CN102321862A - Treatment method for producing ferro-boron alloying on surface of low carbon steel strip base on nanometer technology - Google Patents
Treatment method for producing ferro-boron alloying on surface of low carbon steel strip base on nanometer technology Download PDFInfo
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- CN102321862A CN102321862A CN201110254261A CN201110254261A CN102321862A CN 102321862 A CN102321862 A CN 102321862A CN 201110254261 A CN201110254261 A CN 201110254261A CN 201110254261 A CN201110254261 A CN 201110254261A CN 102321862 A CN102321862 A CN 102321862A
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Abstract
The invention relates to a treatment method for treating a ferro-boron alloyed coating on a surface of a low carbon steel strip, which integrates the hot spot research fields of a surface treatment technology of the metal coating, a nanometer preparation method, steel plate surface alloying and the like. The method comprises the following steps: preparing nanometer paint by combining a mechanical mill method, an ultrasonic treatment and the like, spraying boron-rich nanometer paint on the surface of the low carbon steel. Under the reducing atmosphere of H2, nanometer Fe2O3 in coating can be reduced to generate new ecological Fe atom which has high activity, FeB is continuously attacked to generate Fe2B phase on the metal surface. Fe2B has advantages of high hardness, good toughness, high corrosion resistance, small expansion coefficient with a substrate and the like. The other part is dissolved into the substrate by the reduced metal Fe, so that the combination force of a boron alloyed layer and the substrate can be enhanced, the uniformity can be greatly raised, so that the modification of the surface of the low carbon steel can be realized. The method of the invention is capable of effectively raising the corrosion resistance, surface microscopic hardness, fracture strength and the like of the low carbon steel, and effectively solving the problems of high temperature, long heat treatment time and the like existed in traditional boronisation.
Description
Technical field
The present invention relates to do the modification processing method of ferro-boron coating, belong to heat treatment technics field, metallic surface at surface of low-carbon steel.
Background technology
Nanotechnology is the novel method of the material modification that gets up of development in recent years, has been widely used in the preparation and the metal surface modification of nano material.Greatly about the nineties in 20th century just the someone begin to prepare TiO at alloy surface
2, Al
2O
3And SiO
2Coating, and their application carried out extensive studies, be proved have good high temperature resistance, corrosion resistant ability.But the oxide coatings of one-component or two-pack has certain limitation; In order better to improve the performance of coating; People begin to attempt preparation multi-component oxide coating, can be that film is more continuous and fine and close like this, improve the erosion resistance and the thermostability of material.Nano science is to be born also just in the frontier nature of fast development, the high-tech new branch of science field of intercrossing late 1980s.The metallic particles of nano-scale is owing to have special nature such as small-size effect, quantum ruler effect, surface effects and macro quanta tunnel effect; Thereby have optics, electromagnetism and a chemical property that is different from the respective masses material; Compare with conventional material; It has unrivaled meliority in fields such as Materials science, information science, catalysis and life sciences, in practical application with all have great researching value in theory.In addition, along with the continuous development of technology, the preparation of nano-powder and nano thin-film, research and application are also more and more widely.
Metal surface alloyization is to generate the various particular compound layers that passive film or acquisition and matrix have metallurgical binding at the ambient conditions lower surface; Make hardness, wear resistance, corrosion resistance nature and the high temperature oxidation resistance of material improve, this is a kind of method of important raising Mechanical Property of Metal.Wherein, a kind of very important alloying treatment method for surface is exactly the metallic surface boron alloyization.Because boride layer has hardness height (Fe
2B is 1290-1680HV, and FeB is 1890-2340HV), solidity to corrosion, wear resistance be good, advantage such as high temperature oxidation resistance and red hardness are good.But because the boronising treatment temperature is higher at present; Reasons such as the distortion of part greatly and infiltration layer is thin, infiltration layer fragility is bigger after boronising is handled; Limited applying of boronizing technology; Experts and scholars both domestic and external have for this reason done a large amount of exploratory developments in this regard, as take to obtain monophasic Fe after the boronising
2Carry out the vacuum diffusion after B or the boronising and obtain single-phase Fe
2The eutectic processing of B boronising and ooze the fragility that reduces boride layer with technology such as composite cementation altogether; Present research direction mainly is to reduce the boronising temperature; Polynary compound boronising improves infiltration layer microstructure, microhardness, fragility and wear resistance; And the boronising eutecticization makes infiltration layer and matrix be metallurgical binding, thereby the boride layer fragility of improving in the past is big, problem such as peels off easily.
Based on previous finding, the present invention combines the hot research fields such as process for treating surface, nanometer preparation method and surface of steel plate alloying of metallic coating.Earlier, spray rich boron nano paint at surface of low-carbon steel through technology such as mechanical milling method and the supersound process preparation nano paint that combines, and at H
2Nanometer Fe in the coating under the reducing atmosphere
2O
3Be reduced the Fe atom that generates nascent state, it has higher activity, constantly attacks FeB and makes it the generation Fe in the metallic surface
2The B phase.Fe
2B hardness is high, and good toughness is with advantages such as the substrate coefficient of expansion are little.The metal Fe atom that a part restores dissolves in the matrix, has strengthened the bonding force of boron alloy layer and matrix, and homogeneity also is greatly improved, thereby surface of low-carbon steel has been carried out modification.
Summary of the invention
The present invention proposes the preparation method of nano surface ferro-boron coating alloyization (B-Fe) structure, it has not only strengthened the corrosion resistance nature of mild steel plate effectively, performances such as surface microhardness, but also solved the problem that exists in traditional boronising effectively.
The present invention is a kind of in mild steel plate nano surface ferro-boron coating treatment process, it is characterized in that having following process and step:
(1) mild steel plate of desire being handled is through absolute ethyl alcohol, acetone and deionized water ultrasonic cleaning successively, and dry back is subsequent use;
(2) preparation of nanometer ferro-boron coating:
Adopt the mechanical ball milling method, with commercially available FeB powder and analytical pure Fe
2O
3By putting into ball grinder behind the certain mol proportion uniform mixing, add the certain liquid-solid ratio of a certain amount of EtOH control, ball milling number hour.Preparation technology parameter is following:
FeB:Fe
2O
3=1: (1 ~ 4) (mol ratio);
FeB/Fe
2O
3: EtOH=15:80 (mass ratio);
Ball milling time=20 ~ 30h; Finally make nanometer ferro-boron coating;
(3) the above-mentioned nanometer ferro-boron coating that makes is sprayed at the surface of low-carbon steel of handling well equably, after the seasoning, in tube type resistance furnace, heat-treats under the atmosphere of hydrogen, its processing parameter is following:
Temperature: 700 ~ 1000 ℃;
Heating gradient: 10 ℃/min;
Heat treatment time: 2 ~ 8h;
The cooling gradient: stove is cold;
H
2Airshed is: 150 ~ 200mL/min.
Characteristics of the present invention are: the metallic surface heat treating method that it is different from the past, and the present invention is based on nanotechnology, prepares rich boron alloy layer in the metallic surface, under hydrogen reducing atmosphere, Fe
2O
3Be reduced the Fe atom that produces nascent state and have higher activity, constantly attack FeB and make it generation Fe in the metallic surface
2The B phase.Fe
2B hardness is high, good toughness, with advantages such as the substrate coefficient of expansion are little, and FeB to be us mutually do not hope to obtain, though his hardness is very high, fragility is big, and is very easily cracked in the subsequent disposal.After the inventive method is carried out the reduction heat processing, make the mild steel plate surface obtain Fe even, strong adhesion
2The B alloy structure, its hardness rises to 1100HV from 99HV.Through electro-chemical test, the sample corrosion potential after the alloying is shuffled, and becomes-788.4 from-832.6mv, and corrosion electric current density also obviously reduces, from 59.388 μ A/cm of beginning
2Be reduced to 8.784 μ A/cm
2, anti-corrosion efficient reaches 85.2%. and shows that fully the sample after the alloying has higher hardness, and solidity to corrosion is good.
In conjunction with existing manufacturing technique, can realize extensive continuous industry production, and the various mechanical propertys of raising mild steel plate are to prolong its service life.
Embodiment
Practical implementation of the present invention is described in down at present:
Embodiment 1:Get some of mild steel plate 10 * 10 * 1.6mm, its workplace is polished with abrasive paper for metallograph, after absolute ethyl alcohol, acetone and deionized water cleaned several minutes successively, drying was positioned in the loft drier subsequent use.
In anhydrous ethanol medium, FeB and Fe
2O
31:1 in molar ratio, after liquid-solid mass ratio 15:80 batching is accomplished, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.With evenly spraying to the mild steel plate surface behind the ultra-sonic dispersion 10min before, seasoning is heat-treated in tube type resistance furnace then; Its heat treatment process parameter is: temperature is 700 ℃; Temperature rise rate is 10 ℃/min, and soaking time is 2h, and the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
The soft steel that the surface is obtained the ferro-boron structure carries out breaking tenacity, hardness, tests such as solidity to corrosion.
Embodiment 2:Method according to embodiment 1 is handled the cold-rolling mild steel plate sample.
In anhydrous ethanol medium, FeB and Fe
2O
31:4 in molar ratio, after liquid-solid mass ratio 15:80 batching is accomplished, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.With evenly spraying to the mild steel plate surface behind the ultra-sonic dispersion 10min before, seasoning is heat-treated in tube type resistance furnace then; Its heat treatment process parameter is: temperature is 700 ℃; 10 ℃/min of temperature rise rate, soaking time is 8h, the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
The soft steel that the surface is obtained the ferro-boron structure carries out breaking tenacity, hardness, tests such as solidity to corrosion.
Embodiment 3:Method according to embodiment 1 is handled the cold-rolling mild steel plate sample.
In anhydrous ethanol medium, FeB and Fe
2O
31:1 in molar ratio, after liquid-solid mass ratio 15:80 batching is accomplished, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.With evenly spraying to the mild steel plate surface behind the ultra-sonic dispersion 10min before, in tube type resistance furnace, to heat-treat then, its heat treatment process parameter is: temperature is 900 ℃, 10 ℃/min of temperature rise rate, soaking time is 2h, the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
The soft steel that the surface is obtained the ferro-boron structure carries out breaking tenacity, hardness, tests such as solidity to corrosion.
Embodiment 4:Method according to embodiment 1 is handled the cold-rolling mild steel plate sample.
In anhydrous ethanol medium, FeB and Fe
2O
31:4 in molar ratio, after liquid-solid quality is accomplished than stuck-at-5:80 batching, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.With evenly spraying to the mild steel plate surface behind the ultra-sonic dispersion 10min before, seasoning is heat-treated in tube type resistance furnace then; Its heat treatment process parameter is: temperature is 900 ℃; Temperature rise rate is 10 ℃/min, and soaking time is 8h, and the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
The soft steel that the surface is obtained the ferro-boron structure carries out breaking tenacity, hardness, tests such as solidity to corrosion.
Embodiment 5:Method according to embodiment 1 is handled the cold-rolling mild steel plate sample.
In anhydrous ethanol medium, FeB and Fe
2O
31:1 in molar ratio, after liquid-solid quality is accomplished than stuck-at-5:80 batching, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.Evenly spray to the mild steel plate surface behind the ultra-sonic dispersion 10min before using, seasoning is heat-treated in tube type resistance furnace then; Its heat treatment process parameter is: temperature is 1000 ℃; Temperature rise rate is 10 ℃/min, and soaking time is 2h, and the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
The soft steel that the surface is obtained the ferro-boron structure carries out breaking tenacity, hardness, tests such as solidity to corrosion.
Embodiment 6:Method according to embodiment 1 prepares the cold-rolling mild steel plate sample.
In anhydrous ethanol medium, FeB and Fe
2O
31:4 in molar ratio, after liquid-solid ratio stuck-at-5:80 batching is accomplished, ball milling 30h on ball mill, preparation nanometer ferro-boron coating.Evenly spray to the mild steel plate surface behind the ultra-sonic dispersion 10min before using, seasoning is heat-treated in tube type resistance furnace then; Its heat treatment process parameter is: temperature is 1000 ℃; Temperature rise rate is 10 ℃/min, and soaking time is 8h, and the cooling gradient is that stove is cold.H
2Airshed is 180mL/min.
Claims (1)
1. one kind based on nanotechnology surface of low-carbon steel ferro-boron coating treatment process, it is characterized in that having following process and step:
(1) mild steel plate of desire being handled is through absolute ethyl alcohol, acetone and deionized water ultrasonic cleaning successively, and dry back is subsequent use;
(2) preparation of nanometer ferro-boron coating: adopt the mechanical ball milling method, with commercially available FeB powder and analytical pure Fe
2O
3By putting into ball grinder behind the certain mol proportion uniform mixing, add the certain liquid-solid ratio of a certain amount of EtOH control, ball milling number hour; Preparation technology parameter is following:
FeB:Fe
2O
3=1: (1 ~ 4) (mol ratio);
Powder: EtOH=15:80 (mass ratio);
Ball milling time=20 ~ 30h; Finally make nanometer ferro-boron coating;
(3) the above-mentioned nanometer ferro-boron coating that makes is sprayed at the surface of low-carbon steel of handling well equably, after the seasoning, in tube type resistance furnace, heat-treats under the atmosphere of hydrogen, its processing parameter is following:
Temperature: 700 ~ 1000 ℃;
Heating gradient: 10 ℃/min;
Heat treatment time: 2 ~ 8h;
The cooling gradient: stove is cold;
H
2Airshed is: 150 ~ 200mL/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864449A (en) * | 2012-09-28 | 2013-01-09 | 上海大学 | Method for alloying surface of aluminum based on nano technology |
| CN103255409A (en) * | 2013-05-13 | 2013-08-21 | 上海大学 | Method of preparing stainless steel coating on surface of low carbon steel based on nanotechnology |
| CN107502944A (en) * | 2016-06-14 | 2017-12-22 | 张家港贸安贸易有限公司 | The preparation method of surface of low-carbon steel Fe FeB sedimentaries |
Citations (3)
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|---|---|---|---|---|
| CN101235478A (en) * | 2008-02-26 | 2008-08-06 | 上海大学 | Steel plate surface nano induction nitrogen alloying 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 |
| CN102021570A (en) * | 2010-12-15 | 2011-04-20 | 上海大学 | Treatment process for forming SiO2 coating/Ni-Si alloyed layer composite structure on surface of cold-rolled mild steel plate |
-
2011
- 2011-08-31 CN CN201110254261A patent/CN102321862A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235478A (en) * | 2008-02-26 | 2008-08-06 | 上海大学 | Steel plate surface nano induction nitrogen alloying 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 |
| CN102021570A (en) * | 2010-12-15 | 2011-04-20 | 上海大学 | Treatment process for forming SiO2 coating/Ni-Si alloyed layer composite structure on surface of cold-rolled mild steel plate |
Non-Patent Citations (1)
| Title |
|---|
| JIBO JIANG ET. AL.: "Preparation of Fe2B boride coating on low-carbon steel surfaces and its evaluation of hardness and corrosion resistance", 《SURFACE & COATINGS TECHNOLOGY》, vol. 206, 26 July 2011 (2011-07-26), pages 473 - 478, XP028283873, DOI: doi:10.1016/j.surfcoat.2011.07.053 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864449A (en) * | 2012-09-28 | 2013-01-09 | 上海大学 | Method for alloying surface of aluminum based on nano technology |
| CN103255409A (en) * | 2013-05-13 | 2013-08-21 | 上海大学 | Method of preparing stainless steel coating on surface of low carbon steel based on nanotechnology |
| CN107502944A (en) * | 2016-06-14 | 2017-12-22 | 张家港贸安贸易有限公司 | The preparation method of surface of low-carbon steel Fe FeB sedimentaries |
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Application publication date: 20120118 |