CN109609844B - Method for improving high silicon steel plate blank thermal deformation plasticity by adding heavy rare earth yttrium element - Google Patents

Method for improving high silicon steel plate blank thermal deformation plasticity by adding heavy rare earth yttrium element Download PDF

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CN109609844B
CN109609844B CN201811531176.4A CN201811531176A CN109609844B CN 109609844 B CN109609844 B CN 109609844B CN 201811531176 A CN201811531176 A CN 201811531176A CN 109609844 B CN109609844 B CN 109609844B
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silicon steel
rare earth
high silicon
equal
percent
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CN109609844A (en
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秦镜
曹艳燕
赖朝彬
赵鸿金
刘德福
罗呼学
徐星星
聂金成
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • Y02P10/25—Process efficiency

Abstract

The invention belongs to the technical field of metal material preparation, and discloses a method for improving high silicon steel slab temperature deformation plasticity by adding heavy rare earth yttrium elements; the chemical components in percentage by mass are: si:6.0 to 6.6 percent, Y: 0.005-0.03 percent, less than or equal to 0.004 percent of C, less than or equal to 0.003 percent of S, less than or equal to 0.005 percent of O, less than or equal to 0.005 percent of N, less than or equal to 0.008 percent of P, and the balance of Fe. After 0.005% -0.03% of yttrium element is added into high silicon steel, the tensile fracture elongation of the forging plate blank is improved from 0.8% to 2.3% at 200 ℃, from 1.8% to 6.1% at 400 ℃ and from 2.5% to 45% at 600 ℃, and the tensile strength is also obviously improved. The invention adds trace heavy rare earth yttrium element in the high silicon steel, plays roles of deep purification, grain refinement and microalloying, reduces the generation of ordered phases of the high silicon steel, and obviously improves the high silicon steel temperature deformation plasticity.

Description

Method for improving high silicon steel plate blank thermal deformation plasticity by adding heavy rare earth yttrium element
Technical Field
The invention belongs to the technical field of metal material preparation, and particularly relates to a method for improving high-silicon steel slab temperature deformation plasticity by adding heavy rare earth yttrium elements.
Background
Currently, the current state of the art commonly used in the industry is as follows: the high silicon steel generally refers to Si-Fe alloy containing 4.5% -6.7% of Si by mass, and the common high silicon steel is 6.5% of Si-Fe. The resistivity ρ=82 μΩ·cm of the 6.5% si high silicon steel is about one time higher than that of the 3% si silicon steel (3% si silicon steel ρ=48 μΩ·cm), the saturation induction B s =1.80T, lower relative to 3% si silicon steel (3% si silicon steel B s =2.03t), magnetostriction coefficient λ s Approximately zero, magnetic anisotropy constant K 1 About 40% lower than 3% si silicon steel. The magnetic characteristic of the high silicon steel is that the iron loss is obviously reduced at high frequency, the maximum magnetic permeability is high and the coercive force is low. Positive directionBecause of the excellent soft magnetic properties such as low iron loss, high magnetic permeability and low magnetostriction coefficient, the high silicon steel is most suitable for manufacturing high-speed high-frequency motors, audio and high-frequency transformers, choke coils, magnetic shielding under high frequency and the like, has wide application prospects in the fields of energy conservation, equipment noise reduction and the like, and can meet the development demands of high efficiency, miniaturization, high speed, high frequency and low noise of electromechanical equipment in the industrial fields such as power, electronics and the like.
The high silicon steel becomes hard and brittle due to the occurrence of ordered phases at low temperature, the processability is rapidly reduced, cold working deformation is difficult, rolling forming by using a conventional process is difficult, other special preparation methods such as a Chemical Vapor Deposition (CVD) method, a hot dipping diffusion method, a chilled melt-spinning method, a powder rolling sintering method, a spray forming method and the like are adopted to avoid large-scale plastic deformation, but the large-scale industrial production is difficult due to high cost, complex technology and low efficiency, and the only CVD method which is put into production is difficult to carry out because of equipment corrosion and easy environmental pollution, and the environment protection requirement of people is not met. The plasticity can be improved by mastering the deformation softening and annealing hardening rules of the iron-based ordered solid solution and controlling multiple ordered transformation and formulating reasonable processing and heat treatment processes to carry out toughening plasticization treatment on the high-silicon steel. The high silicon steel sheet prepared based on the rolling method has the advantages of uniform components, good surface quality and the like, can fully utilize the tissue heredity, such as the hereditary property of the initial <100> oriented columnar crystal, optimally control the deformation and the recrystallization texture, and finally obtain the strong lambda texture (< 001>// ND) or the strong eta texture (< 001>// RD) to improve the magnetic performance. Therefore, the high silicon steel sheet strip prepared based on the rolling method has high industrial application value.
The research on preparing high silicon steel sheet by rolling method is from overcoming the intrinsic brittleness, continuously improving the processing and heat treatment technology to toughening and plasticizing the high silicon steel sheet, to improving the magnetic performance by optimizing and controlling the texture. Despite the great progress in rolling high silicon steel sheet, the toughness, plasticity and magnetic properties of the rolled high silicon steel sheet are still to be improved. To overcome the intrinsic brittleness of high silicon steel, the deformation is promoted by improving the rolling and heat treatment processDisorder of matrix structure. Namely, a method of combining hot rolling, warm rolling and cold rolling is adopted, and a method of oil quenching, water quenching and other rapid cooling methods are adopted for the high silicon steel in the A2 state of a high Wen Moxu structure, so that unordered states are kept to low temperature as much as possible, and ordered phases B2 and D0 are restrained 3 The method is characterized in that the size of ordered domains is reduced, a large number of dislocation is introduced to continuously slide through large plastic deformation, and the low-temperature ordered structure is destroyed, so that the low-temperature plastic deformation capacity of the high-silicon steel is improved, and the method is called as a gradual toughening plasticization rolling method for short. On the other hand, the plastic deformation capability of the high silicon steel is improved by adding micro-alloy elements such as Ni, mn, B, nb, cr. Microalloying can remarkably reduce the inversion domain boundary energy of the iron-based ordered solid solution and improve the independent sliding capacity of partial dislocation; the trace B element can strengthen the binding force of the grain boundary, so that dislocation activation and the regulation effect on slippage at the grain boundary are improved, and the slippage can be started and transferred at the grain boundary at a lower stress accumulation level; nb is favorable for solidifying harmful elements such as carbon, nitrogen and the like, forming fine carbon nitride to be dispersed and separated out, preventing dislocation line movement, improving recrystallization nucleation density, refining grain structure and improving strength and plasticity; while adding Cr element refines grains, the dislocation density is reduced and the ordered phase is reduced. A method for preparing 6.5% high silicon steel by adopting a twin-roll thin strip continuous casting technology is provided, and the tensile ductility of the high silicon steel is enhanced by adding rare earth element Ce. The research result shows that Ce is generated 2 O 2 The S precipitate plays a role of a nucleating agent, refines a solidification structure, improves the elongation of the casting belt from 22.8% (without Ce) to 56.8% at 600 ℃, and the rare earth element Ce plays a role of refining grains, strengthening grain boundaries and improving plasticity and toughness, thereby having remarkable effect of improving the mechanical property of the high silicon steel. However, if the addition of rare earth elements affects the ordered transformation of 6.5% Si high silicon steel, the rare earth microalloying pair B2 and D0 3 The influence of the domain boundary density and the domain boundary energy is not clear, and the mechanism of improving the plasticity is still to be studied deeply.
The effect of rare earth in steel can be generally summarized into purification effect, deterioration effect and microalloying effect, and the research results of a large number of steel grades prove that trace rare earth can effectively improve carbon steel,The impact toughness and plasticity of low alloy steel and alloy steel, and the improvement of magnetic properties by adding rare earth elements Ce and La into silicon steel are also reported. Mainly improves the magnetic performance by purifying molten steel, modifying inclusions, refining cast structure and improving recrystallization texture. Because the rare earth has active chemical property and strong affinity with oxygen and sulfur elements, the oxygen and sulfur sites in the molten steel after rare earth treatment are rapidly reduced, the inclusions are effectively deteriorated, and high-melting-point spherical or approximately spherical rare earth oxides, sulfides and oxysulfides are easily generated, thereby playing a role in desulfurization and deoxidation. 0.0055wt% of Ce is added to 2.9% silicon steel, which not only can obviously inhibit the precipitation of MnS, but also can effectively deteriorate AlN and Al 2 O 3 And the inclusions are alike, so that the maximum average size of the inclusions and the minimum average density of the inclusions are obtained, and the harm of the inclusions to magnetic performance is reduced. On the premise that the cleanliness of molten steel is high and the sulfur-oxygen content can be controlled at a low level, rare earth elements are added, and micron-sized or smaller rare earth oxysulfide can be generated as second phase particles to promote non-uniform nucleation, so that the cast structure is refined, and the steel matrix is strengthened. The magnetic properties of electrical steels are largely dependent on texture and texture. When 0.003wt% of rare earth element Ce is added to 1.15% Si non-oriented electrical steel, {110}<001>The texture is strongest, the magnetic induction is highest, the grain size is optimal, and the iron loss reaches the minimum. In the non-oriented electrical steel containing 1.2 percent Si-0.4 percent Al of rare earth Ce, the proportion of the favorable texture components in the steel is firstly increased and then reduced along with the increase of the Ce content, and the proportion of the favorable texture components is largest when the Ce content is 0.0051 weight percent, and due to the purification effect of adding a proper amount of Ce, the effect of blocking the migration of the original inclusion to the grain boundary is weakened, and the nucleation and growth of {111} grains are effectively inhibited. With the increase of Ce content in 2.9Si% high grade non-oriented electrical steel, the texture factors {100}/{111} and ({ 100} + {110 })/{ 111} are increased and then decreased, when the Ce content is 0.0055wt%, the texture factor reaches the maximum value, and the optimal Ce content in 3.0% Si silicon steel is 0.0062wt%. The research results show that the rare earth content which is most favorable for magnetic performance shows an ascending trend along with the increase of the silicon content, so that whether the optimal rare earth content conforms to the trend in the 6.5 percent Si high silicon steel,whether the high silicon steel has certain specificity due to the ordered structure transformation exists or not is yet to be studied.
At present, rare earth elements added into electrical steel by scholars at home and abroad only adopt Ce and La, and the rare earth elements belong to light rare earth elements, and the application of heavy rare earth yttrium (Y) element in the electrical steel is not reported yet. At present, light rare earth Ce and La are adopted in China, on one hand, the light rare earth is huge in yield and mainly derived from Bute rare earth ores of internal Mongolia bayan, and heavy rare earth Y is mainly derived from Gannan ionic rare earth ores, so that the yield is small, and the price is more expensive than that of the light rare earth Ce and La, and the light rare earth Ce and La are developed and applied later. Technically, the advantages of adopting heavy rare earth Y compared with light rare earth Ce and La are as follows: (1) The density of the compound YOxSy formed by the rare earth element Y in the molten steel is about 4.25, and the density of the compound La (Ce) OxSy formed by La and Ce reaches 6.0. According to Stocks formula, the floating speed of YOxSy composite inclusion in molten steel is doubled compared with La (Ce) OxSy composite inclusion, thereby being more beneficial to the impurity removal of molten steel and having better purifying effect. (2) The atomic radius of the heavy rare earth element Y is smaller than that of the light rare earth elements La and Ce, and the atomic radius of Y isThe atomic radii of La and Ce are +.>And->Y has a solid solubility in steel greater than La and Ce, and Y diffuses faster in alpha-Fe than La and Ce, because of the higher binding energy of solute atoms to vacancies, the microalloying effect is more pronounced.
In summary, the problems of the prior art are: at present, rare earth elements added into electrical steel by scholars at home and abroad only adopt Ce and La, and the rare earth elements belong to light rare earth elements, and the application of heavy rare earth yttrium (Y) element in the electrical steel is not reported yet.
Difficulty and meaning for solving the technical problems:
the invention plays a positive role in improving the processing and forming performance of 6.5% high-silicon electrical steel, improving the yield and promoting the large-scale industrialized application of the high-silicon steel. Meanwhile, a new direction is opened up for the application of rare earth Y, the sustainable development of the heavy rare earth industry is promoted, the industrialized development of high-silicon steel is promoted, the advantages of rare earth resources are converted into the varieties and economic advantages of steel, and the method has important academic value and economic value.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for improving the temperature deformation plasticity of a high silicon steel plate blank by adding heavy rare earth yttrium elements.
The invention is realized in such a way that the heavy rare earth yttrium element is added to improve the high silicon steel plate blank temperature deformation plasticity, and the method for adding the heavy rare earth yttrium element to improve the high silicon steel plate blank temperature deformation plasticity comprises the following steps:
firstly, casting a high-silicon steel ingot by vacuum induction melting, wherein the ingot comprises the following chemical components in percentage by mass: si:6.0 to 6.6 percent, Y: 0.005-0.03%, C less than or equal to 0.004%, S less than or equal to 0.003%, O less than or equal to 0.005%, N less than or equal to 0.005%, P less than or equal to 0.008%, and the balance being Fe;
step two, forging the high silicon steel ingot into a plate blank at 1050-800 ℃.
Further, the heavy rare earth yttrium element is added in a pure rare earth yttrium metal mode.
Another object of the present invention is to provide a high silicon steel slab prepared by the method for improving the thermal deformation plasticity of a high silicon steel slab by adding heavy rare earth yttrium element, wherein the tensile elongation at break of the high silicon steel slab is increased to 2.3% at 200 ℃, to 6.1% at 400 ℃ and to 45% at 600 ℃. The tensile sample is a cylindrical sample selected from a plate blank along the length direction, the standard sample size is 5mm multiplied by 80mm, the sample gauge length is 25mm, the threads at two ends of the sample are 2 multiplied by M12-6h, the surface is smooth, and the roughness is Ra0.8.
In summary, the invention has the advantages and positive effects that: the high-temperature deformation toughness and plasticity of the high-silicon steel forging stock are obviously improved, and the subsequent warm deformation processing is facilitated. In molten steel at high temperature, Y reacts with S, O, P, C, N to form YS, Y 2 O 3 、YP、Compounds such as YC and YN to realize purification and impurity removal, and Y and impurities such as Al 2 O 3 Reacting MnS to form Y 2 O 3 And YS, and Al 2 O 3 MnS becomes Mn and Al. Thus, precipitation of second phase particles such as MnS, A1N and the like finely dispersed in the electrical steel can be inhibited, and iron loss is reduced. The rare earth element Y forms a compound in molten steel in the form of YO x S y Mainly, the density is about 4.25, and La and Ce form a compound of La (Ce) O x S y Mainly, its density reaches 6.0. YO according to the Stocks formula x S y The floating speed of the composite inclusion in the molten steel is higher than that of La (Ce) O x S y Double the composite inclusion, and is more beneficial to impurity removal. In addition, the atomic radius of the heavy rare earth element Y is smaller than that of the light rare earth elements La and Ce, and the atomic radius of Y isLa and Ce have atomic radii ofAnd-> It can be inferred that the solid solubility of Y in steel is greater than that of La and Ce in steel. Recently, a scholars calculate the diffusion property of rare earth elements Y, la and Ce as solutes in alpha-Fe by using the first sexual principle. The results indicate that Y diffuses most rapidly in alpha-Fe and exceeds the self-diffusion coefficient of Fe below 970K. Y has an order of magnitude greater diffusion coefficient than La, while Ce has the lowest diffusion rate, Y has higher binding energy of solute atoms and vacancies, and the microalloying effect is more obvious.
The invention opens up a new direction for the application of rare earth Y for fully exerting the advantages of Jiangxi provinces on rare earth Y resources, promotes the sustainable development of rare earth industry, promotes the industrialized development of high silicon steel, converts the advantages of rare earth resources into the variety and economic advantages of steel, and has important academic value and economic value.
Drawings
FIG. 1 is a flow chart of a method for improving the thermal deformation plasticity of a high silicon steel slab by adding heavy rare earth yttrium elements.
FIG. 2 is a graph showing the tensile true stress-true strain curve of a high silicon steel sample without rare earth and with 0.03% Y provided in the example of the present invention;
in the figure: (a) 200 ℃; (b) 400 ℃; (c) 600 ℃.
FIG. 3 is a schematic drawing of the tensile fracture morphology of a rare earth-free and 0.03% Y high silicon steel sample at 400 ℃ provided by an embodiment of the present invention;
in the figure: (a) tensile fracture morphology of a Y-0 high silicon steel sample; (b) the tensile fracture morphology of the Y-0.03 high silicon steel sample.
FIG. 4 is a schematic drawing of the tensile fracture morphology of a rare earth-free and 0.03% Y high silicon steel sample at 600 ℃ provided by an embodiment of the present invention;
in the figure: (a) tensile fracture morphology of a Y-0 high silicon steel sample; (b) the tensile fracture morphology of the Y-0.03 high silicon steel sample.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
At present, rare earth elements added into electrical steel by scholars at home and abroad only adopt Ce and La, and the rare earth elements belong to light rare earth elements, and the application of heavy rare earth yttrium (Y) element in the electrical steel is not reported yet. The invention opens up a new direction for the application of rare earth Y, promotes the sustainable development of the rare earth industry, promotes the industrialized development of high silicon steel, converts the advantages of rare earth resources into the variety and economic advantages of steel, and has important academic and economic values.
The principle of application of the invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the method for improving the high-silicon steel slab temperature deformation plasticity by adding the heavy rare earth yttrium element provided by the embodiment of the invention comprises the following steps:
s101: vacuum induction melting is adopted to cast high silicon steel ingots, and the chemical components of the ingots are as follows by mass percent: si:6.0 to 6.6 percent, Y: 0.005-0.03%, C less than or equal to 0.004%, S less than or equal to 0.003%, O less than or equal to 0.005%, N less than or equal to 0.005%, P less than or equal to 0.008%, and the balance being Fe;
s102: the high silicon steel ingot is forged into a plate blank at 1050-800 ℃.
In a preferred embodiment of the invention, the heavy rare earth yttrium element is added in the form of pure rare earth yttrium metal.
In the preferred embodiment of the invention, the tensile elongation at break of the high silicon steel slab is increased to 2.3% at 200 ℃, 6.1% at 400 ℃ and 45% at 600 ℃.
The application effect of the present invention will be described in detail with reference to the detection results.
As shown in FIG. 2, the tensile strength and the tensile elongation at break after adding rare earth Y are obviously improved greatly by comparing the tensile true stress-true strain curves of the high silicon steel samples without rare earth and with 0.03% of Y.
And observing the stretching fracture morphology of the high silicon steel samples with different rare earth contents at different temperatures by using a Sigma type field emission scanning electron microscope, and analyzing the fracture mechanism according to the fracture morphology.
FIG. 3 is a drawing of the tensile fracture morphology of a high silicon steel specimen at 400 ℃. FIG. 3 (a) shows the appearance of a tensile fracture of a Y-0 high silicon steel sample, wherein cleavage steps can be seen on the section of a crystal grain, and after local enlargement, a plurality of tiny micropores on a tearing edge are clearly visible, and the fracture belongs to cleavage fracture-quasi cleavage fracture mixed fracture. FIG. 3 (b) shows the appearance of a tensile fracture of a Y-0.03 high silicon steel sample, wherein a large number of dimples appear on the fracture surface, the dimples are fine and shallow, and dense small dimples are arranged around the large dimples, and the fracture belongs to typical ductile fracture. Illustrating that 0.03% rare earth Y converts the fracture form of high silicon steel from a cleavage fracture-quasi-cleavage fracture mixture fracture to a ductile fracture upon stretching at 400 ℃.
FIG. 4 is a drawing of the tensile fracture morphology of a high silicon steel specimen at 600 ℃. Fig. 4 (a) shows the tensile fracture morphology of the Y-0 high silicon steel sample, and the obvious cleavage step can be seen, and the cleavage fracture belongs to a cleavage fracture-quasi cleavage fracture mixed fracture mode. FIG. 4 (b) shows the appearance of a tensile fracture of a Y-0.03 high silicon steel sample, and a large number of ductile pits are visible at the fracture, and are large and deep, and a plurality of small ductile pits are arranged around the large ductile pits, which belong to ductile fracture. It can be seen that the addition of 0.03% Y improves the high temperature tensile toughness of the high silicon steel.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (1)

1. The method for improving the high-silicon steel slab thermal deformation plasticity by adding the heavy rare earth yttrium element is characterized by comprising the following steps of:
firstly, casting a high silicon steel ingot by vacuum induction melting, wherein the ingot comprises the following chemical components in percentage by mass: si:6.0 to 6.6 percent, Y: 0.005-0.03%, C less than or equal to 0.004%, S less than or equal to 0.003%, O less than or equal to 0.005%, N less than or equal to 0.005%, P less than or equal to 0.008%, and the balance being Fe;
step two, forging the high silicon steel ingot into a plate blank at 1050-800 ℃;
the heavy rare earth yttrium element is added in a pure rare earth yttrium metal mode;
the tensile fracture elongation of the high silicon steel plate blank is improved to 2.3% at 200 ℃ and is improved to 6.1% at 400 ℃.
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CN110042312A (en) * 2019-05-30 2019-07-23 江西理工大学 A kind of high silicon steel plate and preparation method thereof that rare-earth yttrium is modified
CN110387502B (en) * 2019-07-23 2020-12-08 辽宁石油化工大学 High-silicon steel sheet and cryogenic rolling process for preparing same
CN112359287A (en) * 2020-11-16 2021-02-12 湖南上临新材料科技有限公司 Non-oriented silicon steel for high-efficiency motor and preparation method thereof

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