CN1103114A - Method for removing certain oxide films from metal surfaces - Google Patents
Method for removing certain oxide films from metal surfaces Download PDFInfo
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- CN1103114A CN1103114A CN94108006.4A CN94108006A CN1103114A CN 1103114 A CN1103114 A CN 1103114A CN 94108006 A CN94108006 A CN 94108006A CN 1103114 A CN1103114 A CN 1103114A
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- 238000000034 method Methods 0.000 title claims description 74
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 107
- 239000010959 steel Substances 0.000 claims abstract description 107
- 230000035882 stress Effects 0.000 claims abstract description 21
- 230000008646 thermal stress Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 5
- 230000006378 damage Effects 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 239000007888 film coating Substances 0.000 claims 1
- 238000009501 film coating Methods 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 238000005498 polishing Methods 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 208000037656 Respiratory Sounds Diseases 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000137 annealing Methods 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 229910000754 Wrought iron Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 229910000734 martensite Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010011376 Crepitations Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
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- 239000006210 lotion Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/82—Descaling by thermal stresses
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
- C25F1/06—Iron or steel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Mechanical stress is applied to a manufactured metal member (e.g., steel wire) having a magnetite film on the surface to crack the magnetite film against the surface of the metal member. The metal piece is then passed through an electrolytic cell, where the metal piece forms the anode in the cell and the vertically disposed steel strip forms the cathode. Pulsed Direct Current (DC) power is applied to the anode and cathode. The current flows through cracks in the oxide to the surface of the metal article, maintaining the metal article anode in a depassivated state. The bond between the oxide film and the metal piece is loosened. The loosened magnetite is then easily removed from the metal part. A thermal stress step may also be applied before applying the mechanical stress.
Description
The application is the U.S. series No.08/095 that submitted on July 21st, 1993,689 part continuation application.
The present invention relates generally to the technology of removing certain oxide film (for example Z 250) from the metallic surface, relate in particular to a kind of like this method of not using acid bath.
In the manufacturing of raw material metal (for example steel wire, steel bar etc.), because oxygen in the end forms layer oxide film on the product with the iron reaction of heat after annealing or other thermal treatment and before quenching.In an important embodiment, on ferruginous steel surface, produced Z 250 (Fe
3O
4) film.When the same oxygen-containing gas of metallic substance (for example air) when directly contacting, produced ferriferrous oxide film under the elevated temperature during pushing.For example, under the steel wire situation, require elevated temperature to reduce the stress that produces owing to extrusion process usually.Must remove this special oxide compound (being Z 250) from steel wire in that any subsequent technique (for example zinc-plated and/or silver-plated) is preceding.Unless remove Z 250 from bottom steel wire metallic surface, otherwise this subsequent disposal will can not succeedd.Therefore, effectively and fully to remove Z 250 from the underlying metal product be quite important and very need.
The traditional method of removing this oxide film is that the metal product with capping oxide is immersed in the acid bath, is commonly referred to pickling.
Hydrochloric acid and sulfuric acid are two kinds of examples of appropriate acid lotion.These acid can be dissolved ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4) and iron monoxide (FeO).Acid bath can be removed oxide compound and produce water and various molysite with the chemical reaction of knowing effectively.After removing oxide compound, the iron in the bottom product made from steel continues dissolving, produces oxygen simultaneously and dissolved molysite.
Oxide compound is rapid although pickling is removed, and it exists some shortcomings, comprises the hydrogen embrittlement of possible underlying metal product, because metal product absorption hydrogen causes bubble, crackle and scale flaking in metal product.In addition, chemical substance used in acid cleaning process has sizable corrodibility usually, and generally all quite expensive, thereby has increased the cost of technological process.This technological process also produces deleterious waste liquid, and this waste liquid must be handled.At last, owing to the solution in institute's dissolved salt quantitative changeization during the technological process and the acid bath changes, the concentration that pickling is bathed can change continuously.
The method of having attempted using some to be different from pickling removes oxide compound.In the U.S. Patent No. 4,795,537 of authorizing Timewell, narrated a kind of like this trial.Though ' 537 methods are effectively in removing many oxide compounds, it is stable to described Timewell pulse direct current electrolysis system that some oxide compound (for example Z 250) is but arranged.
Therefore, need a kind of method of removing Z 250 and similar oxide compound mulch film from the metal product (for example, steel wire, rod iron etc.) effectively, after making (extruding) this metal product, so that can carry out subsequent disposal, for example silver-plated.
So, the present invention includes a kind ofly from the get on method of oxide film dissolving (for example Z 250) of metalwork and product made from steel, this method may further comprise the steps: to the metalwork stress application, to destroy the oxide film near the metalwork surface; Make metalwork by having the electrolyzer of two electrodes that separate each other, wherein metalwork itself forms an electrode; And apply pulse direct current (DC) signal to an electrode and another electrode, wherein the oxide film on the metalwork is by completely destroy, pulse direct current (DC) signal flows into metalwork by damaged zone, make the metalwork electrode remain on depassivation state so that do not produce any oxygen thereon, oxide film on the metalwork is got loose so that can be at an easy rate from the metalwork oxide film dissolving that gets on.
Fig. 1-5 shows the various technology that are used for broken ferriferrous oxide film surface, and this is the first step of the inventive method.
Fig. 6 and 7 shows all processes of the present invention.
Fig. 8 is the synoptic diagram of expression thermal stresses step.
The present invention includes from metal base (for example steel wire, steel bar, rod iron or metal sheet etc.) and remove ferriferrous oxide film or other similar oxide compound.Above-mentioned explanation is particularly related to and is called Z 250 (Fe
3O
4) oxide compound, and frangible (through broken) and electrical conductivity also can use the inventive method to be removed than other oxide compound of metal base difference.As mentioned above, can produce ferriferrous oxide film when the same at elevated temperatures oxygen-containing gas in the surface of ferrous metal (for example steel) (for example air) contacts, elevated temperature is desired during steel wire pushes.High temperature can be used to reduce racking stress in extrusion process.As implied above, if steel wire or other product made from steel will carry out subsequent disposal (for example zinc-plated or silver-plated), it is very important removing ferriferrous oxide film.
In the method for the invention, at first partly broken or destruction ferriferrous oxide film is so that provide the inlet that leads to the beneath metal base of film.Fig. 1-5 shows and carries out several different technologies of suitable destructive, although also can use other method.In first kind of technology shown in Figure 1, axially apply tensile stress to steel wire that is coated with Z 250 or rod iron 10 through extruding.Steel wire one speech used herein also comprises rod iron, because rod iron is counted as heavy wire usually.This can produce strain on the outside surface 11 of ferriferrous oxide film, thereby causes the expansion than crackle and surface imperfection that exists in the ferriferrous oxide film, so that as among Figure 1A shown in 12, they are around the steel wire circumferential expansion.As being entitled as " Fensile Fracture of Magnetite Film " in Corrosion Science at P.L.Harrison, 1967, Vol.7, discussed in the document of pp.789-794 like that, the fact shows that these crackles occur in 0.8-3.2 * 10
-3The tension strain scope in.
Figure 2 illustrates second kind of breaking method.In the method, crooked steel wire 16 is to produce tensile stress on the outside surface 18 of steel wire.For thickness is the oxide compound of 2 μ m, produces the common and above-mentioned strain facies that produces according to Fig. 1 of the required strain of suitable crackle together.
Fig. 3 shows the changing method of Fig. 2 method, in the method, usually use two cylinders that separate each other (illustrating) with plane form, crooked steel wire 20 at first in one direction, the crooked steel wire 20 that on same level, (promptly turns to 180 °) more in the opposite direction then, so that on the bilateral of steel wire, produce stress, thereby on the surface of ferriferrous oxide film, produce many crackles.
Fig. 4 shows the changing method of Fig. 3 method, in the method, also is to use two cylinders that are separated from each other, and sequential forming steel wire 24 on both direction only is offset two parallel planes 25,26 a little.This can produce required crackle or breakage on Z 250 surface 27.Fig. 5 shows the another kind of changing method of Fig. 3 method, in the method, crooked steel wire 28 on the both direction on a plane 30 at first, crooked steel wire 28 once more on the both direction on another plane 32 then, 5 °-90 ° of first plane 30 rotations are left on plane 32.Method shown in Figure 5 can be used as replenishing of earlier figures 1-4 method, cracks with the whole surface at steel wire.
Except above specific method, other method that is used to produce the oxide film surface crack also is possible, comprises using ultrasonic vibration (especially when product is not had by water logging), particle collision technology (for example sandblast) and wire brush brushing.Employed specific crushing technology will change with the shape of raw material metal, and promptly whether metal products is other shape of steel wire/rod iron, steel bar, steel plate or certain.
After any " anterior-posterior " treatment step (for example annealing etc.), the metal products of above-mentioned all shapes of design is so that produce the crackle or the breakage of oxide film unanimity along the length of metal base.This crackle must be greater than surface crack, and promptly they must extend downwardly on the surface of metal base.
Whole treating processess have been shown in Fig. 6 and 7, carry out usually with 2 plain bendings (Fig. 5) 40 shown in destruction/broken step after, with the electrolyzer shown in 43, in this electrolyzer, steel wire 43 is its anode parts to the steel wire 42 of covering Z 250 by general.Authorize Timewell ' 537 patents shown in and narrated above-mentioned electrolyzer, thereby can be in conjunction with reference to this patent.
Usually, electrolyzer medium 44 is the sodium chloride solutions under the room temperature.The steel wire 42 that covers Z 250 is anodes, and the anode (not shown) of power supply is connected on the roller in front 46, and it contacts with steel wire 42.
Usually, steel bar 54(Fig. 7 such as one or more vertically disposed L shaped or U-shaped) form negative electrode, and also generally all very close steel wire anode, about 0.5 inch of closest approach.Steel wire 42 is continuously by being equipped with the elongated and narrow groove 48 of sodium chloride solution.This solution 44 overflows from the end of groove 48 and flows into recycle tank 50.Use pump 52 with solution 44 blowback grooves 48 at this place.The negative terminal of power supply is connected on the steel bar negative electrode 54.
Signal from power supply is pulse direct current (DC) signal.The tectum that electric current is walked around Z 250 by crackle or breakage is bypassed on the metal base under it, rather than flows through ferriferrous oxide film.This will cause anode surface (being the wire substrate surface) to remain on the depassivation state, so that can not produce any oxygen in this substrate.Described as ' 537 patents, the speed dissolving of the anode in the depassivation state to be exceedingly fast, and do not produce any oxygen.This will cause the mechanical bond intensity between Z 250 and the metal base obviously to reduce, thereby the ferriferrous oxide film on its substrate surface is got loose.
At this moment, some oxide film comes off usually.Can remove residue (Z 250 residue) at an easy rate by various technology.With reference to figure 6, make the steel wire that leaves residue by flushed channel 58, this flushed channel 58 comprises all shower nozzle 60, the current that shower nozzle 60 makes 40psi or bigger pressure are the steel wire to having handled directly.Another kind of alternative method can be immersed in steel wire in the water of being furnished with ultrasonic oscillator, but must with ultrasonic oscillator be tuned to the natural frequency or the resonant frequency of steel wire.Pump 64 infeeds shower nozzle with the water in the groove.At last, use standard machinery instrument (for example wiper 66) to remove last residue from steel wire.Also can use other technology, comprise making steel wire pass through damp sand, or use ultrasonic wave.Steel wire comes out by two stern rolls 68 then, and this cylinder 68 also is connected to the anode of power supply.
After above-mentioned steps, can make products obtained therefrom lead to follow-up treatment station, for example zinc-plated.Make steel wire pass through electrolyzer continuously although said process comprises, it also one by one segmentation handle i.e. fed batch.
Below be that the present invention uses above-mentioned general method shown in Figure 6 to remove the several concrete operation embodiment of Z 250.In one embodiment, making steel wire cross radius with 45 ° is that 5/8 inch cylinder is with its bending stretch.Then steel wire is immersed in and is equipped with in the electrolyzer of sodium chloride solution that concentration is 40 grams per liters.Pulse direct current (CD) electricity is applied to the two ends of steel wire.By being parallel to steel wire and forming negative electrode apart from the vertical steel negative electrode of its about 1/2 inch two.In this structure, anode is in the depassivation state and goes up without any chlorine or oxygen generation at steel wire (anode).The pulse direct current of power supply (DC) signal is about 7.8 volts (peak point current 9.8 peaces), 60 hertz of frequencies (working cycle 50%), and the average anode peak current density that produces on Steel Wire Surface is 451 milliamperes/centimetre
2
In second kind of embodiment, at two plane in-draw crooked steel wires: beginning is crossed 5/8 inch cylinder deflection steel wire with 45 °, and half-twist is crossed 5/8 inch cylinder crooked steel wire once more with 45 ° again then.Then steel wire being immersed in concentration is housed is that 40 grams per liters, temperature are in 42 ℃ the electrolyzer of sodium chloride electrolyte.The average peak of pulse direct current (DC) electricity is 7.2 volts (peak point current 38.5 peaces), 60 hertz of frequencies (working cycle 13%), and the average anode peak current density of Steel Wire Surface is 1784 milliamperes/centimetre
2
In the third embodiment, at first crossing radius with 45 is 5/8 inch cylinder deflection steel wire, and half-twist is crossed 5/8 inch cylinder crooked steel wire once more with 45 ° again then.Then steel wire being immersed in concentration is housed is that 40 grams per liters, temperature are in 45 ℃ the electrolyzer of sodium chloride electrolyte.The crest voltage of pulse direct current (DC) signalling current is 10.0 volts (average peak electric current 55 peaces), 60 hertz of frequencies (working cycle 19%), and the average anode peak current density of Steel Wire Surface is 2548 milliamperes/centimetre
2
In embodiment 4, at two plane inner bending steel wires, at first cross 5/8 inch cylinder with 45, then along peripheral half-twist, cross 5/8 inch cylinder with 45 again.Then steel wire being immersed in concentration is housed is that 40 grams per liters, temperature are in 45 ℃ the electrolyzer of sodium chloride electrolyte.The average peak voltage of pulse direct current (DC) is 7.55 volts (average peak electric current 36.7 peaces), 60 hertz of frequencies (working cycle 13%), and the average anode peak current density of Steel Wire Surface is 2156 milliamperes/centimetre
2
Above-mentioned four kinds of embodiment can both successfully peel off Z 250 from the steel base surface of steel wire form.Does not wait required time about 10 seconds from 30 seconds of embodiment 1 to embodiment 4.Water washes away or cleans and remove residual Z 250.In various situations, with the removal situation of electron microscope scanning inspection Z 250.
Thereby, the mechanical means that is used for removing from metal base (for example ferruginous steel) Z 250 and similar oxide film has been described.
Fig. 8 show a kind of can be in conjunction with above-mentioned mechanical stress technology, the perhaps heating means that can use separately in some cases are to improve the traditional method of removing Z 250 or other oxide compound from the underlying metal silk.In the embodiment that illustrates, from fluidized-bed 80, draw the steel wire of capping oxide, steel wire is with about 1400 annealing temperature in fluidized-bed 80.Other metals then have different annealing temperatures.Except fluidized-bed, also can use other annealing technology.As everyone knows, annealing is in order to reduce the strain that wire takes place during pushing.Yet annealing steps only is used for illustrating, because annealing is dispensable in an application of the invention.When steel wire under regulation high temperature fluidized-bed or other anneal draw and when cooling off in air, steel wire usually will be through a series of different crystallisation stages.The variation of crystal structure during cooling also will be different for different metals.
When having moved 20 feet or its downstream (typical rate with 215 feet per minutes moves) to steel wire, steel wire generally will reach about 800 temperature.At this moment, make the steel wire that is coated by tube bank 82, spray the cold water with suitable high pressure facing to oxide coated steel wire in tube bank 82, oxide compound (being generally Z 250) surface film is cooled off rapidly, promptly quenches.If zone of oxidation has lower thermal expansivity than its beneath wire, then cooling will make Z 250 produce stress fast, so that in this oxide compound, produce little break, eyelet or breach, perhaps in other words, Z 250 will be from the underlying metal delaminate slightly, just curl, swelling or peel off.
No matter any situation takes place, can both very easily thoroughly break/destroy by above-mentioned mechanical step and bear the ferriferrous oxide film of thermal stresses, perhaps in some cases, do not need to apply mechanical stress and directly use electrolyzer can remove ferriferrous oxide film.
Especially under the steel situation, importantly fully carry out hot quenching after the cooling at steel wire, steel wire is therefore and through the crystallisation stage of several successive, so that quenches and can not produce martensite, and martensite is a kind of very frangible and undesirable steel crystal structure.When steel wire is still overheated, quench and to produce martensite.In addition, with regard to steel, the carbon content of steel wire is crucial again.Preferably the quite low steel of carbon content produce martensitic possibility because this can reduce.As implied above, the wire temperature before quenching should be about 800 °F or lower.
According to the hot quenching step, after the steel wire that coats leaves tube bank or other quenching device, in short range (about 12 feet) steel wire is once more by air cooling, yet above-mentioned distance can change.When steel wire leaves when quenching tube bank 82, its temperature has been lowered to about 150 °F usually.Wire temperature further is lowered in air gradually then, arrives tank 84 up to steel wire, and tank 84 is about 4 feet in the illustrated embodiment, 110 of temperature.After the steel wire that is coated passed through tank, its temperature was about 110 °F.
As above indication as above describedly in detail applies mechanical stress to steel wire like that, for example adopts crooked method, perhaps in some cases, can avoid the mechanical stress step and steel wire is directly fed electrolyzer.When applying mechanical stress, it does not need reactive force big as in other cases or violent bending like that.
When oxide coated steel wire has been in room temperature, also can finish the thermal stresses step.In this case, steel wire element is heated to about 800 °F, so that set up thermograde and by the stress gradient of its generation, oxide compound is in than under the higher temperature of steel wire between oxide film and underlying metal.This can cause oxide on surface to enter swelling state, and the bottom wire material still is in compressed state.After this thermal stresses step, add and reduce temperature gradually, perhaps, if necessary, add the quenching step as mentioned above,, increase the stress on the oxide film to form the thermal stresses circulation.Can apply mechanical stress to steel wire as mentioned above then, perhaps in some cases, can directly enter electrolyzer.
Yet much less, more than the special parameter that provides for thermal stresses be only applicable to steel wire, and will be different for other metal.
Although disclose optimum implementation, much less those skilled in the art can carry out various modifications and changes to disclosed embodiment.Limit the inventive method by following claims.
Claims (33)
1, a kind of from the get on method of oxide film dissolving of metalwork, this method may further comprise the steps:
To the metalwork stress application, to destroy oxide film near the metalwork surface;
Make metalwork by having the electrolyzer of 2 electrodes that separate each other, wherein metalwork forms an electrode in the electrolyzer; And
An electrode and another electrode in electrolyzer apply pulse direct current (DC) signal, wherein the oxide compound on the metalwork is fully destroyed, thereby make pulse direct current (DC) signal arrive metalwork by the destruction region, and the metalwork electrode remained on the depassivation state, so that on the metalwork electrode, do not produce oxygen fully, and oxide film is got loose from metalwork, so that from metalwork, remove oxide film at an easy rate.
2,1 method as requested, wherein, oxide film is a Z 250, and metalwork is made with ferruginous steel.
3, according to the process of claim 1 wherein, metalwork is the steel wire that has elongated, and pulse direct current (DC) electricity is applied to the part that the steel wire that extends through electrolyzer is separated from each other.
4, according to the method for claim 3, wherein, pulse direct current (DC) electricity is applied on the steel wire by the cylinder that is separated from each other.
5, according to the process of claim 1 wherein, metalwork forms the anode in the electrolyzer.
6, according to the process of claim 1 wherein that electrolyzer comprises the electrolytic solution that contains sodium oxide and water.
7,, comprise from metalwork and remove the step of any residual oxide film with the clean surface that stays metalwork according to the method for claim 1.
8, according to the method for claim 7, wherein, from electrolyzer, draw the back water at steel wire and wash away on the steel wire to remove residual oxide compound.
9, according to the process of claim 1 wherein, make metalwork pass through electrolyzer continuously.
10, according to the process of claim 1 wherein, the sequential portion of metalwork is entered, leave electrolyzer then.
11,, comprise by using polishing particles to remove the step of any residual oxide film from metalwork according to the method for claim 1.
12, according to the process of claim 1 wherein, comprise the step of bending metals spare to the step of metalwork stress application.
13,, comprise the step of using ultrasonic wave to remove any residual oxide film from metalwork according to the method for claim 1.
14, according to the process of claim 1 wherein, comprise the step of usefulness ultrasonic vibration metalwork to the step of metalwork stress application.
15, a kind of metalwork of making, this metalwork comprises:
Metalwork has the surface, from this surface through at first disruptive oxidation film, then electrolyzer to metalwork apply pulse direct current (DC) thus electricity gets loose oxide film makes it remove from this surface, wherein metalwork forms an electrode of electrolyzer.
16, according to the goods of claim 15, wherein, metal oxide is a Z 250, and metalwork comprises ferruginous steel.
17, according to the goods of claim 15, wherein, metalwork is a steel wire.
18,, be included in the step that before oxide film applies mechanical stress, applies thermal stresses earlier to oxide film according to the method for claim 1.
19, according to the method for claim 18, wherein, the step that applies thermal stresses comprises makes the metalwork that coats oxide film cool down rapidly from the temperature that raises, thereby sets up thermograde between oxide film and metalwork.
20, according to the method for claim 19, wherein, the temperature of rising approximately is no more than 800 °F.
21, according to the method for claim 18, wherein, the step that applies thermal stresses comprises that the metalwork that will coat oxide film is heated to the temperature of rising, thereby sets up the step of thermograde between oxide film and metalwork.
22, according to the method for claim 21, wherein, the temperature of rising is about 800 °F.
23, according to the method for claim 21, wherein, thereby the step that applies thermal stresses comprises that also cooling off oxide film rapidly from the temperature that raises makes thermograde reverse further step rapidly.
24, a kind of from the get on method of oxide film dissolving of metalwork, this method may further comprise the steps:
Apply thermal stresses to the metalwork that coats oxide film, thereby setting up thermograde between oxide film and the metalwork with contacting directly between disruptive oxidation film and the metalwork;
Make metalwork by having the electrolyzer of 2 electrodes that are separated from each other, wherein metalwork forms an electrode in the electrolyzer; And
In electrolyzer, apply pulse direct current (DC) signal to an electrode and another electrode, when the quilt of the oxide compound on the metalwork is fully broken, pulse direct current (DC) signal flows to metalwork, make the metalwork electrode remain on the depassivation state and consequently do not produce any oxygen thereon, and make oxide film get loose so that can be easy to get on except that oxide compound from metalwork from metalwork.
25,, wherein, pulse direct current (DC) electricity is applied to the part that the steel wire that extends through electrolyzer is separated from each other according to the method for claim 24.
26,, comprise from metalwork and remove any residual oxide film to stay the step of the clean surface on the metalwork according to the method for claim 24.
27, according to the method for claim 26, wherein, after steel wire was drawn from electrolyzer, water flushing steel wire was to remove residual oxide.
28, according to the method for claim 26, wherein, remove residual oxide by the using ultrasound ripple.
29, according to the method for claim 26, wherein, by the application grinding particle residual oxide of making a return journey.
30, according to the method for claim 24, wherein, the step that applies thermal stresses comprises from the temperature that raises cools off the steel wire of coating oxide film rapidly to form the step of described thermograde.
31, according to the method for claim 30, wherein, the temperature of rising is lower than about 800 °F.
32, according to the method for claim 24, wherein, the step that applies thermal stresses comprises makes the oxide film coating layer be elevated to about 800 temperature to form the step of described thermograde from envrionment temperature.
33,, also comprise the heated steel wire of rapid cooling, with the further step of formation temperature gradient round-robin between oxide film and metalwork according to the method for claim 32.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US095,689 | 1993-07-21 | ||
| US08/095,689 US5407544A (en) | 1993-07-21 | 1993-07-21 | Method for removal of certain oxide films from metal surfaces |
| US08/266,673 US5464510A (en) | 1993-07-21 | 1994-06-28 | Method for removal of certain oxide films from metal surfaces |
| US266,673 | 1994-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1103114A true CN1103114A (en) | 1995-05-31 |
Family
ID=26790492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108006.4A Pending CN1103114A (en) | 1993-07-21 | 1994-07-21 | Method for removing certain oxide films from metal surfaces |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0668940A1 (en) |
| JP (1) | JPH08502322A (en) |
| CN (1) | CN1103114A (en) |
| AU (1) | AU7343394A (en) |
| CA (1) | CA2145167A1 (en) |
| IL (1) | IL110297A0 (en) |
| WO (1) | WO1995003439A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379900C (en) * | 2002-04-08 | 2008-04-09 | 西门子公司 | Apparatus and method for removing surface areas of components |
| CN103151544A (en) * | 2013-02-04 | 2013-06-12 | 武汉孚安特科技有限公司 | Activation method and device for activating primary lithium battery in pulse mode |
| CN103898525A (en) * | 2012-12-28 | 2014-07-02 | 周宜锦 | Method for removing rust on steel |
| CN104611759A (en) * | 2015-02-12 | 2015-05-13 | 广州市精源电子设备有限公司 | Polarity-variable pulse acid-pickling control method |
| CN109234789A (en) * | 2017-07-10 | 2019-01-18 | 三星显示有限公司 | For removing the wash mill of oxide and using its washing methods |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19604971A1 (en) * | 1996-02-02 | 1997-08-07 | Mannesmann Ag | Method and system for treating stainless steel strips |
| GB9607810D0 (en) * | 1996-04-15 | 1996-06-19 | Maysonic Ultrasonics Ltd | Removal of contaminants from steel surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1012626B (en) * | 1953-06-12 | 1957-07-25 | Rech S Et D Applic Pour L Ind | Process for producing easily removable layers of scale on the surfaces of iron and its alloys |
| DE1446001A1 (en) * | 1960-03-19 | 1969-05-08 | Herbert Kenmore | Method and device for the continuous electrolytic pickling of wire |
| US3338809A (en) * | 1966-06-23 | 1967-08-29 | United States Steel Corp | Method of cleaning ferrous metal strands electrolytically, including moving said strands in a horizontal plane through an electrolyte while under the influence of alternating electrical fields |
| US3546084A (en) * | 1969-05-19 | 1970-12-08 | Purex Corp Ltd | Cleaning method for jet engine parts |
| GB1338357A (en) * | 1972-07-21 | 1973-11-21 | Selas Corp Of America | Methods of descaling strip metal |
| LU71852A1 (en) * | 1975-02-14 | 1977-01-05 | ||
| SU529265A1 (en) * | 1975-03-10 | 1976-09-25 | Предприятие П/Я В-2058 | The way to clean the product |
| JPS6011511B2 (en) * | 1976-04-29 | 1985-03-26 | ソニー株式会社 | Recorded recording medium |
| JPS53116231A (en) * | 1977-03-22 | 1978-10-11 | Sumitomo Metal Ind Ltd | Direct electrolytic descaling method for steel wire |
| JPS56152998A (en) * | 1980-04-30 | 1981-11-26 | Hitachi Cable Ltd | Pretreatment of plated metallic wire body |
| JPS5778628A (en) * | 1980-10-31 | 1982-05-17 | Matsushita Electric Ind Co Ltd | Manufacture of magnetic recording medium |
| US4397451A (en) * | 1981-06-10 | 1983-08-09 | Chugai Ro Kogyo Co., Ltd. | Furnace for the heat treatment of scale-covered steel |
| US4795537A (en) * | 1987-04-10 | 1989-01-03 | H.P.G. Research Ltd. | Electrical conditioning system for electrodes in an electrolysis cell |
| JPH0670256B2 (en) * | 1987-12-26 | 1994-09-07 | 川崎製鉄株式会社 | Method for manufacturing low iron loss grain oriented silicon steel sheet in which characteristics are not deteriorated by strain relief annealing |
-
1994
- 1994-07-12 IL IL11029794A patent/IL110297A0/en unknown
- 1994-07-21 AU AU73433/94A patent/AU7343394A/en not_active Abandoned
- 1994-07-21 CN CN94108006.4A patent/CN1103114A/en active Pending
- 1994-07-21 JP JP7504832A patent/JPH08502322A/en active Pending
- 1994-07-21 WO PCT/CA1994/000400 patent/WO1995003439A1/en not_active Ceased
- 1994-07-21 EP EP94922206A patent/EP0668940A1/en not_active Withdrawn
- 1994-07-21 CA CA002145167A patent/CA2145167A1/en not_active Abandoned
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379900C (en) * | 2002-04-08 | 2008-04-09 | 西门子公司 | Apparatus and method for removing surface areas of components |
| CN103898525A (en) * | 2012-12-28 | 2014-07-02 | 周宜锦 | Method for removing rust on steel |
| CN103151544A (en) * | 2013-02-04 | 2013-06-12 | 武汉孚安特科技有限公司 | Activation method and device for activating primary lithium battery in pulse mode |
| CN103151544B (en) * | 2013-02-04 | 2016-04-20 | 武汉孚安特科技有限公司 | The Activiation method of pulse activation disposable lithium-battery and device thereof |
| CN104611759A (en) * | 2015-02-12 | 2015-05-13 | 广州市精源电子设备有限公司 | Polarity-variable pulse acid-pickling control method |
| CN109234789A (en) * | 2017-07-10 | 2019-01-18 | 三星显示有限公司 | For removing the wash mill of oxide and using its washing methods |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0668940A1 (en) | 1995-08-30 |
| IL110297A0 (en) | 1994-10-21 |
| WO1995003439A1 (en) | 1995-02-02 |
| AU7343394A (en) | 1995-02-20 |
| CA2145167A1 (en) | 1995-02-02 |
| JPH08502322A (en) | 1996-03-12 |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |