment fluid；The temperature change for the treatment of fluid；The material of workpiece, the gross area and shape；Surface of the work active center distribution；Reducing electrode surface contamination etc..If it is improper to control, surface of the work oxide skin can be caused to remove not thorough or excessive corrosion, stainless steel decorated sheet class workpiece big to area especially, its process parameters is less susceptible to control, is difficult to accomplish stable reproduction.2. electrode.When electric current is by electrode, electrode is polarized, has novel substance to generate on the surface of electrode, makes the bad stability of electrode, electro-catalysis efficiency reduce；Meanwhile, will produce electrochemical heat at electrode and treatment fluid interface, the charger transfer coefficient of electrode, diffusion coefficient and electrode reaction speed all can change at different temperatures.Visible, there is more deficiency in currently available technology scale removal, is therefore highly desirable to develop a kind of new technology more effectively scale removal, to meet current stainless plated film demand.
Summary of the invention
It is an object of the invention to provide a kind of method removing stainless steel watch surface oxidized skin, the cleanest, uneven to solve removal stainless steel watch surface oxidized skin existence removal, it is difficult to the problem meeting plated film demand.
It is an object of the invention to be achieved through the following technical solutions: a kind of method removing stainless steel watch surface oxidized skin, comprise the following steps:
A pending workpiece and discharge plate are relatively fixed with the spacing of 10～30cm and are arranged in insulating vessel by (), hold composite buffering working solution in described insulating vessel；nullDescribed composite buffering working solution includes that by Acetic acid-sodium acetate buffer solution and citric acid-sodium citrate buffer solution be 1: 0.5～2 cocktail buffer formed by volume，And in cocktail buffer every liter described add AEO 0.1～3g、Polyethyleneglycol nonylplenyl ether 0.2～5g、Thiosemicarbazides 0.1～1 g、Hexamethylenetetramine 5～20g、BTA 0.01～0.15g、Oxalic acid 10～50g、Disodium ethylene diamine tetraacetate 10～20g、Aniline 0.1～0.5g、Sulphur monooctyl acid monooctyl ester 0.1～0.4g、Organic acid 0.1～0.5g、Organic silicon defoamer 0.01～0.1g、Ethyoxyl propargyl alcohol 1～3g、Pyridine 10～20 g、Propine sodium sulfonate 0.05～1.1g；
B the negative pole end of high-voltage pulse power source is connected by () with described discharge plate, the positive terminal of high-voltage pulse power source is connected with described workpiece；The crest value of impulse voltage of described high-voltage pulse power source is 3000V～10000 V, the peak value of pulse current about 350～600A, pulse frequency 10～40 Hz；
C () connects high-voltage pulse power source, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the workpiece that is immersed in described composite buffering working solution is processed 3～10 min, disconnects described high-voltage pulse power source, taking-up process after workpiece, clean, be dried.
Organic acid described in step (a) of the present invention is one or both and the mixture of two or more arbitrary proportion in tartaric acid, lactic acid, malic acid, chelidonamic acid, succinic acid, propionic acid, adipic acid, butanedioic acid, amion acetic acid, alanine, cystine and cysteine.
Organic acid described in step (a) of the present invention is tartaric acid, adipic acid, the mixture of three kinds of arbitrary proportions of amion acetic acid.
The formulation of organic silicon defoamer described in step (a) of the present invention: ZJ-822 type；Its manufacturer is: Guangzhou end Chemical Industry Science Co., Ltd；
Described Acetic acid-sodium acetate buffer solution is containing glacial acetic acid 60mL and anhydrous sodium acetate 160g in every liter of buffer solution；Described citric acid-sodium citrate buffer solution is containing monohydrate potassium 8.6g and two citric acid monohydrate trisodiums 15.2g in every liter of buffer solution.
The initial conductivity 400～800 μ S/cm of composite buffering working solution described in step (a) of the present invention.
The some eletrode tips pointing to described stainless steel work-piece surface scale it are provided with on discharge plate described in step (b) of the present invention；Described eletrode tip is the tip, edge being distributed in projecting apertures on described discharge plate；Described eletrode tip maybe can also can change the point discharge bar of length for being arranged on the stainless steel lag screws on described discharge plate；Described eletrode tip is different in size；Described eletrode tip is that matrix is arranged on described discharge plate.
High-voltage pulse power source described in step (b) of the present invention includes DC high-voltage power supply, current-limiting resistance, triggering switch, electric capacity and wire, described DC high-voltage power supply is in series by wire with current-limiting resistance, electric capacity, described electric capacity is in parallel with described switch, discharge plate and the workpiece of triggering, and described discharge plate is connected with the negative pole end of high-voltage pulse power source, described workpiece is connected with the positive terminal of high-voltage pulse power source；Described triggering switch is used for controlling high-voltage pulse power source provides electric discharge and power-off for described discharge plate and workpiece.
The heretofore described switch that triggers is magnetic pulse compressor (mpc), thyratron switch, arrester switch and electrion triggering switch, and preferably electrion triggers switch, such as CN103198956
Technology contents disclosed in A.
Composite buffering working solution in the present invention, is a kind of faintly acid (pH is about 5) solution, itself has oil removing, molten rust, prevents the suppression of excessive corrosion, acid mist, stablize acidity, prevents precipitation, improves mass transfer, the promotion function such as desorbing gas and light.High-voltage pulse technology is combined by the present invention with composite buffering working solution, is applied to by high voltage pulse on discharge plate and workpiece, under the effect of highfield, makes discharge plate and workpiece form electric discharge in composite buffering working solution；Occur in that the coring shape discharge channel of the high conductivity extended from discharge plate to surface of the work direction, when passage is once arrive the workpiece on opposite, and electric energy will discharge along passage with surge formula；Now, pulse electric energy was poured into discharge channel within the time of Microsecond grade, formed electron avalanche, huge pulse current (103～105A) high electric energy density (10 is formed in making passage2～103J/cm3), thus cause localized hyperthermia (104～105And arc discharge occurs K),；And then by electric energy composite buffering working solution collaborative under be converted into mechanics effect, galvanomagnetic-effect, acoustic effect, calorifics effect, optical effect and chemical effect, make the oxide skin on workpiece under the effect of various effects, quickly, uniformly, remove neatly, goal of the invention is thus achieved.
The method that the present invention provides is better than prior art in the effect removing stainless steel watch surface oxidized skin, and it essentially consists in: the 1. supercritical water oxidation effect under high-temperature high-pressure state.Under high-temperature high-pressure state, thermal expansion causes the density of composite buffering working solution to reduce, and the boundary that the rising of pressure makes gas-liquid two-phase disappears, and becomes the supercriticality of homogeneous system.Composite buffering working solution in this state, unique physicochemical property such as have that reaction speed is fast, the reaction time is short, reaction temperature is low, the oxide skin of stable chemical nature there is the strongest corrosivity, thus accelerates the removal of oxide skin；2. causing ionization or electro transfer at composite buffering work discharge in liquid, element valence changes.The electric charge being gathered in electrode two ends can produce great voltage difference so that the composite buffering working solution near electrode is breakdown, produces the ionization channels from the outward extending high conductivity of high-field electrode, rapidly by energy density (102～103J/cm3) electric energy inject in composite buffering working solution, thus the process of electro transfer occurs, oxide skin discharges in composite buffering working solution or accepts electronics, changes the character of some oxide in selective oxidation cortex, improves the sour water dissolubility of oxide skin；3. the high temperature pyrolysis in high pressure pulse discharge produces plasma channel.In discharge process, it is full of by dense plasma completely in discharge channel, is produced instantaneous temperature up to (104～105K), pressure is up to (102～103MPa) HTHP, produces the shock wave expanded the most rapidly, and this impact to oxide skin is better than far away the effect of sandblasting, shot-peening.Owing to water has incompressible characteristic, under high pressure, composite buffering working solution is pressed in the squama seam of oxide skin and expands, and loosens the oxide skin on workpiece substrate, provides condition for accelerating removal stainless steel watch surface oxidized skin；4., when operating voltage reaches breakdown voltage, at surface of the work, numerous travelling, tiny silvery white arc discharge point occurs, and with slight reaction sound.The time that these arc discharge points exist is the shortest, does not has a fixed position, thus realizes than the purpose relatively evenly removing workpiece oxide skin；5. high-voltage pulse power source combines the synergy of composite buffering working solution by the ingehious design of eletrode tip on discharge plate, though the shape of workpiece and the uneven effect that also can reach satisfaction of surface relief.
High pressure pulse discharge is worked in coordination with by the present invention with composite buffering work liquid phase, convert electrical energy into the various effects such as mechanics effect, acoustic effect, calorifics effect and chemical effect, achieve quick, uniformly, neatly remove stainless steel watch surface oxidized skin, simultaneously, the composite buffering working solution that the present invention uses, without discarded after using activity to reduce, only need to supplement a part of mother liquor can continue cycling through use.Visible, the present invention not only method is simple, with low cost, removal efficiency is high, stainless steel surfaces after job stability and reliability height, the life-span length of discharge plate, scale removal is the brightest and the cleanest, disclosure satisfy that again the demand of plated film；And in the industrial production without frequently discharge work waste liquid, both economically and environmentally beneficial；Compensate for the most methodical deficiency, practical, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the structural representation of oxide skin removal device used by the present invention；
Fig. 2 is the operating diagram of high-voltage pulse power source discharge removal oxide skin of the present invention；
Fig. 3 is the partial structurtes enlarged diagram of discharge plate and eletrode tip；
Fig. 4 is that embodiment 1 processes front stainless steel work-piece surface microscope figure；
Fig. 5 is stainless steel work-piece surface microscope figure after embodiment 1 processes；
Fig. 6 is that comparative example 1 processes front stainless steel work-piece surface microscope figure；
Fig. 7 is stainless steel work-piece surface microscope figure after comparative example 1 processes；
Fig. 8 is that comparative example 2 processes front stainless steel work-piece surface microscope figure；
Fig. 9 is stainless steel work-piece surface microscope figure after comparative example 2 processes.
In figure: 1, adjustable DC high-voltage power supply, 2, discharge capacity, 3, current-limiting resistance, 4, electrion trigger switch, 5, insulating vessel, 6, discharge plate, 7, composite buffering working solution, 8, workpiece, 9, wire, 10, coring shape discharge channel, 11, eletrode tip.
Detailed description of the invention
Example below is used for further describing the present invention, but limits the present invention the most in any form.
Being assembled into oxide skin removal device according to structure shown in Fig. 1, this device includes high-voltage pulse power source and reactor two parts.
Its reactor includes insulating vessel 5, discharge plate 6, workpiece 8 and composite buffering working solution 7, support can be provided with in insulating vessel 5, discharge plate 6 and workpiece 8 are relatively fixed on the support being arranged in insulating vessel 5, to guarantee that workpiece 8 is parallel to each other with discharge plate 6 and is relatively fixed；Then the composite buffering working solution 7 prepared in advance is poured in insulating vessel 5, submergence and exceed discharge plate 6 and workpiece 8 height 2～3cm, needing the height of scale removal to hold composite buffering working solution 7 also dependent on workpiece, discharge plate 6 is 10～30cm with the spacing of workpiece 8.
Insulating vessel 5 can be to be opened rectangular tank suitable for reading by what the insulating materials such as plastics, bakelite was fabricated to, and to have certain intensity, bottom surface install a sewage draining valve, for time periodical blowdown；The capacity of container is determined by three sizes of length；The spacing of length discharge plate to be considered 6 and workpiece 8, both height and with the spacing of insulating vessel 5 container side wall.In embodiments of the invention the actual inside dimension of insulating vessel 5 be long 120cm, wide 45cm, high 120cm, sidewall away from insulating vessel 5 of discharge plate 6, workpiece 8, distance d of bottom surface are about 10 cm, and the liquid level of the composite buffering working solution 7 held is higher than workpiece 8 and discharge plate 6 height 2 cm.
The workpiece 8 of discharge plate 6 and band oxide skin can be all ordinary stainless steel plate, the present invention has selected 1Cr18Ni9 corrosion resistant plate (also referred to as 302 plate), there is good decay resistance, acid with strong oxidizing property for the little≤nitric acid of 65%, corrosion resistance is strong, also has certain corrosion resistance for alkaline solution and major part organic acid, inorganic acid.The thickness of slab selecting sheet material in embodiments of the invention is 0.5cm, and area is 1m2, it may be assumed that long × wide=100
cm×100 cm。
Some eletrode tips 11 it are evenly arranged with on discharge plate 6, discharge plate 6 with eletrode tip 11 can be fabricated to various ways: as stamped out the protruding tip of multiple array on stainless steel flat plate, protruding size can select in (5 ~ 10cm) × (5 ~ 10 cm) scope；Can also refer to former mode, simply change into a kind of point discharge bar changing length is installed by the tip of stamped bumps, to adapt to the scraggly surface of workpiece, make discharging distance substantially keep consistent.As shown in Figure 3, in embodiments of the invention, discharge plate 6 is provided with the multiple eletrode tips 11 pointing to workpiece 8 oxide skin, eletrode tip 11 is in array, eletrode tip 11 is made an annulus by tapering 60 °, the punch of diameter of phi 0.5cm, any two circle ring center's spacing L are 5cm, and average height of projection X of annulus is 0.3cm；Sheet material, in punching course, is torn by drift, and thus the top of annulus is the formation of eletrode tip 11 irregular, scraggly.
nullComposite buffering working solution 7 includes that by Acetic acid-sodium acetate buffer solution and citric acid-sodium citrate buffer solution be 1: 0.5～2 cocktail buffer formed by volume，And in cocktail buffer every liter described add AEO 0.1～3g、Polyethyleneglycol nonylplenyl ether 0.2～5g、Thiosemicarbazides 0.1～1 g、Hexamethylenetetramine 5～20g、BTA 0.01～0.15g、Oxalic acid 10～50g、Disodium ethylene diamine tetraacetate 10～20g、Aniline 0.1～0.5g、Sulphur monooctyl acid monooctyl ester 0.1～0.4g、Organic acid 0.1～0.5g、Organic silicon defoamer 0.01～0.1g、Ethyoxyl propargyl alcohol 1～3g、Pyridine 10～20 g、Propine sodium sulfonate 0.05～1.1g；Cocktail buffer is made up of with citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer solution.The initial conductivity of this composite buffering working solution is 400～800 μ S/cm, and temperature about room temperature, pH are about 5.One or both and the mixture of two or more arbitrary proportion during wherein organic acid is tartaric acid, lactic acid, malic acid, chelidonamic acid, succinic acid, propionic acid, adipic acid, butanedioic acid, amion acetic acid, alanine, cystine and cysteine；Preferably tartaric acid, adipic acid, the mixture of three kinds of arbitrary proportions of amion acetic acid；The formulation of organic silicon defoamer: ZJ-822 type；Manufacturer is: Guangzhou end Chemical Industry Science Co., Ltd.
As shown in Figure 1, high-voltage pulse power source includes that adjustable DC high voltage power supply 1, current-limiting resistance 3, electrion trigger switch 4, discharge capacity 2 and some wires 9, wherein DC high-voltage power supply 1 is in series by wire 9 with current-limiting resistance 3, discharge capacity 2, discharge capacity 2, electrion trigger switch 4 and are in parallel with discharge plate in reactor 6 and workpiece 8, provide high-voltage pulse power source for reactor, discharge plate 6 is connected with the negative pole end of high-voltage pulse power source, described workpiece 8 is connected with the positive terminal of high-voltage pulse power source；Electrion triggering switch 4 is used for controlling high-voltage pulse power source provides electric discharge or power-off for discharge plate 6 and workpiece 8.Mesohigh of the present invention electric discharge triggers switch technology contents disclosed in 4 non-CN103198956 A.Its electrion triggers switch 4 can also replace with magnetic pulse compressor (mpc), thyratron switch and arrester switch etc..
Adjustable DC high voltage power supply in the present invention, the size of its power, the adjustable range of voltage determine depending on the spacing of the work area of workpiece and discharge plate with workpiece；The capacity of discharge capacity, the resistance of current-limiting resistance, electrion trigger the rotational frequency of switch, and also relevant with the spacing of workpiece with the power of DC high-voltage source, voltage and discharge plate, the determination of these parameters belongs to known technology category.
The present invention is when processing stainless steel watch surface oxidized skin, start electrion and trigger switch 4, connect high-voltage pulse power source, make high-voltage pulse power source pass through discharge plate 6 workpiece 8 is discharged, the workpiece being immersed in described composite buffering working solution 7 is processed, turns over on-state, when forming off state when electrion triggers switch 4, DC high-voltage source is charged for discharge capacity 2 by current-limiting resistance 3, and the electric discharge for next on-state is prepared.Time in processing procedure until processing clean by the oxide skin on workpiece 8, disconnect described high-voltage pulse power source, taking-up process after workpiece, clean, be dried.
Electric energy is triggered switch 4 formation high voltage pulse by electrion and is applied on sparking electrode 6 and workpiece 8 by high-voltage pulse power source, and sparking electrode 6 and workpiece 8 form electric discharge in composite buffering working solution.Composite buffering working solution medium between discharge plate, workpiece, under the effect of highfield, occur in that the passage (see figure 2) of bifurcated (such as coring shape) from the outward extending high conductivity of high-field electrode, when passage is once arrive the workpiece on opposite, and electric energy will discharge along passage with surge formula.Now, on capacitor, the electric energy of storage was poured into discharge channel within the time of Microsecond grade, formed electron avalanche, huge pulse current (103～105A) high-energy-density (10 is formed in making passage2～103J/cm3), thus cause localized hyperthermia (104～105And arc discharge occurs K),.It is below concrete Processing Example:
Embodiment 1
To be set to 21cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 4000V, and the peak value of pulse current is about 430A, pulse frequency 30Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 1 1.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 300 g；Polyethyleneglycol nonylplenyl ether (O π-10) 500 g；Thiosemicarbazides 100g；Hexamethylenetetramine 500 g；BTA 15 g；Oxalic acid 5000 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 1000 g；Aniline 10 g；Sulphur monooctyl acid monooctyl ester 40g；Organic acid 50g(tartaric acid 10g, adipic acid 20g, amion acetic acid 20g)；Organic silicon defoamer (ZJ-822 type；Guangzhou end Chemical Industry Science Co., Ltd) 10 g；Ethyoxyl propargyl alcohol 300g；Pyridine 1000 g；Propine sodium sulfonate 5 g, the composition that stirs composite buffering working solution, its electrical conductivity is about 650 μ S/cm, and initial temperature is 27 DEG C；
Start electrion and trigger switch 4, frequency is 30Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 8 min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Embodiment 2
To be set to 10cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 3000V, the peak value of pulse current about 350A, pulse frequency 40 Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 12 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 200 g；Polyethyleneglycol nonylplenyl ether (O π-10) 250 g；Thiosemicarbazides 50g；Hexamethylenetetramine 1000 g；BTA 10 g；Oxalic acid 2500 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 2000 g；Aniline 50 g；Sulphur monooctyl acid monooctyl ester 30g；Organic acid 30g(tartaric acid 10g, adipic acid 10g, amion acetic acid 10g)；Organic silicon defoamer (ZJ-822 type；Guangzhou end Chemical Industry Science Co., Ltd) 5 g；Ethyoxyl propargyl alcohol 150g；Pyridine 2000 g；Propine sodium sulfonate 110g, the composition that stirs composite buffering working solution, its electrical conductivity is about 540 μ S/cm, and initial temperature is 26 DEG C；
Start electrion and trigger switch 4, frequency is 40Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 10 min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Embodiment 3
To be set to 30cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 10000
V, the peak value of pulse current about 600A, pulse frequency 10 Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 1 0.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 250 g；Polyethyleneglycol nonylplenyl ether (O π-10) 150 g；Thiosemicarbazides 10g；Hexamethylenetetramine 2000 g；BTA 1 g；Oxalic acid 4000 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 1500 g；Aniline 35 g；Sulphur monooctyl acid monooctyl ester 10g；Organic acid 10g(tartaric acid 5g, lactic acid 5g)；Organic silicon defoamer (ZJ-822 type；Guangzhou end Chemical Industry Science Co., Ltd) 1 g；Ethyoxyl propargyl alcohol 100g；Pyridine 1500 g；Propine sodium sulfonate 80 g, the composition that stirs composite buffering working solution, its electrical conductivity is about 710 μ S/cm, and initial temperature is 27 DEG C；
Start electrion and trigger switch 4, frequency is 10Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 5 min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Embodiment 4
To be set to 18cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 8000
V, the peak value of pulse current about 520A, pulse frequency 15 Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 11 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 10 g；Polyethyleneglycol nonylplenyl ether (O π-10) 20 g；Thiosemicarbazides 10 g；Hexamethylenetetramine 480 g；BTA 8 g；Oxalic acid 1000 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 1500 g；Aniline 28 g；Sulphur monooctyl acid monooctyl ester 25g；Propionic acid 35g；Organic silicon defoamer (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 4g；Ethyoxyl propargyl alcohol 250g；Pyridine 1700 g；Propine sodium sulfonate 60 g, the composition that stirs composite buffering working solution, its electrical conductivity is about 400 μ S/cm, and initial temperature is 25 DEG C；
Start electrion and trigger switch 4, frequency is 15Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 10min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Embodiment 5
To be set to 20cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 5000
V, the peak value of pulse current about 490A, pulse frequency 35 Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 1 1.8 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 200 g；Polyethyleneglycol nonylplenyl ether (O π-10) 400 g；Thiosemicarbazides 40g；Hexamethylenetetramine 1000 g；BTA 8 g；Oxalic acid 3000 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 1800 g；Aniline 35 g；Sulphur monooctyl acid monooctyl ester 30g；Organic acid 50g(succinic acid 30g, adipic acid 20g)；Organic silicon defoamer (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 7 g；Ethyoxyl propargyl alcohol 180g；Pyridine 1200 g；Propine sodium sulfonate 15 g, the composition that stirs composite buffering working solution, its electrical conductivity is about 700 μ S/cm, and initial temperature is 27 DEG C；
Start electrion and trigger switch 4, frequency is 35Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 8 min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Embodiment 6
To be set to 10cm with the workpiece 8 of oxide skin with the spacing of discharge plate 6, the crest value of impulse voltage arranging high-voltage pulse power source is 8000
V, the peak value of pulse current about 560A, pulse frequency 15 Hz.
Composite buffering working solution is prepared in the following manner: use acetic acid (glacial acetic acid 60mL/L)-sodium acetate (anhydrous sodium acetate 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-sodium citrate (two citric acid monohydrate trisodiums 15.2g/L) water buffer solution system, two kinds of cushioning liquid are 1 1.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer interpolation AEO 300 g；Polyethyleneglycol nonylplenyl ether (O π-10) 500 g；Thiosemicarbazides 100g；Hexamethylenetetramine 500 g；BTA 15 g；Oxalic acid 5000 g；Disodium ethylene diamine tetraacetate (EDTA-2Na) 1000 g；Aniline 10 g；Sulphur monooctyl acid monooctyl ester 40g；Organic acid 50g(tartaric acid 10g, adipic acid 20g, amion acetic acid 20g)；Organic silicon defoamer (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 10 g；Ethyoxyl propargyl alcohol 300g；Pyridine 1000 g；Propine sodium sulfonate 5 g, the composition that stirs composite buffering working solution, its electrical conductivity is about 800 μ S/cm, and initial temperature is 26 DEG C；
Start electrion and trigger switch 4, frequency is 15Hz, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the oxide skin of the workpiece being immersed in described composite buffering working solution is processed 3min, disconnect described high-voltage pulse power source, cooling, taking-up process after workpiece, clean, be dried.
Comparative example 1
Use acid soak washing methods: in insulating vessel 5 in embodiments of the present invention, fill with the salpeter solution that concentration is 6%, by with the workpiece 8 of oxide skin soak in the solution, it is stirred continuously liquid with sticking plaster, make liquid motion, rub with workpiece 8, process time 5～8 min, taking-up process after workpiece, clean, be dried.
Comparative example 2
Use acid soak+supersound washing: in insulating vessel 5 in embodiments of the present invention, hang up (by Suzhou Jia Hui Supersonic Tech Corp. produce JHZ-1048-28 type) ultrasonic vibrating plate, supersonic frequency is 28KHz, rated power 2400W, totally 2 pieces staggered relatively；Fill with the salpeter solution that concentration is 6% in a reservoir, by with the workpiece 8 of oxide skin be placed in the middle of two vibration plates and immersion in the solution, unlatching ultrasonic-frequency power supply switchs, and workpiece 8 processes time 5～8 min in acid soak+ultrasound environments, taking-up process after workpiece, clean, dry.
Embodiment 7
Experimental technique: embodiment is marked randomly selecting a few place on workpiece 8 before treatment, and with 100 times of observation by light microscope surfaces, compare with 100 times of observation by light microscope again in identical position after process.Its result is shown in Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8 and Fig. 9.
Result:
Knowable to the comparison of Fig. 4, Fig. 5, Fig. 5 can clear, significantly see crystal boundary, and fineness is good, the clearance 100% of oxide skin, observes the bright and clean degree of integral surface, substantially uniform.
Knowable to the comparison of Fig. 6, Fig. 7, showing that stainless steel surfaces crystal boundary does not almost see Chu in Fig. 7, oxide skin is not the most removed, and is simply removed by the oil stain dirt on surface, without positive effect.
Knowable to the comparison of Fig. 8, Fig. 9, though showing in Fig. 9 that crystal boundary is visible and ratio is more visible, but surface smoothness is bad, and oxide skin is removed the most completely.
Visible, from testing result it will be seen that the removal effect of the present invention is substantially better than the methods such as conventional acid liquid washing by soaking and acid soak+supersound washing, it is also significantly better than prior art.
The process that the embodiment that the present invention enumerates is intended to further to illustrate this removal stainless steel material oxide skin and the application direction in related industry, and protection scope of the present invention is not constituted any restriction.
Claims (5)
1. the method removing stainless steel watch surface oxidized skin, it is characterised in that comprise the following steps:
A pending workpiece and discharge plate are relatively fixed with the spacing of 10～30cm and are arranged in insulating vessel by (), hold composite buffering working solution in described insulating vessel；Described composite buffering working solution includes that by Acetic acid-sodium acetate buffer solution and citric acid-sodium citrate buffer solution be 1: 0.5～2 cocktail buffer formed by volume, and the AEO 0.1～3g of interpolation, polyethyleneglycol nonylplenyl ether in cocktail buffer every liter described
0.2～5g, thiosemicarbazides 0.1～1 g, hexamethylenetetramine 5～20g, BTA 0.01～0.15g, oxalic acid 10～50g, disodium ethylene diamine tetraacetate 10～20g, aniline 0.1～0.5g, sulphur monooctyl acid monooctyl ester 0.1～0.4g, organic acid 0.1～0.5g, organic silicon defoamer 0.01～0.1g, ethyoxyl propargyl alcohol 1～3g, pyridine 10～20 g and propine sodium sulfonate 0.05～1.1g；
B the negative pole end of high-voltage pulse power source is connected by () with described discharge plate, the positive terminal of high-voltage pulse power source is connected with described workpiece；The crest value of impulse voltage of described high-voltage pulse power source is 3000V～10000 V, the peak value 350～600A of pulse current, pulse frequency 10～40 Hz；
C () connects high-voltage pulse power source, high-voltage pulse power source is made to pass through discharge plate to described workpiece electrical discharge, the workpiece that is immersed in described composite buffering working solution is processed 3～10 min, disconnects described high-voltage pulse power source, taking-up process after workpiece, clean, be dried.
The method of removal stainless steel watch surface oxidized skin the most according to claim 1, it is characterized in that, one or both and the mixture of two or more arbitrary proportion during organic acid is tartaric acid, lactic acid, malic acid, chelidonamic acid, succinic acid, propionic acid, adipic acid, butanedioic acid, amion acetic acid, alanine, cystine and cysteine described in step (a).
The method of removal stainless steel watch surface oxidized skin the most according to claim 2, it is characterised in that organic acid described in step (a) is tartaric acid, adipic acid, the mixture of three kinds of arbitrary proportions of amion acetic acid.
The method of removal stainless steel watch surface oxidized skin the most according to claim 1, it is characterised in that the initial conductivity 400～800 μ S/cm of composite buffering working solution described in step (a).
The method of removal stainless steel watch surface oxidized skin the most according to claim 1, it is characterised in that be provided with the some eletrode tips pointing to described stainless steel work-piece surface scale described in step (b) on discharge plate.
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| CN87105097A (en) * | 1987-10-14 | 1988-03-16 | 刘祥云 | The chemical removal method of stainless steel oxidation skin |
| CN1224644A (en) * | 1996-08-12 | 1999-08-04 | 阿姆科公司 | Descaling metal with laser having very short pulse width and high average power |
| CN1718865A (en) * | 2005-07-05 | 2006-01-11 | 何明威 | Method of removing oxidized skin on hot rolling nickel stainless steel material |
| CN1900384A (en) * | 2006-07-05 | 2007-01-24 | 北京航空航天大学 | Process for removing part surface oxidized skin using supersonic wave and electrolytic combination |
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| FR2836157B1 (en) * | 2002-02-19 | 2004-04-09 | Usinor | METHOD FOR CLEANING THE SURFACE OF A MATERIAL COATED WITH ORGANIC SUSBSTANCE, GENERATOR AND DEVICE FOR IMPLEMENTING SAME |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN87105097A (en) * | 1987-10-14 | 1988-03-16 | 刘祥云 | The chemical removal method of stainless steel oxidation skin |
| CN1224644A (en) * | 1996-08-12 | 1999-08-04 | 阿姆科公司 | Descaling metal with laser having very short pulse width and high average power |
| CN1718865A (en) * | 2005-07-05 | 2006-01-11 | 何明威 | Method of removing oxidized skin on hot rolling nickel stainless steel material |
| CN1900384A (en) * | 2006-07-05 | 2007-01-24 | 北京航空航天大学 | Process for removing part surface oxidized skin using supersonic wave and electrolytic combination |
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