CN104342714A - Method for removing oxide skin on stainless steel surface - Google Patents
Method for removing oxide skin on stainless steel surface Download PDFInfo
- Publication number
- CN104342714A CN104342714A CN201410565105.1A CN201410565105A CN104342714A CN 104342714 A CN104342714 A CN 104342714A CN 201410565105 A CN201410565105 A CN 201410565105A CN 104342714 A CN104342714 A CN 104342714A
- Authority
- CN
- China
- Prior art keywords
- acid
- workpiece
- voltage pulse
- pulse power
- stainless steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for removing oxide skin on a stainless steel surface. The method comprises the following steps: (a) oppositely fixing and arranging a to-be-processed work-piece and a discharge pole plate into an insulated container, containing a composite buffer working solution into the insulated container; (b) connecting a negative end of a high-voltage pulse power supply and the discharge pole plate, the positive end of the high-voltage pulse power supply and the work-piece; and (c) connecting the high-voltage pulse power supply, so that the high-voltage pulse power supply discharges the work-piece through the discharge pole plate, processing the work-piece immersed into the composite buffer working solution for 3-10 minutes, cutting off the high-voltage pulse power supply, taking out the work-piece, cleaning and drying. The method disclosed by the invention is simple and convenient to operate, and the cleaned work-piece is clean and even in surface, the method is high in removal efficiency, good in working stability, high in reliability, long in service life of electrodes, low in cost, and strong in practicability in industrial production.
Description
Technical field
The present invention relates to the purging method of metallic substance oxide skin, specifically a kind of method removing Stainless Steel Watch surface oxidized skin.
Background technology
Along with society development and smelting technology constantly improves, the reduction of cost, stainless material is applied to all trades and professions widely, in industry, building, chemical industry, medical treatment, decoration, food machinery, artwork, household electrical appliance, daily life etc., all play integral effect.Stainless steel has the plurality of advantages such as intensity is high, solidity to corrosion is good, but its color overwhelming majority is argenteous, is no matter the sub-light stainless steel of mirror face stainless steel or frosted, all can give people a kind of icy, sensation of lacking avidity.Therefore, in order to adapt to market diversification demand, in industry, businessman can carry out painted plated film to stainless steel work-piece in recent years.At present, the method for stainless steel coloring plated film mainly contains following several: 1. chemical oxidation staining method; 2. electrochemical oxidation staining method; 3. ion deposition oxide coloring method; 4. high temperature oxidation staining method; 5. vapor-phase thermal cracking staining method.But no matter which kind of film coating method all requires that the coated surface of stainless steel work-piece is clean, smooth.And stainless steel billet is in cold rolling, hot rolling and the annealing course of processing, its surface all can produce one deck compact structure, is combined firmly with matrix and has certain thickness oxide scale layer, generally tens micron dimensions; This just needed staff to remove oxide skin before plated film, if this oxide skin is removed clean, plated film is combined just 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 stainless steel oxidation skin both at home and abroad and mainly adopt following several mode:
1, physical mechanical mode, mainly makes medium and stainless steel surface produce by power and rubs, as sandblasting etc.; This method operation is simple, but this single physical mechanical processing mode, exist processing efficiency low, to the knuckle place of workpiece and to the poor problem of the process planeness of thin plate;
2, chemistry and electrochemical means, mainly produces chemical reaction by pickling, electrolysis and stainless steel surface; This method length consuming time also produces a large amount of oxynitride, comparatively large to environmental hazard, and the insufficient oxide skin that causes of pickling remains, and excessive erosion can cause again workpiece surface planeness to be lost; In addition, because workpiece surface active center distribution uniformity coefficient is poor, only rely on naked eyes to be difficult to detect processing quality, thus cause pickling workpiece quality stability bad;
3, laser ablation method, as CN1224644A discloses a kind of method removing oxide compound from metallic surface, comprise: utilize generation pulse width very short, the laser apparatus of the electromagnetic radiation that pulse-repetition frequency is very high and mean power is very high, produce radiation, make this radiation through at least one optical element with make its be focused into this point of contact place, metallic surface at least about 5MW/cm
2the incoming beam of surface power density, and make the radiation laser beam of focusing cross over the oxide compound on covering metal surface in the horizontal completely, to make by the interaction of one or more pulse by evaporating this oxide removal.The method scale removal is uneven, unclean, and needs expensive laser apparatus just can reach, 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 comparatively extensive in current industry, as CN100402703C discloses a kind of method removing oxidized skin on hot rolling nickel stainless steel material, comprise: stainless steel bars or sheet material chemical pickling liquid are soaked 4 ~ 180min by (1) at 5 ~ 95 DEG C, (2) water ultrasonic generator supersound process 5 ~ 120s will be placed in by cleaning material, the component of described pickle solution and weight proportion are: sulfuric acid or hydrochloric acid 5% ~ 25%, inorganic sulphide 0.5 ~ 15%, all the other are water.CN1900384A discloses a kind of technique adopting ultrasonic wave and electrolytic combination to remove part surface oxidized skin, be in same electrolytic solution, utilize different electrolysis and ultrasonic wave to combine scale removal, by controlling electrolysis, the realization of ultrasonic technique parameter completes and removes metal material surface oxide skin at 20 ± 2 DEG C, in 3 ~ 5min/5 μm time.These methods relative to single one physical method or its effect of chemical Treatment higher, but picture ultrasonic applications is on removal Stainless Steel Watch surface oxidized skin, itself also exists congenital defect: 1. ultrasonic sound field is propagated in liquid medium, must decay, position sound field namely near ultrasonic transducer is strong, more more weak away from sound field; 2. ultrasonic cavatition is also uneven, and cavitation bubble can form the spatial distribution that one deck is strong, one deck is weak, one deck is strong, one deck is weak, removes uneven problem so exist when the Stainless Steel Watch surface oxidized skin removed; 3. ultrasonic wave in a liquid cavitation time be attended by cavitation bubble the non-linear vibration collapse that can produce each harmonic and subharmonic and cavitation bubble can give off continuous noise, these compositions mutually superpose and can form liquid cavitation noise.Noise is through water and Air Interface to working space radiation, and greatly about about 85dB, harm staff is physically and mentally healthy.And electrochemistry removes Stainless Steel Watch surface oxidized skin, also there are some uncertain factors, mainly contain: 1. treatment solution: each state of matter (valence state, activity, acidity, precipitation formation etc.) in treatment solution; The temperature variation for the treatment of solution; The material of workpiece, the total area and shape; Workpiece surface active center distribution; Reducing electrode surface contamination etc.If it is improper to control, workpiece surface oxide skin can be caused to remove not thorough or excessive corrosion, stainless steel decorated sheet class workpiece large to area especially, and its process parameters is more wayward, 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, and the bad stability of electrode, electrocatalysis efficiency are reduced; Meanwhile, will produce electrochemical heat at electrode and treatment solution interface, the charger transfer coefficient of electrode, spread coefficient and electrode reaction speed all can change at different temperatures.Visible, there is more deficiency in currently available technology scale removal, is therefore necessary very much to develop a kind of new technology more effectively scale removal, to meet current stainless plated film demand.
Summary of the invention
Object of the present invention is just to provide a kind of method removing Stainless Steel Watch surface oxidized skin, removes unclean, uneven, be difficult to the problem meeting plated film demand to solve the existence of removal Stainless Steel Watch surface oxidized skin.
The object of the invention is to be achieved through the following technical solutions: a kind of method removing Stainless Steel Watch surface oxidized skin, comprises the following steps:
A pending workpiece is fixedly installed in insulating vessel with discharge plate so that the spacing of 10 ~ 30cm is relative by (), hold composite buffering working fluid in described insulating vessel, it is 1: 0.5 ~ 2 cocktail buffer formed by volume that described composite buffering working fluid comprises by Acetic acid-sodium acetate damping fluid and citric acid-sodium citrate damping fluid, and the fatty alcohol-polyoxyethylene ether 0.1 ~ 3g added in cocktail buffer often liter described, polyethyleneglycol nonylplenyl ether 0.2 ~ 5g, thiosemicarbazide 0.1 ~ 1 g, hexamethylenetetramine 5 ~ 20g, benzotriazole 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, silicone antifoam agent 0.01 ~ 0.1g, oxyethyl group 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 with described discharge plate by (), 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 about 350 ~ 600A of pulsed current, pulse-repetition 10 ~ 40 Hz;
C () connects high-voltage pulse power source, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to workpiece process 3 ~ 10 min be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, take out the workpiece after process, cleaning, drying.
Organic acid described in step (a) of the present invention is the mixture of one or both and two or more arbitrary proportion in tartrate, lactic acid, oxysuccinic acid, chelidonamic acid, succinic acid, propionic acid, hexanodioic acid, succsinic acid, Padil, alanine, Gelucystine and halfcystine.
Organic acid described in step (a) of the present invention is the mixture of tartrate, hexanodioic acid, Padil three kinds of arbitrary proportions.
The formulation of silicone antifoam agent 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 damping fluid is containing Glacial acetic acid 60mL and sodium acetate, anhydrous 160g in often liter of damping fluid; Described citric acid-sodium citrate damping fluid is containing monohydrate potassium 8.6g and two citric acid monohydrate trisodium 15.2g in often liter of damping fluid.
Initial conductivity 400 ~ 800 μ S/cm of composite buffering working fluid described in step (a) of the present invention.
Discharge plate described in step (b) of the present invention is provided with the some eletrode tips pointing to described stainless steel work-piece surface scale; Described eletrode tip is the tip, edge being distributed in projecting apertures on described discharge plate; Described eletrode tip also maybe can change the point discharge bar of length for the stainless steel lag screws be arranged on described discharge plate; Described eletrode tip is different in size; Described eletrode tip is that matrix is arranged on described discharge plate.
Described in step (b) of the present invention, high-voltage pulse power source comprises DC high-voltage power supply, current-limiting resistance, trigger switch, electric capacity and wire, described DC high-voltage power supply and current-limiting resistance, electric capacity are in series by wire, described electric capacity and described trigger switch, discharge plate and workpiece are in parallel, 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 trigger switch discharges and power-off for described discharge plate and workpiece provide for controlling high-voltage pulse power source.
Trigger switch described in the present invention is magnetic pulse compressor (mpc), thyratron switch, arrester switch and electrion trigger switch, and preferred electrion trigger switch, as the technology contents disclosed in CN103198956 A.
Composite buffering working fluid in the present invention, is a kind of slightly acidic (pH is about 5) solution, itself has oil removing, molten rust, prevents excessive corrosion, acid mist from suppressing, stablizes acidity, prevents precipitation, improves mass transfer, promotes the function such as desorbing gas and light.High-voltage pulse technology combines with composite buffering working fluid by the present invention, is applied to by high voltage pulse on discharge plate and workpiece, under the effect of highfield, discharge plate and workpiece is formed in composite buffering working fluid and discharges; Occurred the coring shape discharge channel of the high conductivity extended to workpiece surface direction from discharge plate, when passage is once the workpiece arriving opposite, electric energy will discharge along passage with surge formula; Now, pulsed electrical energy to discharge channel impouring, forms electron avalanche, huge pulsed current (10 within the time of Microsecond grade
3~ 10
5a) make to form high electric energy density (10 in passage
2~ 10
3j/cm
3), cause localized hyperthermia (10 thus
4~ 10
5and occur arc discharge K); And then by electric energy composite buffering working fluid collaborative under be converted into mechanics effect, magnetoresistive effect, acoustic effect, calorifics effect, optical effect and chemical effect, make the oxide skin on workpiece under the effect of various effect, remove fast, evenly, neatly, thus achieve goal of the invention.
Method provided by the invention is better than prior art in the effect removing Stainless Steel Watch surface oxidized skin, and it is mainly: the supercritical water oxidation effect 1. under high-temperature high-pressure state.Under high-temperature high-pressure state, thermal expansion causes the density of composite buffering working fluid to reduce, and the rising of pressure makes the phase interface of gas-liquid two-phase disappear, and becomes the supercritical state of homogeneous system.Composite buffering working fluid in this state, the physico-chemical property that to have that speed of response is fast, the reaction times is short, temperature of reaction is low etc. unique, has very strong corrodibility to the oxide skin of stable chemical nature, thus accelerates the removal of oxide skin; 2. cause ionization or transfer transport at composite buffering work discharge in liquid, element valence changes.The electric charge being gathered in electrode two ends can produce great voltage difference, makes the composite buffering working fluid of ate electrode breakdown, produces the ionization channels from the outward extending high conductivity of high voltage electrode, rapidly by energy density (10
2~ 10
3j/cm
3) electric energy inject composite buffering working fluid, thus occur the process of transfer transport, oxide skin discharges or accepts electronics in composite buffering working fluid, changes the character of some oxide compound in selective oxidation cortex, improves the sour water dissolubility of oxide skin; 3. high pressure pulse discharge produces the high temperature pyrolysis in plasma channel.In discharge process, being full of by dense plasma body completely in discharge channel, producing instantaneous temperature can reach (10
4~ 10
5k), pressure can reach (10
2~ 10
3mPa) High Temperature High Pressure, produces the shockwave of outside undergoes rapid expansion, and this impact to oxide skin is better than the effect of sandblasting, shot-peening far away.Because glassware for drinking water has incompressible characteristic, under high pressure, composite buffering working fluid to be pressed in the squama seam of oxide skin and to expand, and loosening the oxide skin on workpiece substrate, providing condition for accelerating to remove Stainless Steel Watch surface oxidized skin; 4., when operating voltage reaches voltage breakdown, there is numerous travelling, tiny silvery white arc discharge point at workpiece surface, and with slight reaction sound.The time that these arc discharge points exist is very short, does not have fixed position, thus realizes the object removing workpiece oxide skin more equably; 5. high-voltage pulse power source is by the ingehious design at the discharge plate top electrode tip synergy in conjunction with composite buffering working fluid, even if the shape of workpiece and surface relief injustice also can reach satisfied effect.
High pressure pulse discharge and composite buffering work liquid phase are worked in coordination with by the present invention, be the various effects such as mechanics effect, acoustic effect, calorifics effect and chemical effect by electric energy conversion, achieve and remove Stainless Steel Watch surface oxidized skin fast, evenly, neatly, simultaneously, the composite buffering working fluid that the present invention uses, also without the need to discarding after using active reduction, only need supplement a part of mother liquor and can continue to recycle.Visible, not only method is simple, with low cost, removal efficiency is high in the present invention, job stability and reliability is high, the life-span of discharge plate is long, stainless steel surface after scale removal is very bright and clean, the demand that can meet again plated film; And in the industrial production without the need to frequently discharging work waste liquid, not only economy but also environmental protection; Compensate for now methodical deficiency, practical, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention's oxide skin removal device used;
Fig. 2 is the operating diagram of high-voltage pulse power source discharge removal oxide skin of the present invention;
Fig. 3 is the local structure 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 that embodiment 1 processes rear stainless steel work-piece surface microscope figure;
Fig. 6 is that comparative example 1 processes front stainless steel work-piece surface microscope figure;
Fig. 7 is that comparative example 1 processes rear stainless steel work-piece surface microscope figure;
Fig. 8 is that comparative example 2 processes front stainless steel work-piece surface microscope figure;
Fig. 9 is that comparative example 2 processes rear stainless steel work-piece surface microscope figure.
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 fluid, 8, workpiece, 9, wire, 10, coring shape discharge channel, 11, eletrode tip.
Embodiment
Embodiment is for further describing the present invention below, but does not limit the present invention in any form.
Be assembled into oxide skin removal device according to structure shown in Fig. 1, this device comprises high-voltage pulse power source and reactor two portions.
Its reactor comprises insulating vessel 5, discharge plate 6, workpiece 8 and composite buffering working fluid 7, support can be provided with in insulating vessel 5, by on relative with workpiece 8 for discharge plate 6 support be fixedly mounted in insulating vessel 5, to guarantee that workpiece 8 to be parallel to each other with discharge plate 6 and relative fixing; Then the composite buffering working fluid 7 prepared in advance is poured in insulating vessel 5, submergence and exceed discharge plate 6 and workpiece 8 height 2 ~ 3cm, also the height of scale removal can be needed to hold composite buffering working fluid 7 according to workpiece, discharge plate 6 is 10 ~ 30cm with the spacing of workpiece 8.
Insulating vessel 5 can open rectangular tank suitable for reading for what be made into by the insulating material such as plastics, bakelite, and will have certain intensity, a sewage draining valve is installed in bottom surface, for time periodic blow down; The capacity of container is determined by length three sizes; Length will consider the spacing of discharge plate 6 and workpiece 8, both height and the spacing with insulating vessel 5 container side wall.In embodiments of the invention, the actual inside dimension of insulating vessel 5 is long 120cm, wide 45cm, high 120cm, discharge plate 6, workpiece 8 are about 10 cm apart from the distance d of the sidewall of insulating vessel 5, bottom surface, and the liquid level of the composite buffering working fluid 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 all can be ordinary stainless steel plate, 1Cr18Ni9 stainless steel plate (also claiming 302 plates) has been selected in the present invention, there is good corrosion resistance nature, for the acid with strong oxidizing property of the nitric acid of little≤65%, erosion resistance is strong, also has certain erosion resistance for basic solution and most of organic acid, mineral acid.Select the thickness of slab of sheet material to be 0.5cm in embodiments of the invention, area is 1m
2, that is: length × wide=100 cm × 100 cm.
Discharge plate 6 is evenly provided with some eletrode tips 11, discharge plate 6 with eletrode tip 11 can be made into various ways: as stamped out the tip of the projection of multiple array on stainless steel flat plate, and protruding size can be selected in (5 ~ 10cm) × (5 ~ 10 cm) scope; Also can refer to front a kind of mode, just the tip of stamped bumps is changed into and a kind of point discharge bar changing length is installed, to adapt to the scraggly surface of workpiece, discharging distance is consistent substantially.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 makes an annulus by the punch of tapering 60 °, diameter of phi 0.5cm, any two circle ring center spacing L are 5cm, and the average hill height X of annulus is 0.3cm; Sheet material, in punching course, is torn by drift, and the top of annulus just defines irregular, scraggly eletrode tip 11 thus.
It is 1: 0.5 ~ 2 cocktail buffer formed by volume that composite buffering working fluid 7 comprises by Acetic acid-sodium acetate damping fluid and citric acid-sodium citrate damping fluid, and the fatty alcohol-polyoxyethylene ether 0.1 ~ 3g added in cocktail buffer often liter described, polyethyleneglycol nonylplenyl ether 0.2 ~ 5g, thiosemicarbazide 0.1 ~ 1 g, hexamethylenetetramine 5 ~ 20g, benzotriazole 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, silicone antifoam agent 0.01 ~ 0.1g, oxyethyl group propargyl alcohol 1 ~ 3g, pyridine 10 ~ 20 g, propine sodium sulfonate 0.05 ~ 1.1g, cocktail buffer is made up of acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) damping fluid and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water damping fluid.The initial conductivity of this composite buffering working fluid is 400 ~ 800 μ S/cm, and temperature is about room temperature, pH is about 5.Wherein organic acid is the mixture of one or both and two or more arbitrary proportion in tartrate, lactic acid, oxysuccinic acid, chelidonamic acid, succinic acid, propionic acid, hexanodioic acid, succsinic acid, Padil, alanine, Gelucystine and halfcystine; The mixture of preferred tartrate, hexanodioic acid, Padil three kinds of arbitrary proportions; The formulation of silicone antifoam agent: ZJ-822 type; Manufacturer is: Guangzhou end Chemical Industry Science Co., Ltd.
As shown in Figure 1, high-voltage pulse power source comprises 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 and current-limiting resistance 3, discharge capacity 2 are in series by wire 9, discharge capacity 2, electrion trigger switch 4 are in parallel with discharge plate 6 in reactor and workpiece 8, for reactor provides high-voltage pulse power source, 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 trigger switch 4 discharges or power-off for discharge plate 6 and workpiece 8 provide for controlling high-voltage pulse power source.Technology contents disclosed in the non-CN103198956 A of mesohigh electric discharge trigger switch 4 of the present invention.Its electrion trigger switch 4 also can 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 regulation range of voltage are determined depending on the working area of workpiece and the spacing of discharge plate and workpiece; The rotational frequency of the capacity of discharge capacity, the resistance of current-limiting resistance, electrion trigger switch, also relevant with the spacing of the power of DC high-voltage source, voltage and discharge plate and workpiece, the determination of these parameters belongs to known technology category.
The present invention is when processing Stainless Steel Watch surface oxidized skin, start electrion trigger switch 4, connect high-voltage pulse power source, high-voltage pulse power source is discharged by discharge plate 6 pairs of workpiece 8, the workpiece be immersed in described composite buffering working fluid 7 is processed, when electrion trigger switch 4 turns over on-state, when forming trip condition, DC high-voltage source is charged for discharge capacity 2 by current-limiting resistance 3, for the electric discharge of next on-state is prepared.Until by time clean for the oxide skin process on workpiece 8, disconnect described high-voltage pulse power source in treating processes, take out the workpiece after process, cleaning, drying.
Electric energy is formed high voltage pulse by electrion trigger switch 4 and is applied to discharge electrode 6 with on workpiece 8 by high-voltage pulse power source, and discharge electrode 6 and workpiece 8 are formed and discharge in composite buffering working fluid.Composite buffering working fluid medium between discharge plate, workpiece, under the effect of highfield, occurred the passage (see figure 2) of the bifurcated (as coring shape) from the outward extending high conductivity of high voltage electrode, when passage is once the workpiece arriving opposite, electric energy will discharge along passage with surge formula.Now, the electric energy that electrical condenser stores to discharge channel impouring, forms electron avalanche, huge pulsed current (10 within the time of Microsecond grade
3~ 10
5a) make to form high-energy-density (10 in passage
2~ 10
3j/cm
3), cause localized hyperthermia (10 thus
4~ 10
5and occur arc discharge K).Be below concrete Processing Example:
Embodiment 1
Workpiece 8 with oxide skin is set to 21cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 4000V, and the peak value of pulsed current is about 430A, pulse-repetition 30Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 1.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 300 g; Polyethyleneglycol nonylplenyl ether (O π-10) 500 g; Thiosemicarbazide 100g; Hexamethylenetetramine 500 g; Benzotriazole 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(tartrate 10g, hexanodioic acid 20g, Padil 20g); Silicone antifoam agent (ZJ-822 type; Guangzhou end Chemical Industry Science Co., Ltd) 10 g; Oxyethyl group propargyl alcohol 300g; Pyridine 1000 g; Propine sodium sulfonate 5 g, stir and form composite buffering working fluid, its specific conductivity is about 650 μ S/cm, and initial temperature is 27 DEG C;
Start electrion trigger switch 4, frequency is 30Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to oxide skin process 8 min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Embodiment 2
Workpiece 8 with oxide skin is set to 10cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 3000V, and the peak value of pulsed current is about 350A, pulse-repetition 40 Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 2 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 200 g; Polyethyleneglycol nonylplenyl ether (O π-10) 250 g; Thiosemicarbazide 50g; Hexamethylenetetramine 1000 g; Benzotriazole 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(tartrate 10g, hexanodioic acid 10g, Padil 10g); Silicone antifoam agent (ZJ-822 type; Guangzhou end Chemical Industry Science Co., Ltd) 5 g; Oxyethyl group propargyl alcohol 150g; Pyridine 2000 g; Propine sodium sulfonate 110g, stir and form composite buffering working fluid, its specific conductivity is about 540 μ S/cm, and initial temperature is 26 DEG C;
Start electrion trigger switch 4, frequency is 40Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to oxide skin process 10 min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Embodiment 3
Workpiece 8 with oxide skin is set to 30cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 10000 V, and the peak value of pulsed current is about 600A, pulse-repetition 10 Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 0.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 250 g; Polyethyleneglycol nonylplenyl ether (O π-10) 150 g; Thiosemicarbazide 10g; Hexamethylenetetramine 2000 g; Benzotriazole 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(tartrate 5g, lactic acid 5g); Silicone antifoam agent (ZJ-822 type; Guangzhou end Chemical Industry Science Co., Ltd) 1 g; Oxyethyl group propargyl alcohol 100g; Pyridine 1500 g; Propine sodium sulfonate 80 g, stir and form composite buffering working fluid, its specific conductivity is about 710 μ S/cm, and initial temperature is 27 DEG C;
Start electrion trigger switch 4, frequency is 10Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to oxide skin process 5 min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Embodiment 4
Workpiece 8 with oxide skin is set to 18cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 8000 V, and the peak value of pulsed current is about 520A, pulse-repetition 15 Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 1 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 10 g; Polyethyleneglycol nonylplenyl ether (O π-10) 20 g; Thiosemicarbazide 10 g; Hexamethylenetetramine 480 g; Benzotriazole 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; Silicone antifoam agent (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 4g; Oxyethyl group propargyl alcohol 250g; Pyridine 1700 g; Propine sodium sulfonate 60 g, stir and form composite buffering working fluid, its specific conductivity is about 400 μ S/cm, and initial temperature is 25 DEG C;
Start electrion trigger switch 4, frequency is 15Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to the oxide skin process 10min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Embodiment 5
Workpiece 8 with oxide skin is set to 20cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 5000 V, and the peak value of pulsed current is about 490A, pulse-repetition 35 Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 1.8 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 200 g; Polyethyleneglycol nonylplenyl ether (O π-10) 400 g; Thiosemicarbazide 40g; Hexamethylenetetramine 1000 g; Benzotriazole 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, hexanodioic acid 20g); Silicone antifoam agent (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 7 g; Oxyethyl group propargyl alcohol 180g; Pyridine 1200 g; Propine sodium sulfonate 15 g, stir and form composite buffering working fluid, its specific conductivity is about 700 μ S/cm, and initial temperature is 27 DEG C;
Start electrion trigger switch 4, frequency is 35Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to oxide skin process 8 min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Embodiment 6
Workpiece 8 with oxide skin is set to 10cm with the spacing of discharge plate 6, and the crest value of impulse voltage arranging high-voltage pulse power source is 8000 V, and the peak value of pulsed current is about 560A, pulse-repetition 15 Hz.
Composite buffering working fluid is prepared in the following manner: adopt acetic acid (Glacial acetic acid 60mL/L)-sodium-acetate (sodium acetate, anhydrous 160g/L) buffer system and citric acid (monohydrate potassium 8.6g/L)-Trisodium Citrate (two citric acid monohydrate trisodium 15.2g/L) water buffer solution system, two kinds of buffered soln are 1 ︰ 1.5 mixed preparing 100L according to volume ratio, and are added in this cocktail buffer and add fatty alcohol-polyoxyethylene ether 300 g; Polyethyleneglycol nonylplenyl ether (O π-10) 500 g; Thiosemicarbazide 100g; Hexamethylenetetramine 500 g; Benzotriazole 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(tartrate 10g, hexanodioic acid 20g, Padil 20g); Silicone antifoam agent (ZJ-822 Guangzhou end Chemical Industry Science Co., Ltd) 10 g; Oxyethyl group propargyl alcohol 300g; Pyridine 1000 g; Propine sodium sulfonate 5 g, stir and form composite buffering working fluid, its specific conductivity is about 800 μ S/cm, and initial temperature is 26 DEG C;
Start electrion trigger switch 4, frequency is 15Hz, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to the oxide skin process 3min of the workpiece be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, cooling, takes out the workpiece after process, cleaning, drying.
Comparative example 1
Adopt 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, by the continuous stirred liq of sticking plaster, make liquid movement, rub with workpiece 8, treatment time 5 ~ 8 min, takes out the workpiece after process, cleaning, drying.
Comparative example 2
Adopt acid soak+supersound washing: in insulating vessel 5 in embodiments of the present invention, hang up (the JHZ-1048-28 type produced by Suzhou Jia Hui Supersonic Tech Corp.) ultrasonic vibrating plate, ultrasonic frequency is 28KHz, rated output 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 to be placed in the middle of two vibration plates and to soak in the solution, open ultrasonic-frequency power supply switch, workpiece 8 is treatment time 5 ~ 8 min in acid soak+ultrasound environments, takes out the workpiece after process, cleaning, drying.
Embodiment 7
Experimental technique: a few place of random selecting on workpiece 8 is marked by embodiment 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.It the results are shown in Figure 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8 and Fig. 9.
Result:
From Fig. 4, Fig. 5 relatively, Fig. 5 can clear, significantly see crystal boundary, smooth finish is good, the clearance 100% of oxide skin, observes integral surface bright and clean degree, substantially evenly.
From Fig. 6, Fig. 7 relatively, show stainless steel surface crystal boundary in Fig. 7 and almost do not see Chu, oxide skin is not removed substantially, just removes, the oil stain dirt on surface without positive effect.
From Fig. 8, Fig. 9 relatively, though show crystal boundary in Fig. 9 as seen and more clear, surface smoothness is bad, and oxide skin is not removed completely.
Visible, can see from detected result, removal effect of the present invention is obviously better than the method such as conventional acid liquid washing by soaking and acid soak+supersound washing, is also obviously better than prior art.
The embodiment that the present invention enumerates is intended to further illustrate this processing method of removal stainless material oxide skin and the application direction in related industries, and does not form any restriction to protection scope of the present invention.
Claims (5)
1. remove a method for Stainless Steel Watch surface oxidized skin, it is characterized in that, comprise the following steps:
A pending workpiece is fixedly installed in insulating vessel with discharge plate so that the spacing of 10 ~ 30cm is relative by (), hold composite buffering working fluid in described insulating vessel, it is 1: 0.5 ~ 2 cocktail buffer formed by volume that described composite buffering working fluid comprises by Acetic acid-sodium acetate damping fluid and citric acid-sodium citrate damping fluid, and the fatty alcohol-polyoxyethylene ether 0.1 ~ 3g added in cocktail buffer often liter described, polyethyleneglycol nonylplenyl ether 0.2 ~ 5g, thiosemicarbazide 0.1 ~ 1 g, hexamethylenetetramine 5 ~ 20g, benzotriazole 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, silicone antifoam agent 0.01 ~ 0.1g, oxyethyl group 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 with described discharge plate by (), 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 about 350 ~ 600A of pulsed current, pulse-repetition 10 ~ 40 Hz;
C () connects high-voltage pulse power source, make high-voltage pulse power source by discharge plate to described workpiece electrical discharge, to workpiece process 3 ~ 10 min be immersed in described composite buffering working fluid, disconnect described high-voltage pulse power source, take out the workpiece after process, cleaning, drying.
2. the method for removal Stainless Steel Watch surface oxidized skin according to claim 1, it is characterized in that, organic acid described in step (a) is the mixture of one or both and two or more arbitrary proportion in tartrate, lactic acid, oxysuccinic acid, chelidonamic acid, succinic acid, propionic acid, hexanodioic acid, succsinic acid, Padil, alanine, Gelucystine and halfcystine.
3. the method for removal Stainless Steel Watch surface oxidized skin according to claim 2, is characterized in that, organic acid described in step (a) is the mixture of tartrate, hexanodioic acid, Padil three kinds of arbitrary proportions.
4. the method for removal Stainless Steel Watch surface oxidized skin according to claim 1, is characterized in that, initial conductivity 400 ~ 800 μ S/cm of the working fluid of composite buffering described in step (a).
5. the method for removal Stainless Steel Watch surface oxidized skin according to claim 1, is characterized in that, discharge plate described in step (b) is provided with the some eletrode tips pointing to described stainless steel work-piece surface scale.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410565105.1A CN104342714B (en) | 2014-10-22 | 2014-10-22 | A kind of method removing stainless steel watch surface oxidized skin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410565105.1A CN104342714B (en) | 2014-10-22 | 2014-10-22 | A kind of method removing stainless steel watch surface oxidized skin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104342714A true CN104342714A (en) | 2015-02-11 |
| CN104342714B CN104342714B (en) | 2016-08-24 |
Family
ID=52499149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410565105.1A Expired - Fee Related CN104342714B (en) | 2014-10-22 | 2014-10-22 | A kind of method removing stainless steel watch surface oxidized skin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104342714B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106884172A (en) * | 2017-01-19 | 2017-06-23 | 南京百丝胜新材料科技有限公司 | A kind of environment-friendly type metal surface cleaning agent and activation method |
| CN107321586A (en) * | 2017-06-29 | 2017-11-07 | 华中科技大学 | A kind of liquid electric pulse shock wave generation device |
| CN114657545A (en) * | 2021-03-12 | 2022-06-24 | 塞尔纳新材料(武汉)有限公司 | Ecological descaling type rapid sedimentation passivation solution and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20050145174A1 (en) * | 2002-02-19 | 2005-07-07 | Daniel Chaleix | Method of cleaning the surface of a material coated with an organic substrate and a generator and device for carrying out said method |
| 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 |
-
2014
- 2014-10-22 CN CN201410565105.1A patent/CN104342714B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20050145174A1 (en) * | 2002-02-19 | 2005-07-07 | Daniel Chaleix | Method of cleaning the surface of a material coated with an organic substrate and a generator and device for carrying out said method |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106884172A (en) * | 2017-01-19 | 2017-06-23 | 南京百丝胜新材料科技有限公司 | A kind of environment-friendly type metal surface cleaning agent and activation method |
| CN107321586A (en) * | 2017-06-29 | 2017-11-07 | 华中科技大学 | A kind of liquid electric pulse shock wave generation device |
| CN114657545A (en) * | 2021-03-12 | 2022-06-24 | 塞尔纳新材料(武汉)有限公司 | Ecological descaling type rapid sedimentation passivation solution and preparation process thereof |
| CN114657545B (en) * | 2021-03-12 | 2023-11-24 | 塞尔纳新材料(武汉)有限公司 | Ecological descaling type rapid sedimentation passivation solution and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104342714B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0904428B1 (en) | An electrolytic process for cleaning electrically conducting surfaces | |
| CN101605929B (en) | Ceramic coated metal material and production method thereof | |
| JP3847770B1 (en) | Ceramic-coated metal material and method for producing the same | |
| CN101591798A (en) | A kind of metalwork and surface treatment method thereof | |
| CN101709476A (en) | Production method and equipment for deburring aluminum workpieces by continuously alkali washing | |
| CN104342714A (en) | Method for removing oxide skin on stainless steel surface | |
| TW201319326A (en) | Surface processing method on valve metal using plasma electrolytic oxidation | |
| CN108857050A (en) | A kind of preparation method of metal surface rule dimple texture array | |
| CN105018905A (en) | Preparation method for chemically plating nickel-phosphorus coating on surface of anchor rod steel | |
| RU2375506C2 (en) | Method and device for etching of metals | |
| CN105200509A (en) | Cleaning method of electronic energy storage materials | |
| CN103266343B (en) | The surface roughening approach of metallic substance | |
| CN104264200A (en) | Micro-arc oxidation treatment device and method | |
| US5981084A (en) | Electrolytic process for cleaning electrically conducting surfaces and product thereof | |
| CN103834983B (en) | The environment-protecting energy-saving liquor phase plasma cleaning method of shape | |
| CN103952711A (en) | Continuous online treatment technique for metal surface | |
| US20030075456A1 (en) | Electrolytic treatment | |
| CN102899703A (en) | Silicate electrolyte and application of silicate electrolyte in magnesium alloy micro-arc oxidation film preparation | |
| CN105567459B (en) | A kind of green alkaline cleaning solution and preparation method | |
| WO2003027359A2 (en) | External counter electrode and method for chemical milling and cleaning metal | |
| CN101914781B (en) | Titanium electrode material coated with nanometre rhodium iridium coatings and preparation method thereof | |
| CN107338449A (en) | A kind of titanium alloy surface aoxidizes skin laser cleaning method | |
| CN100422390C (en) | Differential arc oxidization abrasive polishing method for stainless steel surface | |
| CN105200476B (en) | A kind of stainless steel bolt electroplating pretreatment method | |
| CN102345126A (en) | Method for treating surface of metal workpiece |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20181022 |