CN1451058A - Continuous electrolytic pickling method for metallic products using alternate current suplied cells - Google Patents
Continuous electrolytic pickling method for metallic products using alternate current suplied cells Download PDFInfo
- Publication number
- CN1451058A CN1451058A CN01815006A CN01815006A CN1451058A CN 1451058 A CN1451058 A CN 1451058A CN 01815006 A CN01815006 A CN 01815006A CN 01815006 A CN01815006 A CN 01815006A CN 1451058 A CN1451058 A CN 1451058A
- Authority
- CN
- China
- Prior art keywords
- electrolytic
- electrolytic pickling
- solution
- concentration
- electrode
- 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
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A continuous electrolytic pickling method for steel, nickel, super alloy, titanium and the alloy, is characterized in that the materials to be treated are immerged or crossed at least a electrolytic bath with electrolytic solution including neutral or acidulous aqueous solution for a time of 3-60 seconds, at the temperature of 20 DEG C - 95 DEG C, in which at least a pair of electrodes are connected with AC supply, the frequency of which is from 1Hz to 1000 Hz, the effective amplitude of current density when electrolysis is carried out is from 10 A/dm<2> to 250 A/dm<2>. Weight reduced process of AISI 409(X6CrTi12) steel to the application time in the embodiment of the inventive electrolytic pickling method is shown in drawing.
Description
The invention relates to a continuous electrolytic pickling process for metal products, in particular iron, nickel, titanium and alloys thereof, based on electrolytic cells using an alternating current power supply, using an acidic or neutral aqueous electrolyte.
As is known, pickling of e.g. stainless steel is to eliminate the hot oxide scale generated in the hot rolling and/or annealing process and to dissolve the underlying chromium-depleted alloy layer (dechroming layer). This conventional method comprises three conceptually distinct steps: the first step is descaling, i.e. physicochemical modification of the scale and partial descaling; the second step is the actual pickling, i.e. the removal and dissolution of the residual scale, and the treatment of the superficial underlayer of the dechromised alloy; the third step, called conditioning, is characterized by surface passivation. The last two steps are often performed simultaneously. In the prior art, various methods are known for carrying out the descaling step, depending on the type of scale present in the metal after metallurgical treatment.
For the scale produced during hot rolling and annealing, the scale removing step is performed by blasting with hard grit, in most cases, capable of breaking up and partially removing the scale.
For cold rolled products and annealed stainless steel and/or titanium, the descaling step cannot be done using surface peening, which is not compatible with the surface quality of the final product. Therefore, different methods are used which can cause significant modification of the oxide to accelerate the subsequent pickling process.
For this purpose, the following methods are very widely used:
a) thermochemically removing oxide scale, and features that the material to be pickled is immersed in molten oxidizing salt bath (400-600 deg.C) to change the oxide scale and increase the oxidation degree of the metal composing the oxide. In particular at temperatures of around 500 deg.CKolene cell (NaOH-NaNO)3NaCl ternary eutectic system) is most widely used;
b) the oxide scale is removed electrolytically using a neutral sulphate solution, partially modifying the oxide scale and the oxidation state of the component metals in the resulting solution.
For hot and cold rolled stainless steels and titanium, the pickling step is usually carried out using a highly oxidizing acid bath capable of dissolving the subsurface gold alloy (Cr-depleted stainless steel) leading to the detachment of the scale adhering thereto.
These baths contain mainly a mixture of mineral acids, among which the most widely used are:
1) a mixture of nitric acid and hydrofluoric acid, generally at a temperature between 60 ℃ and 75 ℃;
2) sulfuric acid, hydrofluoric acid, a mixture of hydrochloric acid and phosphoric acid, and adding a component having a high oxidizing power (sometimes used in a mixture), such as permanganate, persulfate, ferric chloride, ferric sulfate and hydrogen peroxide, at a temperature between 50 ℃ and 100 ℃;
3) hydrochloric acid or sulfuric acid added with corrosion inhibitor for pickling non-alloy steel at the temperature of between 50 and 85 ℃.
In some industrial plants, for all the above mixtures, in order to improve the kinetics of the pickling step, use is made of a mixture capable of providing a continuous current density to the material in the range 3A/dm2And 40A/dm2An electrolytic cell in between.
The purpose of the trimming step is to form a passivation protection film. If this step is not carried out simultaneously with the pickling step, it is generally carried out in a bath having a high redox potential. These baths contain low concentrations of oxidizing agents and the above-mentioned acids, as well as low amounts of ions of the metals and present in the metal products to be pickled.
Usually, between each tank, and necessarily at the end of the production line, a washing section is inserted comprising a water spraying system equipped with rotating brushes. These systems perform the function of removing the pickling solution dragged out by the strip and of removing the scale particles that are not adhering to the strip.
At present, methods are known for descaling and pickling steps for various stainless steels, titanium and their alloys, based on the use of nitric acid-free acid solutions. In particular, the following processes are known for pickling stainless steel and titanium and their alloys: the oxidizing power is provided by the presence of various components, among which iron ions, hydrogen peroxide and persulfuric acid, based on the use of an acid solution that does not contain nitric acid.
In particular, DE-A-19624436, W09826111, EP-A-763609 and JP95-130582 disclose pickling processes in nitric acid-free acid solutions in which iron ions are present, using an electrolytic cell of alternating current power supply (current density at 0.5A/dm)2And 250A/dm2In between). DE-C-3937438 discloses a process for the reoxidation of ferrous ions to ferric ions in hydrochloric acid solution using direct current.
EP-A-838542 discloses ｃA pickling process in aqueous sodium sulfate solution with ｃA concentration of between 10g/l and 350g/l, wherein ｃA steel strip is passed vertically between ｃA pair of counter electrodes, between which ｃA density of 20A/dm is applied2And 250A/dm2With direct current therebetween.
However, the known techniques, which are currently generally described, entail serious environmental and operational safety drawbacks, as well as drawbacks related to the management of the pickling process, both in terms of its control and in terms of its cost.
The main disadvantage of descaling by means of sand blasting or shot blasting machines is the difficulty in removing the silica and metal oxide particle dust, not to mention the severe noise pollution of the surrounding working area, for the descaling step.
Chemical descaling using molten salts proves particularly difficult to manage, due to the high temperatures in the bath (400-600 ℃), and to dispose of the descaling metal product cleaning solution after treatment. In fact, these cleaning solutions contain hexavalent chromium and nitrites and nitrates in non-negligible quantities.
The pickling and finishing steps using baths containing nitric acid cause related environmental problems, for different reasons. Among the various reasons, the most important are:
A. difficult removal of the metal-acid reactionOf severely contaminated NOx；
B. When treating waste liquid associated with high nitrate content, it is difficult to adapt to the existing environmental protection system.
The use of sulfuric or hydrofluoric acid baths, instead of nitric acid, with systems having a high redox potential, produces a complex management linked to the difficulty of maintaining the appropriate concentration of the reagents making it possible to guarantee the envisaged pickling kinetics.
In addition, the efficiency of the process is reduced by considering that a portion of the metal accumulated in the solution reacts with the oxidizing agent, which is costly in terms of reagents, such as stabilized hydrogen peroxide.
The present invention overcomes all of the above-mentioned deficiencies and further provides other advantages as will become apparent hereinafter.
In particular, the object of the present invention is to provide a pickling process for continuously cast products in steel that meets UNI EU 74/20 specifications, as well as for nickel alloys and titanium, based on electrolytic cells using an alternating current power supply in an acidic or neutral aqueous solution.
In practice, the object of the invention is a continuous electrolytic pickling process for steel, nickel superalloys, titanium and alloys thereof, characterized in that the material to be treated is immersed in or passed through at least one electrolytic cell with an electrolytic solution, neutral or acidic in water, at a temperature between 20 ℃ and 95 ℃ for a period of between 3 and 60 seconds, at least one pair of electrodes being connected to an alternating current source, the alternating current source having a frequency ofThe ratio ranges from 1Hz to 1000Hz, and the effective amplitude range of the current density when the electrolysis is carried out is from 10A/dm2And 250A/dm2。
In particular, the frequency of the alternating current may range from 40Hz to 70 Hz.
The electrolytic solution may be an aqueous solution, at a temperature between 20 ℃ and 95 ℃, comprising the following components in concentrations expressed in g/l:
sulfuric acid (H)2SO4) From 20 to 300, and optionally at least one of
Hydrofluoric acid (HF), from 5 to 50
Orthophosphoric acid (H)3PO4) From 5 to 200
Iron ion (Fe)+3) From 5 to 40.
In pickling stainless steel, the electrolytic solution is maintained at a temperature between 70 ℃ and 90 ℃ and contains sulfuric acid at a concentration between 150g/l and 250g/l and, optionally, iron ions (Fe) at a concentration between 5g/l and 40g/l+3)。
For nickel-based superalloys and titanium and its alloys, the electrolytic solution has a temperature between 70 ℃ and 90 ℃, contains sulfuric acid in a concentration between 150g/l and 250g/l, and at least one of hydrofluoric acid in a concentration between 5g/l and 50g/l and hydrochloric acid in a concentration between 5g/l and 50 g/l.
For carbon steel, the electrolytic solution contains sulfuric acid at a concentration between 150g/l and 250g/l at 70 ℃ to 90 ℃.
In another embodiment, the electrolyte solution may be sodium sulfate (Na) at a concentration ranging from 25g/l to 300g/l for any application2SO4) At a temperature between 50 ℃ and 95 ℃.
In an embodiment of the invention, the adjacent electrode pairs are connected to two separate power supplies such that a current line output from a first electrode pair facing one side of the material to be treated crosses the material and closes again at a second electrode pair opposite the first electrode pair facing the other side of the material to be treated, such that the current line is substantially in an X-shaped trajectory.
In another embodiment of the invention, the electrode facing the side of the material to be treated is connected to a power supply, so that the current line exiting from the electrode pair and crossing the material closes again at the other electrode, which is opposite the first electrode and faces the other side of the material to be treated, so that the current line forms a trajectory substantially perpendicular to this side.
The electrolytic pickling process according to the invention can be used to cause a physicochemical modification of the metal oxide scale present on the surface of the material to be pickled, which occurs for a treatment time of between 1 and 10sec for stainless steel.
The continuous electrolytic pickling process according to the invention can be used in a subsequent step which causes the physicochemical modification of the metal oxide scale present on the surface of the material to be pickled. For stainless steel, the treatment time required to apply the pickling process according to the invention is between 2sec and 15 sec.
The electrolytic cell used in the present invention may be a vertical electrode or a horizontal electrode electrolytic cell, and the former is preferably used because it is easy to remove gas generated by electrochemical reaction when forming a circuit.
The electrodes are made of a material that is resistant to the corrosive action of the bath used.
The electrodes of the individual cells can be connected in at least three ways, as illustrated by way of non-limiting example in figures 2, 3 and 4.
If opposing electrodes are connected to the same terminal, the electrodes may form a single toroidal coil (toroid ring).
Another object of the invention is the electrolytic cells characterised in that they have the electrode connections as described hereinafter and as claimed in claims 8 and 9.
Among the most important advantages of the use of the invention, the following may be mentioned:
providing a descaling system that can replace the currently used techniques, minimizing the problems related to pollution and operational safety;
-providing a pickling and conditioning system, after descaling by the currently used techniques, capable of eliminating NO with solutions not containing nitric acidxRelease-related environmental deficiencies;
providing a pickling and conditioning system that eliminates the need to use materials with high redox potentials to provide the required oxidizing power to the solution, such as iron ions and peroxides, and solves problems associated with in-tank reagent control, and associated costs;
-providing a pickling process that is capable of recombining descaling, pickling and finishing steps into a single stage, so that the entire pickling process is performed in a single treatment system;
to provide a pickling process that allows a significant reduction in time and thus in the cost of the treatment.
The positive effects of using the continuous pickling process according to the invention can be illustrated as follows: the AC current causes an overvoltage of the free corrosion potential at the surface of the alloy to be pickled, in order to reach an electrochemical potential on the surface capable of accelerating a plurality of oxidation-reduction reactions involving the alloy and the oxide layer thereon, and also involving the aqueous solution.
Furthermore, a change in the oxidation state of the metals present in the solution of surface oxides (in particular, chromium in stainless steel) and underlying metals occurs. In addition, electrolysis of water is also performed, and hydrogen and oxygen are generated in large quantities.
These reactions, in order of increasing standard potential of the respective redox pairs, are:
oxidation of constituent metals in steel or titanium and alloys thereof, or nickel and alloys thereof
Involving reactions of the hot oxidation skin of the alloy to be pickled
In an acidic solution, the electrolytic reaction of water,
in neutral solution
The chromium constituting the oxide scale is oxidized to produce chromate (hexavalent Cr), which enhances the solution kinetics of the alloy and promotes the oxidation of ferrous ions to ferric ions, by the reaction
The dissolved iron, generated as ferrous ions from the dissolution of the steel, accelerates the reduction of all Cr (VI) to Cr (III) according to the above reaction, leaving the solution free of Cr (VI).
For stainless steel, the presence of the redox couple iron and ferrous ions (E ° -771 mV/SHE) in the solution increases the oxidizing capacity of the bath, providing the bath with the ability to passivate.
The voltage-current difference obtained by electrode impedance spectroscopy (electro impedance spectroscopy) is such that the frequency is between 40Hz and 70Hz, more than 90% of the current across the cell is in phase with the applied voltage (the significant part of the current) and is capable of carrying out the electrochemical reaction described above. Only 10% of the current deviates by 90 ° from the voltage used (the reactive part of the current), which is caused by the charging, discharging of the pseudo-capacitor formed by the electric double layer at the electrode surface. As the frequency increases, the active portion tends to decrease relative to the passive portion, resulting in a decrease in the current required to accelerate the electrochemical reaction for pickling.
The alternation of the hydrogen production reaction, which occurs during cathodic polarization, and the oxygen production reaction, which occurs during anodic polarization, exacerbates the descaling effect, causing rapid detachment of the oxide layer from the substrate.
The solution kinetics of the alloy to be pickled are fast, in particular, considering that the oxides are not subjected to any pre-treatment and conditioning before the electrolytic treatment in the electrolytic cell.
So far, only a general description of the present invention has been given. The drawings and examples are for explanation and not for limitation, and with the aid of them, a more detailed description of specific embodiments will be provided later for purposes of better understanding the objects, features, advantages and modes of operation.
FIG. 1 shows a signal at 200g/l H2SO4In an aqueous solution of (2) to X6CrTi12(AISI 409) Process of weight reduction in g/m with respect to time in the entire pickling treatment of Cold-rolled annealed steels2Is a unit.
Fig. 2 shows a first electrode configuration in which the electrodes 1 are positioned on the same side of the steel strip N and are connected alternately to the two terminals of a phase of the transformer. By this arrangement the electrodes 2 on the opposite side of the strip can be connected to the same terminals of one phase of the transformer which connects them to the corresponding terminals on the other side.
Figure 3 shows a second configuration in which the electrodes 1 are located on the same side of the strip N and are connected to the same terminal of one or more phases of one or more transformers; the opposite electrode 2 is connected to the other terminal of the corresponding phase of the transformer.
Fig. 4 shows a third configuration in which two adjacent opposite electrodes are connected to the two terminals of two independent single-phase transformers, so that the current loops of each single-phase transformer cross inside the strip N, forming an X-shaped trajectory.
Example 1
Pickling of Cold rolled annealed AISI409 LI Steel strip (coil)
The steel strip to be pickled is characterized in that:
| bandwidth of | 1270mm |
| Thickness of belt | 1.5mm |
| Coil weight | 18900kg |
| Length of the roll | 956mm |
Acid pickling solution:
| H2SO4concentration of | 200g/l |
| Temperature of the solution | 60℃±5℃ |
The current was applied using the electrode structure shown in fig. 2. The gap between the electrodes was 80 mm. At the outlet of the electrolytic cell, a brush is inserted and provided withFollowed by a series of wringing rollers. The ratio of the solution in the holding tank to the surface of the immersed steel strip is not less than 1m3Solution/m3A steel strip. The solution is refreshed when the required limits for dissolving the metal are reached.
The loss of steel strip which has not been pickled as a result of the current being closed again between the two poles is assessed to be<8%, and a current density of 60A/dm is set2。
The treatment time, i.e. the time period during which the material is subjected to the alternating current, is set to 15sec, depending on the treatment time and the steel strip velocity and the electrode dimensions.
The weight reduction obtained after the treatment is approximately equal to 40g/m2The steel strip of (1).
Figure 1 shows a graph of the weight reduction of steel as a function of treatment time for the examples, using two different current densities.
Example 2
Pickling of Cold rolled annealed AISI 430 Steel strip (coil) according to the invention
The steel strip to be pickled is characterized in that:
| bandwidth of | 1270mm |
| Thickness of belt | 1.0mm |
| Coil weight | 18900kg |
| Length of the roll | 1907mm |
Acid pickling solution:
| H2SO4concentration of | 250g/l |
| Temperature of the solution | 60℃±5℃ |
The current was applied using the electrode structure shown in fig. 2. The gap between the electrodes is equal to 80 mm. In the electricityAt the outlet of the cell, a water-jet system equipped with brushes is inserted, followed by a series of wringing rollers. The ratio of the solution in the holding tank to the surface of the immersed steel strip is not less than 1m3Solution/m2A steel strip. The solution is refreshed when the required limits for dissolving the metal are reached.
The loss of steel strip which was not subjected to pickling due to the reclosing of the current between the two poles was evaluated as<8%, and a current density of 75A/dm was set2。
The treatment time, i.e. the time period during which the material is subjected to the alternating current, is set between 5sec and 25 sec. The treatment time is related to the strip speed and the electrode size.
The weight reduction obtained after the treatment was about 40g/m2The steel strip of (1).
Claims (16)
1. A continuous electrolytic pickling process for steel, nickel superalloys, titanium and alloys thereof, characterized in that the material to be treated is immersed in or passed through at least one electrolytic cell containing an electrolytic solution, neutral or acidic in aqueous solution, at a temperature between 20 ℃ and 95 ℃ for a period of time between 3 and 60 seconds, said electrolytic cell having at least one pair of electrodes connected to an alternating current source, the alternating current source having a frequency ranging from 1Hz to 1000Hz, the electrolysis being carried out with an effective amplitude of the current density ranging from 10A/dm2And 250A/dm2。
2. The electrolytic pickling method according to claim 1, wherein the frequency of the alternating current ranges from 40Hz to 70 Hz.
3. Electrolytic pickling process according to claim 1 or 2, wherein the electrolytic solution is anaqueous solution, at a temperature comprised between 20 ℃ and 95 ℃, containing the following constituents in concentrations expressed in g/l:
sulfuric acid (H)2SO4) From 20 to 300, and optionally at least one of:
hydrofluoric acid (HF) from 5 to 50
Orthophosphoric acid (H)3PO4) From 5 to 200
Iron ion (Fe)+3) From 5 to 40.
4. The electrolytic pickling method for stainless steel according to any one of claims 1 to 3, wherein the electrolytic solution is maintained at a temperature between 70 ℃ and 90 ℃, contains sulfuric acid at a concentration between 150g/l and 250g/l, and, optionally, contains iron ions (Fe) at a concentration between 5g/l and 40g/l+3)。
5. The electrolytic pickling process for nickel-based superalloys and titanium and its alloys according to claims 1 to 3, wherein the electrolytic solution is maintained at a temperature between 70 ℃ and 90 ℃, contains sulfuric acid at a concentration between 150g/l and 250g/l, and at least one of hydrofluoric acid at a concentration between 5g/l and 50g/l and hydrochloric acid at a concentration between 5g/l and 50 g/l.
6. A process for electrolytic pickling of carbon steel according to any one of claims 1 to 3, the electrolytic solution being maintained at a temperature of 70 ℃ to 90 ℃, comprising sulfuric acid at a concentration between 150g/l and 250 g/l.
7. The electrolytic pickling method according to claim 1 or 2, wherein the electrolytic solution is sodium sulfate (Na) having a concentration ranging from 25g/l to 300g/l2SO4) The neutral aqueous solution of (A) is at 50 deg.CAnd 95 ℃.
8. The electrolytic pickling method according to any one of claims 1 to 7, wherein adjacent pairs of electrodes are connected to two independent power sources so that a current line output from a first pair of electrodes facing one side of the material to be treated crosses the material and is closed again at a second pair of electrodes facing the other side of the material to be treated, the second pair of electrodes being opposite to the first pair of electrodes and making the current line substantially in a locus of X-type.
9. The electrolytic pickling method according to any one of claims 1 to 7, wherein an electrode facing one side of the material to be treated is connected to a power source so that a current line that is outputted from the electrode and crosses the material is closed at the other electrode, the other electrode being opposite to the first electrode and facing the other side of the material to be treated so that the current line forms a trajectory substantially perpendicular to the one side of the material to be treated.
10. Use of the electrolytic pickling process according to claims 1 to 9 for causing a physicochemical modification of the metal oxide scale present on the surface of the material to be pickled.
11. Use of the electrolytic pickling process according to claim 10 for treating stainless steel for a treatment time between 1 and 10 sec.
12. Use of an electrolytic pickling process according to claims 1 to 9, wherein the process is used in a subsequent step causing a physicochemical modification of the metal oxide scale present on the surface of the material to be pickled.
13. Use of the electrolytic pickling process according to claim 12, applied to stainless steel in a subsequent step as a physicochemical modification causing the presence of metal oxide scales on the surface of the material to be pickled, with a treatment time of between 2 and 15 sec.
14. Use of the pickling process according to claims 1 to 13 in combination with other conventional pickling systems.
15. Electrolytic cells, characterized in that they have the electrode connections indicated in claims 8 and 9.
16. A continuous electrolytic pickling process and its use, and an electrolytic cell according to the present disclosure, examples and claims.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITPM2000A000456 | 2000-08-10 | ||
| IT2000RM000456A IT1317896B1 (en) | 2000-08-10 | 2000-08-10 | CONTINUOUS ELECTROLYTIC PICKLING METHOD OF METAL PRODUCTS CONCELLS POWERED BY ALTERNATING CURRENT. |
| PCT/IT2001/000435 WO2002012596A2 (en) | 2000-08-10 | 2001-08-06 | Continuous electrolytic pickling method for metallic products using alternate current supplied cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1451058A true CN1451058A (en) | 2003-10-22 |
| CN1318652C CN1318652C (en) | 2007-05-30 |
Family
ID=11454885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018150063A Expired - Lifetime CN1318652C (en) | 2000-08-10 | 2001-08-06 | Continuous electrolytic pickling method for metallic products using alternate current suplied cells |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20040031696A1 (en) |
| EP (1) | EP1307609B1 (en) |
| CN (1) | CN1318652C (en) |
| AT (1) | ATE262057T1 (en) |
| AU (1) | AU2001282513A1 (en) |
| DE (1) | DE60102387T2 (en) |
| ES (1) | ES2220795T3 (en) |
| IT (1) | IT1317896B1 (en) |
| WO (1) | WO2002012596A2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260899A (en) * | 2010-05-25 | 2011-11-30 | 宝山钢铁股份有限公司 | Method for removing scale on surface of titanium/titanium alloy strip |
| CN103014824A (en) * | 2011-09-21 | 2013-04-03 | 李文志 | Low carbon type alternating current electrochemical degreasing process method |
| CN103492593A (en) * | 2010-12-30 | 2014-01-01 | 劳斯莱斯公司 | System and method for scale removal from a nickel-based superalloy component |
| CN105143523A (en) * | 2013-03-29 | 2015-12-09 | 特诺恩股份公司 | Method for treating in continuous the surface of a laminate made of stainless steel in a solution based on sulfuric acid |
| JP2019119908A (en) * | 2017-12-28 | 2019-07-22 | 株式会社日本科学エンジニアリング | Electrolytic polishing liquid for stainless steel |
| CN110512217A (en) * | 2019-09-23 | 2019-11-29 | 中冶南方工程技术有限公司 | A kind of 201 austenitic stainless steel of cold rolling is without nitric acid acidwashing technique |
| CN110528009A (en) * | 2019-09-23 | 2019-12-03 | 中冶南方工程技术有限公司 | A kind of 304 austenitic stainless steel of cold rolling is without nitric acid acidwashing technique |
| CN110592600A (en) * | 2019-09-23 | 2019-12-20 | 中冶南方工程技术有限公司 | Nitric acid-free pickling process for cold-rolled 430 ferrite stainless steel |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10160318A1 (en) * | 2001-12-07 | 2003-06-18 | Henkel Kgaa | Process for pickling martensitic or ferritic stainless steel |
| DE102008057151A1 (en) * | 2008-11-13 | 2010-05-27 | Henkel Ag & Co. Kgaa | Process for producing an electrolytically galvanized high strength steel sheet |
| JP6144006B2 (en) * | 2011-01-17 | 2017-06-07 | Ｊｆｅスチール株式会社 | Method for producing stainless steel for fuel cell separator, stainless steel for fuel cell separator, fuel cell separator, and fuel cell |
| ITMI20130494A1 (en) | 2013-03-29 | 2014-09-30 | Tenova Spa | METHOD OF TREATING CONTINUOUSLY THE SURFACE OF A STAINLESS STEEL LAMINATE IN A CHLORIDRID ACID-BASED SOLUTION |
| DE102015202963A1 (en) * | 2015-02-18 | 2016-08-18 | Ulrich Schekulin | Method and device for chemically removing material by opening edge structuring |
| CN107525061A (en) * | 2017-08-23 | 2017-12-29 | 大唐东北电力试验研究所有限公司 | A kind of power plant boiler boiler tube dirt, which measures, determines system and method |
| CN107525062A (en) * | 2017-08-23 | 2017-12-29 | 大唐东北电力试验研究所有限公司 | A kind of thermal power plant's superheater tube sample dirt, which measures, determines system and method |
| KR102286367B1 (en) * | 2019-11-11 | 2021-08-05 | 주식회사 포스코 | Manufacturing method of stainless steel for polymer fuel cell seperator |
| CN111621840A (en) * | 2020-05-26 | 2020-09-04 | 大连理工大学 | Bipolar electrochemical removal method for iron pollution on surface of titanium alloy |
| KR102497442B1 (en) * | 2020-11-25 | 2023-02-08 | 주식회사 포스코 | Austenitic stainless steel for polymer fuel cell separator with improved contact resistance and manufacturing method thereof |
| CN113788520A (en) * | 2021-10-08 | 2021-12-14 | 北京首钢吉泰安新材料有限公司 | Iron-chromium-aluminum pickling process, wastewater treatment method and wastewater treatment device |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE19773E (en) * | 1935-12-03 | Euectrocleanuxg process | ||
| US2115005A (en) * | 1936-10-15 | 1938-04-26 | Samuel J Blaut | Electrochemical treatment of metal |
| US2408424A (en) * | 1940-06-15 | 1946-10-01 | Monsanto Chemicals | Pickling steels |
| US4214961A (en) * | 1979-03-01 | 1980-07-29 | Swiss Aluminium Ltd. | Method and apparatus for continuous electrochemical treatment of a metal web |
| GB8517606D0 (en) * | 1985-07-12 | 1985-08-21 | Bekaert Sa Nv | Cleaning by electrochemical pickling |
| US4813395A (en) * | 1987-04-27 | 1989-03-21 | Allied Corporation | Two-cycle engine and method of operation |
| SU1723209A1 (en) * | 1988-11-30 | 1992-03-30 | Уральский научно-исследовательский институт трубной промышленности | Method for electrochemical pickling of steel articles |
| JPH0726240B2 (en) * | 1989-10-27 | 1995-03-22 | ペルメレック電極株式会社 | Electrolytic pickling or electrolytic degreasing method for steel sheet |
| AT399167B (en) * | 1991-06-10 | 1995-03-27 | Andritz Patentverwaltung | METHOD AND DEVICE FOR ELECTROLYTICALLY STICKING CONTINUOUSLY CONTINUOUS ELECTRICALLY CONDUCTIVE GOODS |
| SE501561C2 (en) * | 1993-05-09 | 1995-03-13 | Swedish Pickling Ab | Method and apparatus for machining stainless steel wherein the current is passed through the steel strip in its thickness direction |
| AT401183B (en) * | 1995-02-15 | 1996-07-25 | Andritz Patentverwaltung | METHOD FOR REGENERATING ELECTROLYTES, ESPECIALLY NA2SO4 FROM STAINLESS STEEL, IN PARTICULAR STAINLESS STEEL TAPES |
| IT1276955B1 (en) * | 1995-10-18 | 1997-11-03 | Novamax Itb S R L | PICKLING AND PASSIVATION PROCESS OF STAINLESS STEEL WITHOUT THE USE OF NITRIC ACID |
| IT1302202B1 (en) * | 1998-09-11 | 2000-07-31 | Henkel Kgaa | ELECTROLYTIC PICKLING PROCESS WITH SOLUTIONS FREE FROM ACIDONITRICO. |
| GB2358194B (en) * | 2000-01-17 | 2004-07-21 | Ea Tech Ltd | Electrolytic treatment |
-
2000
- 2000-08-10 IT IT2000RM000456A patent/IT1317896B1/en active
-
2001
- 2001-08-06 AU AU2001282513A patent/AU2001282513A1/en not_active Abandoned
- 2001-08-06 AT AT01961136T patent/ATE262057T1/en not_active IP Right Cessation
- 2001-08-06 CN CNB018150063A patent/CN1318652C/en not_active Expired - Lifetime
- 2001-08-06 US US10/344,254 patent/US20040031696A1/en not_active Abandoned
- 2001-08-06 WO PCT/IT2001/000435 patent/WO2002012596A2/en active IP Right Grant
- 2001-08-06 EP EP01961136A patent/EP1307609B1/en not_active Expired - Lifetime
- 2001-08-06 DE DE60102387T patent/DE60102387T2/en not_active Expired - Lifetime
- 2001-08-06 ES ES01961136T patent/ES2220795T3/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260899A (en) * | 2010-05-25 | 2011-11-30 | 宝山钢铁股份有限公司 | Method for removing scale on surface of titanium/titanium alloy strip |
| CN102260899B (en) * | 2010-05-25 | 2013-04-03 | 宝山钢铁股份有限公司 | Method for removing scale on surface of titanium/titanium alloy strip |
| CN103492593A (en) * | 2010-12-30 | 2014-01-01 | 劳斯莱斯公司 | System and method for scale removal from a nickel-based superalloy component |
| CN103014824A (en) * | 2011-09-21 | 2013-04-03 | 李文志 | Low carbon type alternating current electrochemical degreasing process method |
| CN105143523A (en) * | 2013-03-29 | 2015-12-09 | 特诺恩股份公司 | Method for treating in continuous the surface of a laminate made of stainless steel in a solution based on sulfuric acid |
| CN105143523B (en) * | 2013-03-29 | 2018-06-19 | 特诺恩股份公司 | The method on the surface of laminate made of continuous processing stainless steel in the solution based on sulfuric acid |
| JP2019119908A (en) * | 2017-12-28 | 2019-07-22 | 株式会社日本科学エンジニアリング | Electrolytic polishing liquid for stainless steel |
| JP7177425B2 (en) | 2017-12-28 | 2022-11-24 | 株式会社日本科学エンジニアリング | Electropolishing liquid for stainless steel |
| CN110512217A (en) * | 2019-09-23 | 2019-11-29 | 中冶南方工程技术有限公司 | A kind of 201 austenitic stainless steel of cold rolling is without nitric acid acidwashing technique |
| CN110528009A (en) * | 2019-09-23 | 2019-12-03 | 中冶南方工程技术有限公司 | A kind of 304 austenitic stainless steel of cold rolling is without nitric acid acidwashing technique |
| CN110592600A (en) * | 2019-09-23 | 2019-12-20 | 中冶南方工程技术有限公司 | Nitric acid-free pickling process for cold-rolled 430 ferrite stainless steel |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002012596A9 (en) | 2002-11-28 |
| ITRM20000456A1 (en) | 2002-02-10 |
| CN1318652C (en) | 2007-05-30 |
| ATE262057T1 (en) | 2004-04-15 |
| ITRM20000456A0 (en) | 2000-08-10 |
| EP1307609A2 (en) | 2003-05-07 |
| US20040031696A1 (en) | 2004-02-19 |
| DE60102387T2 (en) | 2005-03-24 |
| IT1317896B1 (en) | 2003-07-15 |
| DE60102387D1 (en) | 2004-04-22 |
| ES2220795T3 (en) | 2004-12-16 |
| AU2001282513A1 (en) | 2002-02-18 |
| EP1307609B1 (en) | 2004-03-17 |
| WO2002012596A2 (en) | 2002-02-14 |
| WO2002012596A3 (en) | 2002-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1451058A (en) | Continuous electrolytic pickling method for metallic products using alternate current suplied cells | |
| JP2014501337A (en) | Eco-friendly high-speed pickling process for producing low chromium ferritic stainless steel cold rolled steel sheets with excellent surface quality | |
| JP5897717B2 (en) | Pickling of stainless steel in an oxidative electrolytic acid bath | |
| EP1115917B1 (en) | Process for electrolytic pickling using nitric acid-free solutions | |
| JP2984736B2 (en) | Electrolytic acid cleaning method and apparatus | |
| CA2573988A1 (en) | Method and device for pickling metals | |
| JP2009504905A (en) | Electropolishing method | |
| JPH04362183A (en) | Method for regenerating aluminum surface cleaning bath | |
| JP3792335B2 (en) | Finishing electrolytic pickling method in descaling of stainless steel strip | |
| JP2577619B2 (en) | Method and apparatus for descaling alloy steel strip | |
| EP4056737A1 (en) | Ionic liquid for pickling stainless steel and method for pickling stainless steel by using same | |
| JP3300673B2 (en) | Method and apparatus for quickly forming a phosphate coating on steel wire | |
| JP2517353B2 (en) | Descaling method for stainless steel strip | |
| JPH05306497A (en) | Phophatizing chemical conversion treatment | |
| JP2577618B2 (en) | Method and apparatus for descaling alloy steel strip | |
| JPH0713320B2 (en) | Electrolytic pickling method for strips of special steel | |
| JP7454045B2 (en) | Electrically assisted pickling of steel | |
| WO2022091049A1 (en) | Novel process for descaling or pickling of steels and stainless steels | |
| JPH0726233B2 (en) | Cladded steel sheet and its continuous manufacturing method and apparatus | |
| JPH03243799A (en) | High-speed electrolytically dissolving method for steel-based metal | |
| JPH02173300A (en) | Method for electrolytically descaling cold rolled stainless steel strip with neutral salt | |
| JPH10110299A (en) | Method for electrolytically descaling steel strip | |
| JPH07252699A (en) | Removal of lead dioxide residue | |
| JPH0368799A (en) | Descaling method for cold rolled stainless steel strip |
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 | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070530 |
|
| CX01 | Expiry of patent term |