CN102021570B - Treatment process for forming SiO2 coating/Ni-Si alloyed layer composite structure on surface of cold-rolled mild steel plate - Google Patents
Treatment process for forming SiO2 coating/Ni-Si alloyed layer composite structure on surface of cold-rolled mild steel plate Download PDFInfo
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- CN102021570B CN102021570B CN2010105881229A CN201010588122A CN102021570B CN 102021570 B CN102021570 B CN 102021570B CN 2010105881229 A CN2010105881229 A CN 2010105881229A CN 201010588122 A CN201010588122 A CN 201010588122A CN 102021570 B CN102021570 B CN 102021570B
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Abstract
The invention relates to a treatment process for forming a SiO2 coating/Ni-Si alloyed layer composite structure on the surface of a cold-rolled mild steel plate, belonging to the technical field of metal surface treatment. The invention is characterized by comprising the following steps: spraying nano SiO2 powder and nano Ni(OH)2 powder on the surface of a cold-rolled mild steel plate to carry out hydrogenation reduction heat treatment, wherein the heat treatment temperature is 450-700 DEG C, and the flow rate of the introduced H2 is 100-200 mL/min; and finally, obtaining the SiO2 coating/Ni-Si alloyed layer composite structure on the surface of the cold-rolled mild steel plate. The corrosion resistance of the cold-rolled mild steel plate treated by the method is obviously enhanced.
Description
Technical field
The present invention relates to a kind of cold-rolling mild steel plate surface and form SiO
2The treatment process of coating/Ni-Si alloying layer composite structure belongs to field of metal surface treatment technology.
Background technology
Metallic corrosion has brought enormous economic loss for the national economy of countries in the world, and the annual because financial loss that corrosion causes of China accounts for 3～5% of gross national product then.Common aseptic technic has reasonable material, surface protection (comprising metal plating and Fei Jin layer coating), surrounding medium processing, electro-chemical protection and protection against corrosion design etc. at present.
The eighties in 20th century; The sufacing that is put into one of 10 gordian techniquies in the world; Through the development in surplus 20 years, become emerging, interdisciplinary, comprehensive strong an advanced basis and an engineering, form and support the important factor that current technical renovation and technological revolution develop.Preparing the inorganics coating technology in the metallic surface is the metal surface treating method that receives much concern in recent years, also is the focus of anti-corrosion of metal technical study.Utilize this technology to prepare the inorganics coating that one deck is fine and close continuously, unreactiveness is good, improve oxidation-resistance, the erosion resistance of matrix with this at metal base surface.People are to TiO
2, SiO
2, ZrO
2And Al
2O
3Made big quantity research Deng the unit system coating, they are proved to be has good anti-oxidant, corrosion resistance nature.People transfer to focus on the multicomponent system coating gradually now, think that polybasic system coating and associativity, oxidation-resistance, the erosion resistance of matrix have greatly improved than unit system coating.
Metal surface alloyization also is a kind of important metal surface treating method in addition.Metal surface alloyization is meant that single or compound penetrates into the surface of various metallic matrixes or tool and mould with alloying elements such as Cr, Al, V, Ti, B, C, Zn etc. through diffusion; Obtain to have the various particular compound layers of metallurgical binding, thereby give part and tool and mould surface with high firmness, high-wearing feature, solidity to corrosion, high-temperature oxidation and electricity, optical characteristics that some are special with matrix.Metal surface alloyization can be divided into by the realization means: the alloying constituent that 1, changes the metallic surface.2, metallic surface soverlay technique.3, improve the metallographic structure of metallic surface, textura epidermoidea is strengthened.
Cold-rolled low carbon steel belongs to structural carbon steel, because its production technique is simple, cheap, use characteristics is good, in machinery manufacturing industry, is widely used.In the cold-rolled steel sheet annealing process, elements such as the Mn in the steel, Si can move to surface of steel plate, react with oxidizing gas micro-in the environment, around surface of steel plate ferritic crystal boundary, form the particulate state oxide compound.In the process of cooling after annealing, when surface of steel plate touched air, the surface did not have the place of oxide particle can form the red stone film of thin layer.Correlative study shows: the surface of cold-rolled steel plate corrosion resisting property is relevant at the enrichment degree of surface of cold-rolled steel plate with elements such as Mn, Si.
The lifting conventional industries technology content that develops into of nanosecond science and technology provides new opportunity.Nanoparticle is owing to have special effectses such as surface effects, small-size effect, quantum size effect, macro quanta tunnel effect; The performance such as light, magnetic, electricity, mechanics that can be used for improving material is improved or gives its new function; Can improve its quality product in Application Areas greatly, have good theoretical investigation value and application prospect.In addition, along with technical progress, the preparation cost of nano-powder and rete also descends significantly, for the nanotechnology large-scale application has been established sturdy basic substance.
Study on the basis forefathers; The present invention hot research field that the metallic surface prepares inorganics coating technology, surface of steel plate alloying, nanosecond science and technology etc. of combining closely; Suitable through processability, quality, price; And can effectively incorporate the metal of iron-based sosoloid and the particle or the rete of respective compound micro-/ nano yardstick thereof, in the cold-rolled low carbon steel surface, the metal that under strongly reducing atmosphere, part is reduced out incorporates iron-based sosoloid with the spraying of above-mentioned powder granule or rete or roll compacting; Or the respective compound of metal is reduced to metal enrichment in surface of steel plate; And keep certain inorganics coating, to obtain inorganics coating/alloying layer compound cold-rolled low carbon steel surface layer structure, in the hope of obtaining excellent corrosion resisting performance and improving other relevant physics and chemical property.
Summary of the invention
The objective of the invention is to provide a kind of cold-rolling mild steel plate surface to form SiO
2The treatment process of coating/Ni-Si alloying layer composite structure, it strengthens the corrosion resistance nature of cold-rolling mild steel plate effectively.
A kind of cold-rolling mild steel plate of the present invention surface forms SiO
2The treatment process of coating/Ni-Si alloying layer composite structure is characterized in that having following process and step:
The pre-treatment on a, cold-rolling mild steel plate surface: the cold-rolling mild steel plate that desire is handled after absolute ethyl alcohol, acetone clean successively, drying, it is subsequent use to be positioned over moisture eliminator;
B, configuration nanometer SiO
2-Ni (OH)
2Complex liquid, the prescription of complex liquid is following:
Nanometer SiO
2Powder 6～20g/L, particle diameter are 40～90nm;
Nanometer Ni (OH)
2Powder 1～8g/L, particle diameter are 70～120nm;
Ethanol: butanols 1:5～8 (volume ratio);
With the nanometer SiO for preparing in advance
2Powder and nanometer Ni (OH)
2Powder joins in the middle of the mixed solution of ethanol and butanols, then ultra-sonic dispersion 30min;
C. with the above-mentioned nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to above-mentioned cold-rolling mild steel plate surface, natural air drying; SiO
2-Ni (OH)
2The composite Nano coat-thickness is 1～10 μ m;
D. above-mentioned area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating leads to H in tube furnace
2Reduction heat is handled; The reduction heat treatment process parameter is:
Temperature: 450～700 ℃
Heating gradient: 2～10 ℃/min
Soaking time: 2～8h
Cooling method: air cooling
H
2Airshed is: 100～300mL/min
Finally form SiO at surface of steel plate
2Coating/Ni-Si alloying layer composite structure.
Characteristics of the present invention:Characteristics of the present invention are to utilize nanometer SiO
2Powder and nanometer Ni (OH)
2Powder sprays to the cold-rolling mild steel plate surface and carries out the reduction heat processing, makes the cold-rolling mild steel plate surface obtain SiO
2Coating/Ni-Si alloying layer composite structure, the perhydro bell-type annealing technology in the cold-rolled steel sheet production process capable of using realizes extensive continuous industry production, improves the corrosion resistance nature of cold-rolling mild steel plate.
Embodiment
After practical implementation of the present invention being described at present.
Embodiment 1:Get some of cold-rolling mild steel plate 10 * 20 * 1.5mm, the surface is with the abrasive paper for metallograph polishing, and after absolute ethyl alcohol, acetone cleaned successively, drying was positioned in the moisture eliminator subsequent use.
Nanometer SiO
2-Ni (OH)
2The complex liquid composition is: nanometer SiO
2Powder 13g/L, nanometer Ni (OH)
2Powder 4g/L, ethanol: butanols=1:5.This complex liquid of ultra-sonic dispersion 30min.With the nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to cold-rolling mild steel plate surface, natural air drying, SiO
2-Ni (OH)
2The composite Nano coat-thickness is 3 μ m.Area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating carries out reduction heat in tube furnace handles, and the reduction heat treatment process parameter is: temperature is 680 ℃, and heating gradient is 3 ℃/min, and soaking time is 6h, and the cooling gradient is an air cooling, H
2Airshed is 160mL/min.
The surface is obtained SiO
2The cold-rolling mild steel plate of coating/Ni-Si alloying layer composite structure carries out salt mist experiment, records salt-fog resistant time; Be immersed in simultaneously in 5% sodium chloride solution behind the 30min, test its polarization curve, record corrosion electric current density.Test result is seen table 1..
Embodiment 2:Method according to embodiment 1 prepares the cold-rolling mild steel plate sample.
Nanometer SiO
2-Ni (OH)
2The complex liquid composition is: nanometer SiO
2Powder 17g/L, nanometer Ni (OH)
2Powder 5g/L, ethanol: butanols=1:5.This complex liquid of ultra-sonic dispersion 30min.With the nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to cold-rolling mild steel plate surface, natural air drying, SiO
2-Ni (OH)
2The composite Nano coat-thickness is 3 μ m.Area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating carries out reduction heat in tube furnace handles, and the reduction heat treatment process parameter is: temperature is 680 ℃, and heating gradient is 3 ℃/min, and soaking time is 6h, and the cooling gradient is an air cooling, H
2Airshed is 160mL/min.
The corrosion resistance nature test of sample is carried out according to the method for embodiment 1.Test result is seen table 1..
Embodiment 3:Method according to embodiment 1 prepares the cold-rolling mild steel plate sample.
Nanometer SiO
2-Ni (OH)
2The complex liquid composition is: nanometer SiO
2Powder 13g/L, nanometer Ni (OH)
2Powder 5g/L, ethanol: butanols=1:5.This complex liquid of ultra-sonic dispersion 30min.With the nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to cold-rolling mild steel plate surface, natural air drying, SiO
2-Ni (OH)
2The composite Nano coat-thickness is 3 μ m.Area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating carries out reduction heat in tube furnace handles, and the reduction heat treatment process parameter is: temperature is 450 ℃, and heating gradient is 3 ℃/min, and soaking time is 6h, and the cooling gradient is an air cooling, H
2Airshed is 160mL/min.
The corrosion resistance nature test of sample is carried out according to the method for embodiment 1.Test result is seen table 1..
Embodiment 4:Method according to embodiment 1 prepares the cold-rolling mild steel plate sample.
Nanometer SiO
2-Ni (OH)
2The complex liquid composition is: nanometer SiO
2Powder 13g/L, nanometer Ni (OH)
2Powder 5g/L, ethanol: butanols=1:8.This complex liquid of ultra-sonic dispersion 30min.With the nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to cold-rolling mild steel plate surface, natural air drying, SiO
2-Ni (OH)
2The composite Nano coat-thickness is 3 μ m.Area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating carries out reduction heat in tube furnace handles, and the reduction heat treatment process parameter is: temperature is 450 ℃, and heating gradient is 3 ℃/min, and soaking time is 6h, and the cooling gradient is an air cooling, H
2Airshed is 160mL/min.
The corrosion resistance nature test of sample is carried out according to the method for embodiment 1.Test result is seen table 1..
Embodiment 5:Method according to embodiment 1 prepares the cold-rolling mild steel plate sample.
Nanometer SiO
2-Ni (OH)
2The complex liquid composition is: nanometer SiO
2Powder 13g/L, nanometer Ni (OH)
2Powder 5g/L, ethanol: butanols=1:5.This complex liquid of ultra-sonic dispersion 30min.With the nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to cold-rolling mild steel plate surface, natural air drying, SiO
2-Ni (OH)
2The composite Nano coat-thickness is 2 μ m.Area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating carries out reduction heat in tube furnace handles, and the reduction heat treatment process parameter is: temperature is 680 ℃, and heating gradient is 3 ℃/min, and soaking time is 4h, and the cooling gradient is an air cooling, H
2Airshed is 160mL/min.
The corrosion resistance nature test of sample is carried out according to the method for embodiment 1.Test result is seen table 1..
The corrosion resistance nature test result of the cold-rolling mild steel plate sample that obtains under the table 1. different treatment condition
| Sample | Corrosion electric current density (A/m 2) | Salt-fog test (h) |
| Blank cold-rolling mild steel plate | 7.29×10 -5 | 0.6 |
| Embodiment 1 | 2.32×10 -7 | 900 |
| Embodiment 2 | 7.43×10 -7 | 760 |
| Embodiment 3 | 9.83×10 -7 | 520 |
| Embodiment 4 | 1.06×10 -6 | 270 |
| Embodiment 5 | 5.31×10 -6 | 110 |
The instance proof utilizes the surperficial corrosion electric current density of the cold-rolling mild steel plate of technical finesse of the present invention lower, and the salt-fog test time is longer, explains through surface treatment method of the present invention its corrosion resistance nature is improved greatly.
Claims (1)
1. a cold-rolling mild steel plate surface forms SiO
2The treatment process of coating/Ni-Si alloying layer composite structure is characterized in that having following process and step:
The pre-treatment on a, cold-rolling mild steel plate surface: the cold-rolling mild steel plate that desire is handled after absolute ethyl alcohol, acetone clean successively, drying, it is subsequent use to be positioned over moisture eliminator;
B, configuration nanometer SiO
2-Ni (OH)
2Complex liquid, the prescription of complex liquid is following:
Nanometer SiO
2Powder 6～20g/L, particle diameter are 40～90nm;
Nanometer Ni (OH)
2Powder 1～8g/L, particle diameter are 70～120nm;
Ethanol: butanols 1:5～8 (volume ratio);
With the nanometer SiO for preparing in advance
2Powder and nanometer Ni (OH)
2Powder joins in the middle of the mixed solution of ethanol and butanols, then ultra-sonic dispersion 30min;
C. with the above-mentioned nanometer SiO for preparing
2-Ni (OH)
2Complex liquid sprays to above-mentioned cold-rolling mild steel plate surface, natural air drying; SiO
2-Ni (OH)
2The composite Nano coat-thickness is 1～10 μ m;
D. above-mentioned area load there is SiO
2-Ni (OH)
2The cold-rolling mild steel plate of composite Nano coating leads to H in tube furnace
2Reduction heat is handled; The reduction heat treatment process parameter is:
Temperature: 450～700 ℃
Heating gradient: 2～10 ℃/min
Soaking time: 2～8h
Cooling method: air cooling
H
2Airshed is: 100～300mL/min
Finally form SiO at surface of steel plate
2Coating/Ni-Si alloying layer composite structure.
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|---|---|---|---|
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|---|---|---|---|
| CN2010105881229A CN102021570B (en) | 2010-12-15 | 2010-12-15 | Treatment process for forming SiO2 coating/Ni-Si alloyed layer composite structure on surface of cold-rolled mild steel plate |
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| CN102021570B true CN102021570B (en) | 2012-08-08 |
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| CN102321862A (en) * | 2011-08-31 | 2012-01-18 | 上海大学 | Treatment method for producing ferro-boron alloying on surface of low carbon steel strip base on nanometer technology |
| CN109530855B (en) * | 2018-12-24 | 2021-09-10 | 合肥紫金钢管股份有限公司 | Welding method of large-opening longitudinal submerged arc welded steel pipe for offshore wind power |
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|---|---|---|---|---|
| CN101597739A (en) * | 2009-06-30 | 2009-12-09 | 北京科技大学 | A kind of borax salt bath tungstenized coating on steel matrix surface preparation method |
| CN101892487A (en) * | 2010-06-29 | 2010-11-24 | 上海大学 | Corrosion resistance processing method for composite structure layer formed on surface of cold-rolling mild steel plate |
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| US6595263B2 (en) * | 2001-08-20 | 2003-07-22 | Ford Global Technologies, Inc. | Method and arrangement for utilizing a psuedo-alloy composite for rapid prototyping and low-volume production tool making by thermal spray form techniques |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597739A (en) * | 2009-06-30 | 2009-12-09 | 北京科技大学 | A kind of borax salt bath tungstenized coating on steel matrix surface preparation method |
| CN101892487A (en) * | 2010-06-29 | 2010-11-24 | 上海大学 | Corrosion resistance processing method for composite structure layer formed on surface of cold-rolling mild steel plate |
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Effective date of registration: 20140410 Address after: 200444 Baoshan District Road, Shanghai, No. 99 Patentee after: Shanghai University Patentee after: State Grid Shanghai Municipal Electric Power Company Address before: 200444 Baoshan District Road, Shanghai, No. 99 Patentee before: Shanghai University |