CN115976320B - Surface treatment method for high-carbon martensitic stainless steel wire rod - Google Patents
Surface treatment method for high-carbon martensitic stainless steel wire rod Download PDFInfo
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- CN115976320B CN115976320B CN202211692013.0A CN202211692013A CN115976320B CN 115976320 B CN115976320 B CN 115976320B CN 202211692013 A CN202211692013 A CN 202211692013A CN 115976320 B CN115976320 B CN 115976320B
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 17
- 238000004381 surface treatment Methods 0.000 title claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002161 passivation Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000002265 prevention Effects 0.000 claims abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 26
- 238000005554 pickling Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 230000000630 rising effect Effects 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013556 antirust agent Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005422 blasting Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010301 surface-oxidation reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Heat Treatment Of Strip Materials And Filament Materials (AREA)
Abstract
The invention relates to the technical field of stainless steel heat treatment and surface treatment production, in particular to a surface treatment method of a high-carbon martensitic stainless steel wire rod, which comprises the following procedures of annealing, rust removal, re-annealing, acid washing, passivation and rust prevention of the produced wire rod in sequence, the high-carbon martensitic stainless steel wire rod treated by the method has good surface quality, few surface defects and smooth surface, does not reduce the processing plasticity, and can improve the surface protection effect.
Description
Technical Field
The invention relates to the technical field of stainless steel heat treatment and surface treatment production, in particular to a surface treatment method of a high-carbon martensitic stainless steel wire rod.
Background
The stainless steel wire rod is produced by adopting hot forming and high-temperature heat treatment, a layer of high-temperature metal oxide exists on the surface of the stainless steel wire rod after heat treatment, and the oxide has high hardness, is fragile and easy to peel off, and is easy to generate defects in direct processing. The cleaning of the oxide skin on the surface of the wire rod is an indispensable procedure before the subsequent cold rolling, cold drawing and other processing.
The cleaning mode of the oxide skin on the surface of the stainless steel wire rod adopts a chemical pickling method and a mechanical shot blasting method. The high-carbon martensitic stainless steel has relatively high carbon content, so that the wire rod has relatively poor corrosion resistance, and the conventional chemical pickling method is easy to generate surface defects such as roughness, pit corrosion and the like, so that the pickling process is difficult to control, the pickling time is long, and the pickling loss is high. The surface of the wire rod is cleaned by adopting a mechanical shot blasting mode, shot blasting pits with the thickness of 0.02-0.05 mm are formed, and the surface is subjected to work hardening, so that the plasticity of the wire rod is reduced. The wire rod surface protection effect is poor, and long-time storage and transportation process are easy to appear its condition of corrosion.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the surface treatment method for the high-carbon martensitic stainless steel wire rod, and the high-carbon martensitic stainless steel wire rod treated by the method has the advantages of good surface quality, few surface defects, smooth surface, no reduction of processing plasticity and improvement of surface protection effect.
In order to achieve the above purpose, the present invention provides the following technical solutions: a surface treatment method of a high-carbon martensitic stainless steel wire rod comprises the following steps:
S1, annealing: the wire rod is put into an annealing furnace to be subjected to the procedures of heating, heat preservation and cooling in sequence;
S2, rust removal: removing oxide skin and decarburized layers on the surface of the wire rod treated in the step S1 by adopting a wire rod abrasive belt derusting machine;
s3, re-annealing: putting the wire rods treated in the step S2 into an annealing furnace again, and sequentially carrying out the procedures of heating, heat preservation and cooling;
S4, acid washing: removing oxidation products formed in the re-annealing process of the wire rod by adopting acid liquor to the wire rod treated in the step S3, and eliminating sand marks in the rust removal process;
S5, passivating: passivating the wire rod treated in the step S4 by adopting nitric acid solution;
s6, rust prevention: and (3) performing rust prevention treatment on the wire rod treated in the step (S5) by adopting an aqueous rust inhibitor solution.
Preferably, in the step S1, the temperature rising rate in the temperature rising stage is 100 ℃/h, the temperature keeping temperature is 800-920 ℃, and the temperature reducing rate is not more than 25 ℃/h.
Preferably, the step S2 abrasive belt derusting machine is characterized in that three machine boxes are connected in series, wherein the first two groups of machine boxes use coarse abrasive belts, the granularity of the abrasive belts is 30-100 meshes, the third group of machine boxes use fine abrasive belts, the granularity of the abrasive belts is not less than 100 meshes, and the derusting depth is 0.02-0.06 mm.
Preferably, in the step S3, the temperature rising rate is 100 ℃/h, the heat preservation temperature is 700-780 ℃, the heat preservation time is 8-14 hours, and the temperature falling rate in the temperature falling stage is controlled to be not more than 30 ℃/h.
Preferably, in the step S4 pickling process, HCl solution is adopted for pickling, the concentration of HCl is 80-145 g/L, the pickling temperature is 20-60 ℃, the pickling time is 30-60 min, and residual oxide skin on the surface is flushed out by adopting a high-pressure water gun after pickling.
Preferably, in the step S5 passivation procedure, the concentration of the nitric acid solution is 10-30 g/L, the temperature is 20-40 ℃ and the passivation time is 2-5 min.
Preferably, before the step S6 rust prevention process is carried out, the wire rod treated in the step S5 is subjected to neutralization treatment by adopting alkali liquor; in the step S6, an aqueous antirust agent solution is adopted, the concentration of the antirust agent is controlled according to the density, the density is more than or equal to 1.02g/ml, the PH value is 10-14, the temperature of the antirust liquid is more than or equal to 80 ℃, and the antirust treatment time is more than or equal to 180min.
Preferably, the treated high-carbon chromium stainless steel wire rod comprises the following main chemical elements in percentage by mass: 0.50 to 1.20 percent of C; si is less than or equal to 1.00%; mn is less than or equal to 1.00%; 12.00 to 19.00 percent of Cr; ni is less than or equal to 0.6%; cu is less than or equal to 0.6%; mo is less than or equal to 1.5 percent; n is less than or equal to 0.1 percent; the balance of Fe and unavoidable impurities.
Compared with the prior art, the invention has the beneficial effects that:
(1) The wire abrasive belt deruster is adopted to pretreat the high-carbon martensitic stainless steel wire rod oxide skin, so that the defects of roughness, corrosion holes and the like caused by direct acid washing are avoided. The treated surface is smooth, the surface roughness Ra is less than or equal to 2.0um, the surface roughness Rz is less than or equal to 15um, the pickling process after rust removal is simple, the control is easy, and the production efficiency is high.
(2) The abrasive belt derusting machine adopts three machine boxes to be processed in series, and the wire rods can completely remove the oxide skin after undergoing one uncoiling and coiling procedures, so that the production efficiency is improved, and meanwhile, the breakage caused by multiple uncoiling and coiling procedures is avoided.
(3) The wire rod is annealed before the abrasive belt derusting machine derusting, meanwhile, the strength and the elongation of the wire rod are definitely limited, the derusting process is uniform due to the lower strength, the loss is reduced, and the breakage of the abrasive belt derusting process is avoided due to the better elongation, so that the production efficiency is influenced. And the abrasive belt is annealed again after rust removal, so that the stress generated in the rust removal process of the abrasive belt can be eliminated, the strength of the wire rod can be effectively reduced by combining with the improvement of the surface quality after pickling, and the elongation and the shrinkage are improved.
(4) And the wire rod is subjected to passivation and rust prevention after being pickled, so that rust generated in the long-time placing or marine transportation process is effectively avoided.
Drawings
Fig. 1 is a surface morphology of a wire rod after removal of surface scale by a conventional pickling process.
Fig. 2 is a surface topography of a wire rod after removal of scale using the method of the present invention.
Detailed Description
The following detailed description of the invention, taken in conjunction with the accompanying drawings, will provide those skilled in the art with a more readily understood understanding of how the invention may be practiced. While the present invention has been described in connection with the preferred embodiments thereof, these embodiments are set forth only and are not intended to limit the scope of the invention.
The following specific examples are chosen to provide a detailed description of embodiments of the invention, and it is to be understood that the specific embodiments described herein are merely illustrative of the invention and not limiting of the invention. The main chemistries of the example materials are shown in Table 1.
TABLE 1 example materials Main chemical Components (%)
(1) And (3) annealing the wire rod by adopting a nitrogen protection cover type annealing furnace, wherein the wire rod is subjected to the stages of heating, heat preservation and cooling. Wherein the temperature rising speed is 100 ℃/h in the temperature rising stage, the temperature keeping temperature is 880 ℃ in the heat keeping stage, the heat keeping time is 10 hours, the temperature reducing speed is 25 ℃/h in the temperature reducing stage, the cooling cover is adopted to rapidly cool after the temperature is reduced to 600 ℃, and the cooling cover is taken out of the furnace for air cooling after the cooling is cooled to 300 ℃.
The high-carbon martensitic stainless steel wire rod is annealed to obtain good mechanical properties, and the nitrogen protection bell-type furnace is adopted for annealing to reduce the surface oxidation and decarburization layer depth of the wire rod, reduce the rust removal depth and reduce the loss. The lower strength can facilitate subsequent processing, the strength is too high, the rust removing process is not straight, the oxide skin on the surface of the bent place cannot be completely removed, and the better extensibility can avoid fracture in the rust removing process.
(2) And grinding off surface oxide skin, decarburized layers and fine defects by adopting an abrasive belt derusting machine. The three cases are adopted to be connected in series, the first two groups adopt abrasive belts with 40 meshes and mainly remove surface oxide skin and defects, the second group adopts fine abrasive belts with 100 meshes, and the rust removal depth is 0.02-0.06 mm and is greater than the surface oxidation and decarburization layer depth of the wire rod after annealing in the step S1.
The three rust removing machine boxes are connected in series, so that the production efficiency can be improved, the once and clean removal is ensured, the elongation of the high-carbon martensitic stainless steel wire rod is lower, the yield is increased more after the rust removing process, the elongation is obviously reduced, and the problem of fracture caused by continuous uncoiling and coiling is avoided. The first two groups adopt coarse abrasive belts, so that the grinding depth can be effectively increased, disposable removal is guaranteed, and the third group adopts fine abrasive belts, mainly for reducing the surface roughness, and the surface abrasive belts influence plasticity.
(3) And (3) annealing the wire rod by adopting a nitrogen protection cover type annealing furnace, wherein the wire rod is subjected to a heating stage, a heat preservation stage and a cooling stage, the heating rate is 100 ℃/h, the heat preservation temperature is 760 ℃ in the heat preservation stage, the heat preservation time is 10 hours, the cooling rate is 25 ℃/h in the cooling stage, the wire rod is cooled to 600 ℃ and then is rapidly cooled by adopting a cooling cover, and the wire rod is discharged for air cooling after being cooled to 300 ℃.
The nitrogen protection bell-type furnace is adopted for annealing, so that the surface oxidation and decarburized layer depth of the wire rod can be reduced, the subsequent pickling and cleaning are facilitated, the pickling treatment can remove partial residual oxide skin, the rust removal process is performed in uncoiling and straightening processes, in grinding processes, the drawing force is applied, the annealing treatment can eliminate stress, and the surface quality is good, so that the elongation and the area shrinkage rate are better than those before rust removal.
(4) And (3) removing oxidation products formed in the re-annealing process of the wire rod by adopting an acid washing solution, wherein the concentration of HCl is 80-145 g/L, the acid washing temperature is 20-60 ℃, the acid washing time is 30-60 min, and residual oxide skin on the surface is washed off by adopting a high-pressure water gun after the acid washing.
The acid washing can remove oxidation products formed in the re-annealing process, and simultaneously can remove fine sand marks in the abrasive belt rust removal process, so that the surface of the wire rod is smooth. The surface roughness and unevenness after pickling are shown in table 2.
(5) And (3) passivating the wire rod by using a nitric acid solution, wherein the nitric acid concentration in the passivation process in the step S5 is 10-30 g/L, the temperature is 20-40 ℃, and the passivation time is 2-5 min.
The passivation treatment can lead the surface of the wire rod to generate a layer of compact oxide film, thereby obtaining the rust-proof effect.
(6) Neutralizing the wire rod treated in the step (5) by alkali liquor before the rust-proof treatment; the aqueous antirust agent is adopted, the concentration of the antirust agent is controlled according to the density, the density of the solution is more than or equal to 1.02g/ml, the PH value is 10-14, the temperature of the solution is more than or equal to 80 ℃, and the antirust treatment time is more than or equal to 180 ℃.
The rust-proof treatment makes the surface of the wire rod form a compact protective film, has the effect of isolating air, water vapor and other corrosive media, improves the rust-proof performance, and is suitable for long-time storage and marine processes.
Table 2 example materials surface treatment surface quality conditions
TABLE 3 mechanical Properties of example materials before and after surface treatment
As can be seen from comparison of FIG. 1 and FIG. 2, the surface of the high-carbon martensitic stainless steel wire rod treated by the method has no corrosion hole defect and smooth surface, and the data in Table 2 show that the surface roughness Ra is less than or equal to 2.0um and the surface roughness Rz is less than or equal to 15um.
As can be seen from the data in Table 3, the tensile strength of the high-carbon martensitic stainless steel wire rod treated by the method is obviously reduced, and the elongation and the shrinkage are obviously improved due to the re-annealing treatment and the improvement of the surface quality.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The surface treatment method of the high-carbon martensitic stainless steel wire rod is characterized by comprising the following steps of:
S1, annealing: the wire rod is put into an annealing furnace to be subjected to the procedures of heating, heat preservation and cooling in sequence; in the step S1, the temperature rising rate in the temperature rising stage is 100 ℃/h, the heat preservation temperature is 800-920 ℃, and the temperature reducing rate is not more than 25 ℃/h;
S2, rust removal: removing oxide skin and decarburized layers on the surface of the wire rod treated in the step S1 by adopting a wire rod abrasive belt derusting machine; the step S2 of the abrasive belt derusting machine is carried out by adopting three machine boxes in series, wherein the first two groups of machine boxes use coarse abrasive belts, the granularity of the abrasive belts is 30-100 meshes, the third group of machine boxes use fine abrasive belts, the granularity of the abrasive belts is not less than 100 meshes, and the derusting depth is 0.02-0.06 mm;
S3, re-annealing: putting the wire rods treated in the step S2 into an annealing furnace again, and sequentially carrying out the procedures of heating, heat preservation and cooling; the temperature rising rate in the temperature rising stage in the step S3 is 100 ℃/h, the heat preservation temperature is 700-780 ℃, the heat preservation time is 8-14 hours, and the temperature falling rate in the temperature falling stage is controlled to be not more than 30 ℃/h;
S4, acid washing: removing oxidation products formed in the re-annealing process of the wire rod by adopting acid liquor to the wire rod treated in the step S3, and eliminating sand marks in the rust removal process; in the step S4 pickling process, a HCl solution is adopted for pickling, the HCl concentration is 80-145 g/L, the pickling temperature is 20-60 ℃, the pickling time is 30-60 min, and a high-pressure water gun is adopted for flushing off the surface residual oxide skin after pickling;
S5, passivating: passivating the wire rod treated in the step S4 by adopting nitric acid solution;
S6, rust prevention: performing rust prevention treatment on the wire rod treated in the step S5 by adopting a water-based rust inhibitor solution;
The processed high-carbon stainless steel wire rod comprises the following main chemical elements in percentage by mass: 0.50 to 1.20 percent of C; si is less than or equal to 1.00%; mn is less than or equal to 1.00%; 12.00 to 19.00 percent of Cr; ni is less than or equal to 0.6%; cu is less than or equal to 0.6%; mo is less than or equal to 1.5 percent; n is less than or equal to 0.1 percent; the balance of Fe and unavoidable impurities.
2. The surface treatment method of the high-carbon martensitic stainless steel wire rod according to claim 1, characterized in that: in the step S5 passivation procedure, the concentration of the nitric acid solution is 10-30 g/L, the temperature is 20-40 ℃ and the passivation time is 2-5 min.
3. The surface treatment method of the high-carbon martensitic stainless steel wire rod according to claim 1, characterized in that: before the step S6 of rust prevention, neutralizing the wire rod treated in the step S5 with alkali liquor; in the step S6, an aqueous antirust agent solution is adopted, the concentration of the antirust agent is controlled according to the density, the density is more than or equal to 1.02g/ml, the PH value is 10-14, the temperature of the antirust liquid is more than or equal to 80 ℃, and the antirust treatment time is more than or equal to 180min.
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| EP0923420A1 (en) * | 1996-12-26 | 1999-06-23 | J & L Specialty Steel, Inc. | Brushing process for corrosion and oxidation resistance |
| CN102162075A (en) * | 2010-02-23 | 2011-08-24 | 宝山钢铁股份有限公司 | Austenitic stainless steel with excellent polishing performance and manufacturing method thereof |
| CN102199695A (en) * | 2010-03-25 | 2011-09-28 | 宁波宝新不锈钢有限公司 | Processing method for ferrite antibacterial stainless steel plate strip |
| FR2980803B1 (en) * | 2011-09-30 | 2013-10-25 | Areva Np | METHOD FOR PRODUCING A STAINLESS STEEL CORROSION RESISTANT STAINLESS STEEL PIECE FOR A NUCLEAR REACTOR, CORRESPONDING PART AND CONTROL CLUSTER. |
| EP3640357A4 (en) * | 2017-06-15 | 2020-09-30 | Nippon Steel Corporation | Rolled wire for spring steel |
| CN114107638A (en) * | 2021-10-25 | 2022-03-01 | 浙江腾龙精线有限公司 | Processing method of steel wire for armored cable |
| CN114733910A (en) * | 2022-03-31 | 2022-07-12 | 天津太钢天管不锈钢有限公司 | Manufacturing method of austenitic stainless steel suitable for surface sand blasting processing |
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| CN109706402A (en) * | 2018-12-27 | 2019-05-03 | 浙江腾龙精线有限公司 | A kind of preparation method of two phase stainless steel gas metal-arc welding silk |
| CN112981069A (en) * | 2021-02-04 | 2021-06-18 | 山西太钢不锈钢股份有限公司 | Preparation method of low-glossiness stainless steel panel material |
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