CN104611713B - 400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle and acid washing method - Google Patents
400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle and acid washing method Download PDFInfo
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- CN104611713B CN104611713B CN201510025143.2A CN201510025143A CN104611713B CN 104611713 B CN104611713 B CN 104611713B CN 201510025143 A CN201510025143 A CN 201510025143A CN 104611713 B CN104611713 B CN 104611713B
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Abstract
It is stainless steel hot-rolling annealing wire rod nitration mixture pickle and acid washing method the present invention relates to 400.Pickle is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：The 22wt% of hydrochloric acid 8, the 2wt% of hydrofluoric acid 0.1, the 1wt% of corrosion inhibiter -0.01, acid fog inhibitor addition is 0.1 0.5wt%, and surplus is water.Acid washing method, for pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and carries out pickling, 45 85 DEG C of pickling temperature, the 40min of pickling time 10.The wire rod any surface finish that the present invention is handled is bright in vain, is remained without iron scale, it is not necessary to which carrying out follow-up passivation just can normal use and storage.
Description
Technical field
The invention belongs to stainless steel surfaces processing technology field, more particularly to 400 be stainless steel hot-rolling annealing wire rod nitration mixture
Pickle and acid washing method.
Background technology
400 be wire rod, refers to C content 0.001-0.4%, Cr content in 12-18.5%, siliceous containing manganese 0.5% or so
Measure 0.5-2%, wire rod of the other elements sum below 1%, equivalent to steel such as 0Cr13,0Cr17,1Cr13,1Cr17 in national standard
Kind, such steel grade is free of or containing micro-nickel, scale on surface is very fine and close after annealing, and conventional acid washing method can not be effective
Remove iron scale.Using 304 grade steel grades acid washing method nitric acid and hydrofluoric acid pickling when be very easy to overpickling, stayed on surface
Lower spot corrosion hole.So the wire rod pickling after Cr13 and Cr17 type stainless steel annealings after annealing always is the technology of the industry
Difficult point.Particularly when client needs high annealing（860 DEG C more than -900 DEG C）, with the raising of annealing temperature, Cr and Si etc. are more
Aoxidize out more, add the difficulty of pickling.
Also there are some researchs on this respect in industry at present, wherein most acid washing methods that can not be said to be annealing material,
But the acid washing method of hot rolling material, and be short in understanding for the complexity of the wire rod after high annealing and normarzing annealing wire rod.
Number of patent application 200710061665.3 and a kind of technique of nitration mixture pickling, but the ratio of its hydrofluoric acid is up to more than 10%, this
For the hydrofluoric acid of sample concentration in production using the health that can have a strong impact on worker, the corrosion inhibiter of the formula in its text only uses one
Kind, actually show that a kind of effect of inhibition does not have the composite effect of a variety of corrosion inhibiter good.Number of patent application 20101032939.2 carries
To a kind of wiredrawing wire rod pickling additive, but the steel grade of not specified pickling and the sour species and addition of pickling, the additive
There is no solution stabilizer and accelerator.The patent No. 20081055045.3 mentions a kind of oxide skin minimizing technology of hot-rolled stainless steel,
Pickle adds the corrosion inhibiter such as hydrochloride, thiocarbamide composition using sulfuric acid as pickling medium, and the pickling of inapplicable annealing material, and
And use sulfuric acid washing.
The content of the invention
In order to solve the above technical problems, the problem of being not easy pickling when being directed to annealed material, especially high annealing, this hair
Bright to propose 400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle and acid washing method, and this method pickling effect is good, table after pickling
Face is pure white, attractive in appearance, without overpickling and the phenomenon of deficient pickling.
An object of the present invention be to provide one kind 400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle, the pickling
Liquid is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：Hydrochloric acid 8-22wt%,
Hydrofluoric acid 0.1-2wt%, corrosion inhibiter 0.01-1wt%, acid fog inhibitor addition are 0.1-0.5wt%, and surplus is water.
Corrosion inhibiter of the present invention be methenamine, sodium benzoate, quaternary ammonium salt, citric acid, thiocarbamide, natrium nitrosum it is any
It is one or more of.
Acid fog inhibitor of the present invention is any in sulfonate, benzene sulfonate, OP-10, AEO
It is one or more of.
Sulfonate of the present invention is dodecyl sodium sulfate.
It is stainless steel hot-rolling annealing wire rod nitration mixture acid washing method it is a further object of the present invention to provide one kind 400, including such as
Lower step：Pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath carries out pickling, pickling
45-85 DEG C of temperature, pickling time 10-40min.
Pickle of the present invention is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material matter
Amount ratio is as follows：Hydrochloric acid 8-22wt%, hydrofluoric acid 0.1-2wt%, corrosion inhibiter 0.01-1wt%, acid fog inhibitor addition are 0.1-
0.5wt%, surplus are water.
Corrosion inhibiter of the present invention be methenamine, sodium benzoate, quaternary ammonium salt, citric acid, thiocarbamide, natrium nitrosum it is any
It is one or more of.
Acid fog inhibitor of the present invention is any in sulfonate, benzene sulfonate, OP-10, AEO
It is one or more of.
Sulfonate of the present invention is dodecyl sodium sulfate.
Of the present invention 400 be wire rod, refers to C content 0.001-0.4%, Cr content 12-18.5%, containing manganese 0.5% or so, contains
Silicon amount 0.5-2%, wire rod of the other elements sum below 1%, equivalent to steel such as 0Cr13,0Cr17,1Cr13,1Cr17 in national standard
Kind.
The mentality of designing of the present invention is as follows：The iron scale of stainless steel hot-rolling wire surface, after soft annealing, it can contain
There is a small amount of Cr2O3, SiO2, XRD detections Fe2O3Content can reach 50-80wt%, the iron scale surface with ordinary carbon steel
Composition difference it is very big, FeO content is very high in the iron scale of ordinary carbon steel.The iron scale formed after stainless steel annealing is non-
Chang Zhimi, pickle is not easy that displacement reaction occurs with steel substrate through iron scale, so the generation that comes off of iron scale
It is seldom.The iron scale of stainless steel can only lean on limited dissolution to remove, Fe2O3It is substantially high in the meltage in hydrochloric acid
In the meltage in sulfuric acid, so during pickling of stainless steel, it is preferred to use hydrochloric acid.
But in high temperature pickling, iron scale is finer and close, and Si elements more aoxidize out, easily in iron scale
The fine and close SiO of contact is formed on bottom2Coating.SiO2Insoluble in common bronsted lowry acids and bases bronsted lowry, hydrofluoric acid is dissolved only in.Other high annealing
Oxide skin particularly compact afterwards, pickle are not easy to pass through, and add the difficulty of pickling.And F—Radius is small, is easily accessible less
Gap, so hydrofluoric acid is also used as bleeding agent use in pickling, effect is very good.But the addition of hydrofluoric acid is not easy
Excessively, excessively cause air pollution and endanger workers ' health, preferably below 2%.
It is using beneficial effect caused by above-mentioned technical proposal：Wire rod any surface finish after above method pickling is white
It is bright, remained without iron scale, it is not necessary to which carrying out follow-up passivation just can normal use and storage.
Brief description of the drawings
Fig. 1 is scale on surface XRD testing result collection of illustrative plates after 0Cr13 of the present invention annealing.
Embodiment
With reference to specific embodiment, the present invention is further detailed explanation.
Embodiment 1：
0Cr13 annealing and pickling technique
0Cr13 main component：C content<0.05%, Cr content 13%, Si contents 0.5%.The specification 5.5mm- of wire rod
42mm, 700-800 DEG C of annealing temperature.
Pickle is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：Hydrochloric acid
22wt%, hydrofluoric acid 0.1wt%, corrosion inhibiter 1wt%, acid fog inhibitor addition are 0.5wt%, and surplus is water；Corrosion inhibiter is black Lip river
Tropine, quaternary ammonium salt, natrium nitrosum etc. mass mixing thing；Acid fog inhibitor is dodecyl sodium sulfate.
Acid cleaning process：Pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and entered
Row pickling, 85 DEG C of pickling temperature, pickling time 30min, is rinsed and neutralizes after pickling, can be deposited after drying.
The 0Cr13 surfaces non-oxidation iron sheet residual of pickling, outward appearance are silvery white in color in this way.Pickling is lost（Before pickling
Weight before mass loss/pickling afterwards）For 0.8%, no overpickling.
Embodiment 2：
1Cr13 annealing and pickling technique
1Cr13 main component, C content<0.15%, Cr content 13%, Si contents 0.5%.The specification 5.5mm- of wire rod
42mm, 860-920 DEG C of of high temperature anneal temperature
Pickle is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：
Hydrochloric acid 8wt%, hydrofluoric acid 2wt%, corrosion inhibiter 0.1wt%, acid fog inhibitor addition are 0.1wt%, and surplus is water；Corrosion inhibiter is crow
Lip river tropine, thiocarbamide and sodium benzoate etc. mass mixing thing；Acid fog inhibitor is dodecyl sodium sulfate, benzene sulfonate, fat
Alcohol APEO waits mass mixing thing.
Acid cleaning process：Pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and entered
Row pickling, 70 DEG C of pickling temperature, pickling time 40min, is rinsed and neutralizes after pickling, can be deposited after drying.
The 1Cr13 surfaces non-oxidation iron sheet residual of pickling in this way, without residual acid（There is residual acid to form macula lutea）, no dust
（Outward appearance is gloomy at dust）.Appearance off-white, pickling loss（Weight before mass loss/pickling before and after pickling）For 0.6%, nothing
Overpickling.
Embodiment 3：
0Cr17 annealing and pickling technique
0Cr17 main component, C content<0.05%, Cr content 17%, Si contents 0.5%.The specification 5.5mm- of wire rod
42mm, 780-820 DEG C of of annealing temperature
Pickle is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：
Hydrochloric acid 17wt%, hydrofluoric acid 1.2wt%, corrosion inhibiter 0.05wt%, acid fog inhibitor addition are 0.25wt%, and surplus is water；Inhibition
Agent be thiocarbamide, sodium benzoate and citric acid etc. mass mixing thing；Acid fog inhibitor is dodecyl sodium sulfate, fatty alcohol polyoxy
Vinethene waits mass mixing thing.
Acid cleaning process：Pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and entered
Row pickling, 65 DEG C of pickling temperature, pickling time 30min, is rinsed and neutralizes after pickling, can be deposited after drying.
The 0Cr17 surfaces non-oxidation iron sheet residual of pickling in this way, without residual acid.Outward appearance silvery white, pickling loss（Acid
Weight before mass loss/pickling before and after washing）For 0.9%, no overpickling.
Embodiment 4：
1Cr13 annealing and pickling technique
1Cr13 main component, C content<0.15%, Cr content 13%, Si contents 0.5%.The specification 5.5mm- of wire rod
42mm, 860-920 DEG C of of high temperature anneal temperature
Pickle is made up of hydrochloric acid, hydrofluoric acid, corrosion inhibiter, acid fog inhibitor and water；Each material mass ratio is as follows：
Hydrochloric acid 20wt%, hydrofluoric acid 1.6wt%, corrosion inhibiter 0.01wt%, acid fog inhibitor addition are 0.4wt%, and surplus is water；Corrosion inhibiter
For methenamine and sodium benzoate etc. mass mixing thing；Acid fog inhibitor be benzene sulfonate, AEO etc.
Mass mixing thing.
Acid cleaning process：Pickle is injected in descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and entered
Row pickling, 45 DEG C of pickling temperature, pickling time 10min, is rinsed and neutralizes after pickling, can be deposited after drying.
The 1Cr13 surfaces non-oxidation iron sheet residual of pickling in this way, without residual acid（There is residual acid to form macula lutea）, no dust
（Outward appearance is gloomy at dust）.Appearance off-white, pickling loss（Weight before mass loss/pickling before and after pickling）For 0.7%, nothing
Overpickling.
The present invention is described in detail above by embodiment, but the content is only the preferable implementation of the present invention
Example, is designed using technical solutions according to the invention, or those skilled in the art under the inspiration of technical solution of the present invention
Similar technical scheme, and reach above-mentioned technique effect, it is to fall into protection scope of the present invention.
Claims (4)
1.400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle, it is characterised in that the pickle is by hydrochloric acid, hydrofluoric acid, slow
Lose agent, acid fog inhibitor and water composition；Each material mass ratio is as follows：Hydrochloric acid 8-22wt%, hydrofluoric acid 0.1-2wt%, delay
Agent 0.01-0.1wt% is lost, acid fog inhibitor addition is 0.1-0.5wt%, and surplus is water；
The acid fog inhibitor is any one or a few in sulfonate, benzene sulfonate, OP-10, AEO；
The sulfonate is dodecyl sodium sulfate.
2. according to claim 1 400 be stainless steel hot-rolling annealing wire rod nitration mixture pickle, it is characterised in that described slow
Erosion agent is any one or a few in methenamine, sodium benzoate, quaternary ammonium salt, citric acid, thiocarbamide, natrium nitrosum.
3.400 be stainless steel hot-rolling annealing wire rod nitration mixture acid washing method, it is characterised in that is comprised the following steps：By claim 1
In the pickle injection descaling bath, the whole disk of hot rolling wire after annealing is directly placed into descaling bath and carries out pickling, pickling temperature
70-85 DEG C, pickling time 10-40min.
4. according to claim 3 400 be stainless steel hot-rolling annealing wire rod nitration mixture acid washing method, it is characterised in that described
Corrosion inhibiter be methenamine, sodium benzoate, quaternary ammonium salt, citric acid, thiocarbamide, natrium nitrosum any one or a few.
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| CN104988517A (en) * | 2015-07-29 | 2015-10-21 | 河南红东方化工股份有限公司 | Acidic disincrustant and preparation method thereof |
| CN105369266A (en) * | 2015-12-14 | 2016-03-02 | 浙江大学 | Steel acid washing liquid based on Fenton oxidation reaction and acid washing process |
| CN106637244B (en) * | 2017-01-23 | 2019-01-01 | 上海应用技术大学 | A kind of acid cleaning of steel tube liquid nanometer additive and preparation method thereof |
| CN108359911A (en) * | 2018-03-28 | 2018-08-03 | 浙江益宏不锈钢有限公司 | A kind of austenite stainless steel seamless steel tube and its preparation process |
| CN109055946B (en) * | 2018-09-27 | 2021-02-02 | 山西太钢不锈钢股份有限公司 | Pickling solution and pickling method for oxide layers of cutting surfaces of carbon steel and low alloy steel |
| CN112430818A (en) * | 2020-11-20 | 2021-03-02 | 德清县豪鹰金属制品有限公司 | Surface treatment process for steel wire |
| CN113088980B (en) * | 2021-04-02 | 2022-09-20 | 山西太钢不锈钢股份有限公司 | Production method of iron chromium aluminum alloy hot-rolled strip steel surface oxide skin through hydrochloric acid pickling |
| CN113584498B (en) * | 2021-07-23 | 2023-02-24 | 中冶南方工程技术有限公司 | Hot-rolled stainless steel annealing and pickling process and pickling equipment |
| CN113736575A (en) * | 2021-09-28 | 2021-12-03 | 长沙艾森设备维护技术有限公司 | High-speed rail brake resistor sheet cleaning agent and preparation method thereof |
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