CN100999826A - Electrolyting purifying process for enhancing corrosion resisting proferty of continuous annealing IF steel cold rolling plate - Google Patents
Electrolyting purifying process for enhancing corrosion resisting proferty of continuous annealing IF steel cold rolling plate Download PDFInfo
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- CN100999826A CN100999826A CN 200610023166 CN200610023166A CN100999826A CN 100999826 A CN100999826 A CN 100999826A CN 200610023166 CN200610023166 CN 200610023166 CN 200610023166 A CN200610023166 A CN 200610023166A CN 100999826 A CN100999826 A CN 100999826A
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- 238000000137 annealing Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 20
- 238000005260 corrosion Methods 0.000 title claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 title claims description 33
- 239000010959 steel Substances 0.000 title claims description 33
- 238000005097 cold rolling Methods 0.000 title 1
- 230000002708 enhancing effect Effects 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 amine benzoate Chemical class 0.000 claims abstract description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 4
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 4
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000001978 electrochemical passivation Methods 0.000 claims description 12
- 238000002161 passivation Methods 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 claims 1
- 239000010960 cold rolled steel Substances 0.000 abstract description 4
- 230000000415 inactivating effect Effects 0.000 abstract 2
- 238000010791 quenching Methods 0.000 abstract 2
- 230000000171 quenching effect Effects 0.000 abstract 2
- 230000002779 inactivation Effects 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 238000006388 chemical passivation reaction Methods 0.000 description 12
- 238000005554 pickling Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 241000221535 Pucciniales Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The electrolytic inactivation process for raising the anticorrosion of continuously annealed IF cold rolled steel plate is completed in a cold rolled plate continuously annealing production line. The present invention features that two pairs of electrodes are set inside the quenching tank and current in the strength of 0.5-5 A/sq dm is applied; and inactivating solution containing corrosion inhibitor in 1-5 wt% concentration and pH 8-12 is filled into the quenching tank and maintained at 50-70 deg.c. The inactivating solution contains amine benzoate 20-30 wt%, sodium benzoate 20-30 wt%, urotropine 30-40 wt%, monoethanol amine 10-20 wt%, and water as solvent for the rest. The present invention can raise the anticorrosion performance of continuously annealed IF cold rolled steel plate easily and effectively.
Description
Technical field
The present invention relates to the antirust technology of the cold-rolled steel sheet of continuous annealing production, a kind of online electrolytic passivation method to steel plate.
Background technology cold-reduced sheet surface is not because there is the protection of coating or coating; under hot and humid weather condition, be easy to corrosion; especially the IF steel cold-reduced sheet of continuous annealing is because the annealing process of high temperature low speed; easy oxidation element such as a spot of Mn, Si forms granular oxide compound and ferroelectric oxide film formation corrosion microbattery in the substrate on its surface, has quickened the corrosion rate of IF steel cold-reduced sheet.IF steel cold-reduced sheet is in storage, transportation and user's use, and when atmospheric moisture surpasses 65%, its surface is easy to occur the phenomenon of corrosion, has directly influenced the normal use of material and has increased user's processing cost.Therefore, how to suppress, remove or cover Mn, the Si enriched layer on cold-reduced sheet surface, just become the gordian technique of improving annealing IF steel cold-reduced sheet easy-to-rust.
At present, it is antirust to adopt the oiled method to carry out usually before batching after the annealing of annealing IF steel cold-reduced sheet, finished product volume oiling 1000～1500mg/m
2, middle volume oiling 500～800mg/m
2Played certain effect; but have following limitation: the one, antirust timeliness is short: corrosion protection is carried out in oiling can only be in tens hours effectively; and because of the slushing oil skewness on cold-reduced sheet surface; especially through behind long-distance transport, the user Kai Bao, be difficult to play effective rust inhibition.The 2nd, pollution problem: must carry out cleaning by degreasing before use to the oiled cold-reduced sheet and handle, increase use cost, and brought pollution problem.
The bismuthate treatment technology before the cold-reduced sheet annealing has been studied by Kawasaki, Japan iron making technology institute (CAMP-ISIJ 82-S449), suppresses the enrichment of Mn, Si in the IF steel annealing process by formation bismuthate film, thereby improves its solidity to corrosion.But this method has two deficiencies: the one, and bismuthate belongs to muddy type solution, and bottom, preparation back is easy to crystallization, and the actual difficulty of using is bigger.The 2nd, must connect existing cold-reduced sheet and move back facility transformation, promptly before annealing, increase the chemical treatment technology section.
The continuous annealing process of Belgium's Cockerill discovery " HOWAQ " can be eliminated Mn, the Si enriched layer that IF steel cold-reduced sheet forms in the annealing process section, thereby significantly improves its solidity to corrosion.This technology is to take a series of chemical treatments such as water-cooled, pickling, rinsing after annealing.Other has " Nippon Steel " also to increase the processing of flash nickel after the continuous annealing pickling.Japanese Patent JP 56112420 A also propose the technology that neutralizing treatment is carried out in first pickling again.But these methods have following two limitation:
1, the technology more complicated of pickling and aftertreatment thereof, cost is very high.
2, the process section of pickling and aftertreatment thereof is very long, and existing continuous annealing production line does not have enough spaces to transform usually.
Above-mentioned all, all Mn, the Si enriched layer on explanation inhibition or removal cold-reduced sheet surface are expensive technology, and must compare big transformation to existing continuous annealing production line.
Summary of the invention
The purpose of this invention is to provide the corrosion proof electrolytic passivation method of a kind of raising annealing IF steel cold-reduced sheet, needn't transform continuous annealing production line, pollution-free, improve the solidity to corrosion of cold-reduced sheet at low cost.
The corrosion proof electrolytic passivation method of this raising annealing IF steel cold-reduced sheet, utilize the cold-reduced sheet production line facility of continuous annealing, be the passivating solution that contains inhibiter in the hardening groove of the cold-reduced sheet process after it is characterized in that annealing, concentration 1～5%, PH 8～12, inhibiter by the solute weight percent in the passivating solution is: phenylformic acid amine 20--30%, Sodium Benzoate 20--30%, urotropine 30-40%, monoethanolamine 10-20%, and solvent is a water; When 50～70 ℃ of the passivating solution temperature in the maintenance hardening groove, the IF steel cold-reduced sheet of normarzing annealing come out afterwards to pass through the hardening groove with 200m/min from annealing furnace.
Electrolytic passivation method of the present invention does not need equipment is carried out any transformation, just can implement on existing continuous annealing production line.Change the water in the hardening groove into passivating solution, and in the hardening groove, add the electrode of two pairs of homopolarities of respectively doing for oneself, allow the cold-rolled steel sheet that comes out from annealing furnace, in passivating solution, produce twice electrolytic reaction, promote that the chemical passivation reaction of surface of steel plate is more abundant as antipole; Through extracting and the stoving process section on original production line, its surperficial complete drying forms protective layer later on the cold-reduced sheet behind the post-passivation.
The described electrolytic passivation method of this patent should have following characteristic:
1, electrolytic passivation is directly finished on existing continuous annealing production line, and cost is very low.
2, the preparation of electrolytic passivation solution is easy, and supporting electrode is provided with facility, and is workable.
3, obviously improve its corrosion resistance nature behind the cold-reduced sheet electrolytic passivation.
4, the passive film on cold-reduced sheet surface does not change the original condition of surface of matrix.
5, the passive film on cold-reduced sheet surface does not influence the phosphatization of user's later process
Estimate feasibility and prospect that invention is applied: nearly 16 of present domestic continuous annealing production line, about 6,400,000 tons of output, then more what build and plan to build, and the easy-to-rust of the cold-reduced sheet that continuous annealing is produced is the realistic problem that steel mill and final user directly face.The present invention can directly improve the solidity to corrosion of the cold-reduced sheet of continuous annealing production, have easy, effective characteristics, and do not need existing production line is made any change, do not influence the use of user's later process, obtain widespread use on the continuous annealing line at home.
Description of drawings
Accompanying drawing 1 is to implement synoptic diagram in the production of present method after 1550 continuous annealing cold-reduced sheets are come out of the stove;
Accompanying drawing 2.1 is microscopic appearance contrasts of the cold-reduced sheet and the cold-reduced sheet phosphatize phosphate coat after Fig. 2 .2 chemical passivation of unpassivated;
Embodiment
The implementation step of the online chemical passivation rust-proofing method of the cold-reduced sheet produced of 1 explanation continuous annealing in conjunction with the accompanying drawings:
Step 1: select the inhibiter raw material, press weight percentages:
Phenylformic acid amine 20--30%, Sodium Benzoate 20--30%, urotropine 30-40%, monoethanolamine 10-20%:
Step 2: above-mentioned inhibiter is joined in the hardening groove after continuous annealing production line is come out of the stove,, become the passivating solution of concentration 1～5% after the dissolving, add in the hardening groove after 1550 continuous annealing cold-reduced sheets are come out of the stove with 2% concentration in this example with the water dissolution in the groove.
Step 3: use a small amount of yellow soda ash or trolamine, the PH that regulates passivating solution reaches 8～12, or 9～10 scope.
Step 4: the passivating solution in the hardening groove is heated to 50～70 ℃, and in operation process, the passivating solution temperature in the hardening groove is remained in this scope.Passivating solution in this example is heated to 60 ℃.
Step 5: as shown in Figure 1, liquid level is divided into electrode in the hardening groove, and first counter electrode is arranged on the steel plate approaching side, and second counter electrode is arranged on steel plate and walks out side, and the polarity of two counter electrode is opposite, the homopolarity of respectively doing for oneself.The about 1m of area of the every cube electrode that in the hardening groove of 1550 rolling mill production lines, is provided with
2
Step 6: as shown in Figure 1, the 1st counter electrode is set at anode (steel plate is a negative electrode), the 2nd counter electrode is set at negative electrode (steel plate is an anode), applies 0.5～5A/dm
2Electric current.
Step 7: temperature was about 120 ℃ after the IF steel cold-reduced sheet of normarzing annealing came out from annealing furnace, when passing through 60 ℃ of passivating solutions of hardening groove with the speed of 200 meters of per minutes, under electrolytic effect, made surface of steel plate produce passivation.
Step 8: with the cold-reduced sheet behind the post-passivation through 5.4 meters on original production line extract operation, 7.3 meters drying channel (100 ℃), its surperficial complete drying forms chemical coating later on.
Step 9: last, the cold-reduced sheet after electrolysis, the chemical passivation through smooth, the oiling on original production line, batch, the finished product volume.
The service check of the IF steel cold-reduced sheet after present method is handled:
1, wet-hot aging performance
Wet-hot aging performance after the chemical passivation of IF steel cold-reduced sheet (49 ℃, RH＞95%)＞48 hours.
The cold-reduced sheet of cold-reduced sheet after the chemical passivation and unpassivated is carried out humid heat test, red rust promptly appearred in 12 hours in the cold-reduced sheet of unpassivated, and the cold-reduced sheet after the chemical passivation can reach 48 hours no red rusts, has obviously improved the wet-hot aging performance of original IF steel cold-reduced sheet.
2 phosphatizations
Use the scanning electron microscopic observation surface topography, compare phosphatize phosphate coat pattern no significant difference with passivation cold-reduced sheet not.
The cold-reduced sheet analog subscriber technology of cold-reduced sheet after the chemical passivation and unpassivated is carried out degreasing, table accent, bonderizing, adopt the scanning electron microscopic observation surface topography then, contrast as can be seen from the SEM photo of Fig. 2 .1 and Fig. 2 .2, the passivation cold-reduced sheet is not compared, phosphatize phosphate coat pattern no significant difference.The proof chemical passivation does not have influence to the phosphatization crystallization of cold-reduced sheet.Even changes in environmental conditions is bigger, the IF steel cold-reduced sheet after the chemical passivation can keep not corrosion of product in the long time in storage, transportation and user's use, and any variation does not take place on the surface, does not influence the outward appearance on surface.In the later use of cold-reduced sheet, its surface film can be removed along with the cleaning on surface, does not influence the follow-up use of product.
In the validity check process, also carried out smooth influence test: the cold-reduced sheet after the chemical passivation is carried out the smooth of 1% draft to passive film, with without smooth chemical passivation cold-reduced sheet contrast carrying out humid heat test, all rustless behind 48 hours humid heat tests of two kinds of cold-reduced sheets.Prove smooth not influence of passive film solidity to corrosion to the cold-reduced sheet surface.
Claims (3)
1, the corrosion proof electrolytic passivation method of a kind of raising annealing IF steel cold-reduced sheet, utilize the cold-reduced sheet production line facility of continuous annealing, it is characterized in that liquid level is divided into electrode in the hardening groove of the cold-reduced sheet process after annealing: the polarity of two counter electrode is opposite, the homopolarity of respectively doing for oneself, first counter electrode is arranged on the steel plate approaching side, second counter electrode is arranged on steel plate and walks out side, applies 0.5～5A/dm
2Electric current; The passivating solution that contains inhibiter is arranged in the hardening groove, concentration 1～5%, PH8～12,50～70 ℃ of the passivating solution temperature in the maintenance hardening groove, the steel cold-reduced sheet passes through the hardening groove with 200m/min after coming out from annealing furnace.
2, the corrosion proof electrolytic passivation method of a kind of raising annealing IF steel cold-reduced sheet according to claim 1, it is characterized in that the inhibiter in the described passivating solution, per-cent by solute weight is: phenylformic acid amine 20--30%, Sodium Benzoate 20--30%, urotropine 30-40%, monoethanolamine 10-20%, solvent is a water.
3, the corrosion proof electrolytic passivation method of a kind of raising annealing IF steel cold-reduced sheet according to claim 1 is characterized in that the performance evaluation index of the annealed IF steel cold-reduced sheet handled with this method can reach:
(1) 49 ℃ of moisture-proof heat, RH＞95%＞48 hour;
(2) phosphatization: compare phosphatize phosphate coat pattern no significant difference with passivation cold-reduced sheet not.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610023166A CN100999826B (en) | 2006-01-09 | 2006-01-09 | Electrolyting passivating process for enhancing corrosion resisting proferty of continuous annealing IF steel cold rolling plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610023166A CN100999826B (en) | 2006-01-09 | 2006-01-09 | Electrolyting passivating process for enhancing corrosion resisting proferty of continuous annealing IF steel cold rolling plate |
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| Publication Number | Publication Date |
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| CN100999826A true CN100999826A (en) | 2007-07-18 |
| CN100999826B CN100999826B (en) | 2010-05-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107419318A (en) * | 2017-08-11 | 2017-12-01 | 马钢(集团)控股有限公司 | A kind of electrical sheet electrolytic passivation processing method |
| CN107829122A (en) * | 2017-11-24 | 2018-03-23 | 绩溪山合机械有限公司 | A kind of chain inactivating treatment liquid and its passivation process |
| CN110592640A (en) * | 2019-10-14 | 2019-12-20 | 安徽豪鼎金属制品有限公司 | Stainless steel surface corrosion-resistant treatment system and treatment method adopting same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1161298A1 (en) * | 1983-12-20 | 1985-06-15 | Предприятие П/Я Р-6793 | Electrolyte for electrochemical polishing |
| CN1005116B (en) * | 1987-05-15 | 1989-09-06 | 厦门大学 | Corrosion resistance treatment method for stainless steel surface |
| CN1084573A (en) * | 1992-09-12 | 1994-03-30 | 冯绍康 | A kind of compound method of water-soluble organic quenching medium |
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2006
- 2006-01-09 CN CN200610023166A patent/CN100999826B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107419318A (en) * | 2017-08-11 | 2017-12-01 | 马钢(集团)控股有限公司 | A kind of electrical sheet electrolytic passivation processing method |
| CN107419318B (en) * | 2017-08-11 | 2019-08-09 | 马钢(集团)控股有限公司 | A kind of electrical sheet electrolytic passivation processing method |
| CN107829122A (en) * | 2017-11-24 | 2018-03-23 | 绩溪山合机械有限公司 | A kind of chain inactivating treatment liquid and its passivation process |
| CN110592640A (en) * | 2019-10-14 | 2019-12-20 | 安徽豪鼎金属制品有限公司 | Stainless steel surface corrosion-resistant treatment system and treatment method adopting same |
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| CN100999826B (en) | 2010-05-26 |
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