CN109321844B - Rare earth super-strong steel and preparation method thereof - Google Patents
Rare earth super-strong steel and preparation method thereof Download PDFInfo
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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Abstract
The invention belongs to the technical field of metallurgy, and particularly relates to rare earth super-strong steel and a preparation method thereof. According to the invention, trace rare earth elements are added into the maraging steel, so that the usage amount of Ni is reduced, the use of Co is eliminated, and the cost is obviously reduced; the rare earth super-strong steel obtained by the invention has the tensile strength of not less than 2000MPa at room temperature (20 ℃), the elongation of not less than 9%, higher tensile strength and excellent toughness, and overcomes the problems of high strength and low plasticity of the traditional maraging steel.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to rare earth super-strong steel and a preparation method thereof.
Background
The maraging steel takes a carbon-free or low-carbon iron-nickel martensite as a matrix, generates intermetallic compound precipitation strengthened high-strength steel after aging heat treatment at about 500 ℃, and is widely applied to the fields of military industry, aviation, aerospace, atomic energy and the like. Mainly comprises 3 typical series of 18Ni, 20Ni and 25Ni, wherein the manufacturing process of the 18Ni series is easiest and most widely applied. Maraging steel achieves the ultra-high strength of the alloy mainly by a combination of solid solution strengthening, phase transformation strengthening and aging strengthening, wherein the aging strengthening contributes most to the strength. The typical maraging steel such as 18Ni is quenched after solution treatment, and then is subjected to aging treatment at about 500 ℃ to ensure that second phase particles are dispersed and precipitated to achieve the effect of strengthening the matrix. In the early stage of the aging treatment, amplitude-modulated decomposition occurs in the maraging steel firstly, and solute atoms form Ni-Mo-Ti enrichment through upward slope diffusionRegion, thereby forming fine Ni3Mo、Ni3Ti、Fe2Mo and the like precipitate precipitated phases, and the precipitated phases can have strong interaction with dislocation and stacking fault in the deformation process, so that the aim of improving the strength of the material is fulfilled.
The maraging steel achieves the effects of adjusting the structure, controlling the precipitation and the like mainly by adding strong alloy elements such as Co, Mo, Ti, Al and the like into Fe-Ni alloy. As the strength grade increases, the amount of alloying elements used also gradually increases. Among them, the use of a large amount of Co element causes the cost of the maraging steel to be greatly increased, limiting the wide use thereof. In addition, because a semi-coherent interface is formed between precipitated particles and a matrix in the traditional maraging steel, larger non-uniformly distributed coherent distortion can be generated, so that the tendency of cracking of the material in the deformation process is increased, and the alloy has high strength and cannot simultaneously keep good plasticity.
Disclosure of Invention
The invention aims to provide the rare earth super-strong steel, which can reduce the cost and enhance the strength and toughness of the steel.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides rare earth super-strong steel which comprises the following components in percentage by mass: 13.00-16.00% of Ni, 0.30-4.00% of Al, 0-4.00% of Mo, 0.60-0.80% of Nb, 0.03-0.08% of C, 0.01-0.02% of B, 0.10-5.50% of Mn2.005-0.10% of W, 0.005-0.10% of rare earth and the balance of Fe.
Preferably, the rare earth is La and/or Ce.
Preferably, when the rare earth is a mixture of La and Ce, the rare earth super-strong steel comprises the following components in percentage by mass: la more than or equal to 0.01% and less than or equal to 0.1%, Ce more than or equal to 0.005% and less than or equal to 0.09%, Ni 13.00-16.00%, Al 0.30-4.00%, Mo 0-4.00%, Nb 0.60-0.80%, C0.03-0.08%, B0.01-0.02%, Mn 2.10-5.50%, W0.10-0.20%, and the balance of Fe.
Preferably, when the rare earth is La or Ce, the rare earth super-strong steel comprises the following components in percentage by mass: 13.00-15.00% of Ni0.30-4.00% of Al, 0-4.00% of Mo, 0.60-0.80% of Nb, 0.03-0.08% of C, 0.01-0.02% of B, 2.10-5.50% of Mn, 0.10-0.20% of W, 0.005-0.10% of rare earth and the balance of Fe.
Preferably, the mass ratio of B to rare earth is 1-10: 1.
the invention provides a preparation method of rare earth super-strong steel, which comprises the following steps:
(1) sequentially preserving heat and forging the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and air cooling to obtain a forged blank;
(2) heating the forging stock in the step (1) to 905 +/-15 ℃ for heat preservation to obtain a stock;
(3) and (3) carrying out aging treatment on the blank in the step (2) at the temperature of 500 +/-50 ℃ to obtain the rare earth super-strong steel.
Preferably, the heat preservation time in the step (1) is 2-5 h.
Preferably, the forging deformation amount in the step (1) is 0.3-0.4.
Preferably, the heat preservation time in the step (2) is 5-60 minutes.
Preferably, the heat preservation time of the aging treatment in the step (3) is 60-10000 minutes.
The invention provides the rare earth super-strong steel, and the use amount of Ni is reduced by adding trace rare earth elements into the maraging steel, and the use of Co is cancelled, so that the cost is obviously reduced.
The rare earth super-strong steel obtained by the invention has the tensile strength of not less than 2000MPa at room temperature (20 ℃), the elongation of not less than 9%, higher tensile strength and excellent toughness, and overcomes the problems of high strength and low plasticity of the traditional maraging steel.
The invention provides a preparation method of rare earth super-strong steel, which comprises the steps of carrying out heat preservation treatment at 905 +/-15 ℃, taking a precipitated NbC phase as an auxiliary strengthening phase, and precipitating a large amount of Ni (Al, Fe) with a B2 structure as a main strengthening phase in the heat preservation aging heat treatment process at 500 +/-50 ℃; and the interfacial energy of a coherent interface is further reduced through the segregation of rare earth atoms in the interface region of Ni (Al, Fe) and a martensite matrix in the heat preservation process, so that the dispersion distribution and precipitation of small-size Ni (Al, Fe) are promoted, and the effect of stabilizing precipitated particles of Ni (Al, Fe) is achieved, thereby ensuring the strength of the rare earth super-strong steel and enhancing the toughness of the rare earth super-strong steel.
Drawings
FIG. 1 is a graph showing the change in hardness during aging of test steels # 1 and # 2 according to the example of the present invention;
FIG. 2 is a tensile stress-strain curve of test steels # 1 and # 2 according to the present invention in examples;
FIG. 3 is a morphology chart of a precipitated phase of 2# test steel at an aging peak in the embodiment of the invention;
FIG. 4 is a graph showing a differential charge density distribution between La atoms and Ni atoms in an example of the present invention.
Detailed Description
The invention provides rare earth super-strong steel which comprises the following components in percentage by mass: 13.00-16.00% of Ni, 0.30-4.00% of Al, 0-4.00% of Mo, 0.60-0.80% of Nb, 0.03-0.08% of C, 0.01-0.02% of B, 0.10-5.50% of Mn2.005-0.10% of W, 0.005-0.10% of rare earth and the balance of Fe.
The rare earth super-strong steel provided by the invention comprises 13.00-16.00% of Ni by mass, preferably 13.5-15.5%, and more preferably 14-15%. In the present invention, the Ni element can be dissolved into the matrix, plays a role in solid solution strengthening and changing the lattice constant of the matrix, and forms a Ni (Al, Fe) strengthening phase with Al during aging heat treatment.
The rare earth super-strong steel provided by the invention comprises 0.30-4.00% of Al by mass, preferably 1.00-3.00%, and more preferably 1.50-2.50%. In the invention, the Al element can be dissolved in the matrix to play a role of solid solution strengthening, and forms Ni (Al, Fe) strengthening phase with Ni in the aging heat treatment process, and simultaneously can increase the martensite transformation starting temperature of the rare earth super-strong steel.
The rare earth super-strong steel provided by the invention comprises 0-4.00% of Mo, preferably 0.50-3.50%, and more preferably 1.00-2.50% by mass. In the invention, after the Mo element exists in a solid solution state in the matrix, the lattice constant of the matrix can be increased to be close to that of Ni (Al, Fe), so that the effect of regulating and controlling the degree of mismatching of the interface between the Ni (Al, Fe) precipitation phase and the matrix is achieved.
The rare earth super-strong steel provided by the invention comprises 0.60-0.80% of Nb by mass percentage, and preferably 0.65-0.75%. In the invention, the Nb element and C can form NbC precipitates, which play a role in strengthening a matrix and can prevent the grain growth behavior of the rare earth super-strong steel in the heat preservation process of 905 +/-15 ℃. In addition, the Nb can not only play a role in solid solution strengthening after being dissolved into the matrix, but also play a role in delaying the growth of crystal grains in the heat preservation process of 905 +/-15 ℃.
The rare earth super-strong steel provided by the invention comprises 0.03-0.08% of C by mass, preferably 0.04-0.07%, and more preferably 0.05-0.06%. In the invention, when the mass percent of C is more than 0.05%, the mass percent of W is preferably more than 0.15%, the mass percent of Mo is preferably 0, namely Mo is not added, at the moment, the mass percent of each component of the rare earth super strong steel is preferably 13.00-16.00%, 0.30-4.00%, 0.60-0.80% of Nb, more than 0.05% < C < 0.08%, 0.01-0.02% of B, 2.10-5.50% of Mn, more than 0.15% < W < 0.20%, 0.005-0.10% of rare earth and the balance of Fe. In the invention, the C element can form NbC precipitates with Nb, play a role in precipitation strengthening and effectively control the grain size. According to the invention, the content of C is 0.03-0.08%, so that the formation of large-size carbides can be avoided, and the plasticity and toughness and the welding performance of the rare earth super-strong steel are enhanced; since the rare earth addition reduces C, Mo solubility in the ferrite matrix, Mo is not added when the mass percent of C is greater than 0.05% in order to avoid MoC formation.
The rare earth super-strong steel provided by the invention comprises 0.01-0.02% of B by mass, preferably 0.012-0.018%, and more preferably 0.015-0.014%. In the invention, the mass ratio of B to rare earth is preferably 1-10, and more preferably 3-8. In the invention, the B element can purify grain boundaries and improve the toughness of the steel; the B element can promote the segregation behavior of the rare earth element in the grain boundary and enhance the function of purifying the grain boundary by the rare earth element.
The rare earth super-strong steel provided by the invention comprises 2.10-5.50% of Mn by mass, preferably 2.50-5.00%, and more preferably 3.00-4.50%. In the present invention, the Mn element promotes the precipitation behavior of Ni (Al, Fe) during the aging heat treatment, and enhances the precipitation strengthening effect by improving the interfacial energy through the distribution in the precipitation interfacial region.
The rare earth super-strong steel provided by the invention comprises 0.10-0.20% of W by mass, preferably 0.12-0.18%, and more preferably 0.15-0.16%. In the invention, the W element is a solid solution strengthening element and can form carbide with C, which is beneficial to improving the strength of the rare earth super-strong steel.
The rare earth super-strong steel provided by the invention comprises 0.005-0.10% of rare earth by mass, preferably 0.01-0.08%, and more preferably 0.02-0.05%. In the present invention, the rare earth is preferably La and/or Ce. In the invention, when the rare earth is a mixture of La and Ce, the mass percentage of each component of the rare earth super-strong steel is preferably as follows: la more than or equal to 0.01% and less than or equal to 0.1%, Ce more than or equal to 0.005% and less than or equal to 0.09%, Ni 13.00-16.00%, Al 0.30-4.00%, Mo 0-4.00%, Nb 0.60-0.80%, C0.03-0.08%, B0.01-0.02%, Mn 2.10-5.50%, W0.10-0.20%, and the balance of Fe.
In the invention, when the rare earth is La or Ce, the mass percentage of each component of the rare earth super-strong steel is preferably as follows: 13.00-15.00% of Ni, 0.30-4.00% of Al, 0-4.00% of Mo, 0.60-0.80% of Nb, 0.03-0.08% of C, 0.01-0.02% of B, 0.10-5.50% of Mn2.005-0.10% of W, 0.005-0.10% of rare earth and the balance of Fe.
In the invention, when the La element is added independently, La and Ni have an attraction effect and can promote the precipitation of Ni (Al, Fe), so that less C content can be combined to achieve the effect of integral strengthening, and meanwhile, the reduction of the C content is also beneficial to improving the ductility and weldability of the alloy; when the element Ce is added independently, Ce and Al have an attraction effect, so that Al is promoted to be enriched around Ce atoms, and a potential nucleation point is provided for Ni (Al, Fe) precipitation; when a mixture of La and Ce is added, the effect of promoting the precipitation of Ni (Al, Fe) is also remarkable.
The invention provides a preparation method of rare earth super-strong steel in the technical scheme, which comprises the following steps:
(1) sequentially preserving heat and forging the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and air cooling to obtain a forged blank;
(2) heating the forging stock in the step (1) to 905 +/-15 ℃ for heat preservation to obtain a stock;
(3) and (3) carrying out aging treatment on the blank obtained in the step (2) at 500 +/-50 ℃ to obtain the rare earth super-strong steel.
The invention sequentially carries out heat preservation and forging on the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and obtains a forged blank after air cooling. In the present invention, the casting blank made of the raw materials is preferably prepared by a method of smelting and then pouring, and the method of smelting and pouring is not particularly limited in the present invention, and the casting blank can be obtained by smelting and pouring in a manner well known to those skilled in the art. In the invention, the heat preservation time is preferably 2-5 h, and more preferably 3-4 h.
In the present invention, the forging deformation amount is preferably 0.3 to 0.4. In the present invention, it is preferable that the billet obtained after forging is air-cooled to room temperature to obtain a forged billet. In the invention, the casting blank is preferably forged to 30mm and then cooled in air.
After obtaining the forging stock, the invention heats the forging stock to 905 +/-15 ℃ for heat preservation to obtain the blank. The invention preferably cools the forging stock after heat preservation by water and then carries out heat preservation and aging. In the invention, the heat preservation time is preferably 5-60 min, and more preferably 20-40 min. The forging stock is subjected to heat preservation for 5-60 min at the temperature of 905 +/-15 ℃, and precipitated phases can be fully dissolved back to a matrix.
After the blank is obtained, the blank is subjected to aging treatment at 500 +/-50 ℃ to obtain the rare earth super-strong steel. In the invention, the heat preservation time of the aging treatment is preferably 60-10000 min, and more preferably 200-8000 min. According to the invention, rare earth elements can be fully diffused through aging treatment, and Ni (Al, Fe) particles are precipitated.
The rare earth super strong steel and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Manufacturing a test steel casting blank (the specific alloy components are shown in table 1) with two components by a conventional method of smelting firstly and then casting, heating the casting blank (the size of the casting blank is 300 multiplied by 250 multiplied by 50mm) to 1200 +/-15 ℃, preserving heat for 30 minutes, forging to the thickness of 30mm, and then air cooling to room temperature to obtain a forging blank;
heating the forging stock to 900 ℃, preserving heat for 2 hours, and then cooling with water to obtain a blank;
a specimen having a size of 20X 130mm was cut out of the above-mentioned blank, and the specimen was heated to 500 ℃ and then subjected to aging heat treatment, and after the aging heat treatment was completed, the specimen was cooled to room temperature by air cooling.
Table 1 alloy composition (wt.%) of test steels
| Serial number | Ni | Al | Mo | Nb | C | B | Mn | W | La | Ce | Fe |
| Test No. 1 Steel | 15.332 | 2.619 | 0.059 | 0.763 | 0.026 | 0.017 | 3.394 | 0.182 | 0.008 | 0 | Balance of |
| 2# test Steel | 14.906 | 2.641 | 0.057 | 0.751 | 0.033 | 0.021 | 3.507 | 0.187 | 0.012 | 0.008 | Balance of |
A20X 10mm sample was cut out from the aged heat-treated sample, and the surface was polished with sandpaper and then subjected to a surface hardness test, wherein the aging-course hardness change curves of the two test steels are shown in FIG. 1. As can be seen from fig. 1, both test steels reached the peak aged hardness after 8 hours of aging.
The samples after the aging heat treatment were prepared as tensile samples, and tensile tests (room temperature, 20 ℃) were carried out on a tensile testing machine, and the tensile stress-strain curves are shown in FIG. 2, and it can be seen that the tensile strengths at the aging peak of the test steels No. 1 and No. 2 reached 2171MPa and 2203MPa, respectively, and the elongations were 10.18% and 9.66%, respectively. From this, it is found that the test steel does not decrease in elongation while being significantly age-hardened, but rather increases in uniform elongation.
The appearance of precipitated phase of 2# test steel when the hardness of the aging heat treatment reached the peak was observed using a transmission electron microscope, as shown in fig. 3. FIG. 3(a) shows that the matrix consists mainly of laths of martensite with dense dislocation networks distributed within the laths; as can be seen from FIG. 3(b), fine and dispersedly distributed nearly spherical precipitates are precipitated in the matrix, and the average diameter of the precipitates is about 2-3 nm; selective electron diffraction analysis of the precipitated phase showed the precipitated phase to be a typical B2 structure.
A calculation result of the bonding energy of La in bcc-Fe and different close Ni and Al shows that the La and 1-5 close Al atoms have obvious repulsion, and the La and the Ni atoms have obvious attraction. From this fact, it is considered that in La-containing bcc-Fe, the La atom occupied region can serve as a potential nucleation site for the Ni (Al, Fe) precipitate phase, and after long-term heat-retention aging, Ni atoms are concentrated around La atoms, and then Al atoms are also concentrated in the Ni-concentrated region by diffusion, and finally, the Ni (Al, Fe) precipitate phase is formed. Further, the present invention calculates the differential charge density of the system when the La and Ni atoms are in the first vicinity, as shown in fig. 4. As can be seen from fig. 4, the region between the La atom and the Ni atom has a significant charge enrichment, indicating that a bonding effect occurs between La and Ni, which is represented by the existence of a higher binding energy between La and Ni. This indicates that during aging, a Ni-rich region tends to be preferentially formed around La atoms, thereby lowering the nucleation energy barrier of Ni (Al, Fe) precipitate phase.
The results show that the precipitation of Ni (Al, Fe) strengthening phase is accelerated due to the obvious attraction between La and Ni atoms, and the fine dispersion distribution of Ni (Al, Fe) is further promoted, so that the toughness of the rare earth super-strong steel is improved.
According to the embodiments, trace rare earth elements are added into the maraging steel, so that the use amount of Ni is reduced, the use of Co is eliminated, and the cost is obviously reduced; the rare earth super-strong steel obtained by the invention has the tensile strength of not less than 2000MPa at room temperature (20 ℃), the elongation of not less than 9%, higher tensile strength and excellent toughness, and overcomes the problems of high strength and low plasticity of the traditional maraging steel.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The rare earth super-strong steel comprises the following components in percentage by mass: la more than or equal to 0.01% and less than 0.10%, Ce more than or equal to 0.005% and less than or equal to 0.09%, Ni 13.00-16.00%, Al 0.30-4.00%, Mo 0-4.00%, Nb0.60-0.80%, C0.03-0.08%, B0.01-0.02%, Mn 2.10-5.50%, W0.10-0.20%, and the balance of Fe; the total content of La and Ce is 0.005-0.10%;
the preparation method of the rare earth super-strong steel comprises the following steps:
(1) sequentially preserving heat and forging the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and air cooling to obtain a forged blank;
(2) heating the forging stock in the step (1) to 905 +/-15 ℃ for heat preservation to obtain a stock;
(3) and (3) carrying out aging treatment on the blank in the step (2) at the temperature of 500 +/-50 ℃ to obtain the rare earth super-strong steel.
2. The rare earth super-strong steel comprises the following components in percentage by mass: 13.00-15.00% of Ni, 0.30-4.00% of Al, 0-4.00% of Mo, 0.60-0.80% of Nb, 0.03-0.08% of C, 0.01-0.02% of B, 2.10-5.50% of Mn, 0.10-0.20% of W, 0.005-0.10% of rare earth and the balance of Fe; the rare earth is La or Ce;
the preparation method of the rare earth super-strong steel comprises the following steps:
(1) sequentially preserving heat and forging the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and air cooling to obtain a forged blank;
(2) heating the forging stock in the step (1) to 905 +/-15 ℃ for heat preservation to obtain a stock;
(3) and (3) carrying out aging treatment on the blank in the step (2) at the temperature of 500 +/-50 ℃ to obtain the rare earth super-strong steel.
3. The rare earth super-strong steel according to claim 1 or 2, wherein the mass ratio of B to rare earth is 1-10: 1.
4. the method for preparing rare earth super strong steel according to any one of claims 1 to 3, comprising the steps of:
(1) sequentially preserving heat and forging the casting blank corresponding to the rare earth super-strong steel component at 1200 +/-15 ℃, and air cooling to obtain a forged blank;
(2) heating the forging stock in the step (1) to 905 +/-15 ℃ for heat preservation to obtain a stock;
(3) and (3) carrying out aging treatment on the blank in the step (2) at the temperature of 500 +/-50 ℃ to obtain the rare earth super-strong steel.
5. The preparation method according to claim 4, wherein the heat preservation time in the step (1) is 2-5 h.
6. The production method according to claim 4 or 5, wherein the forging in the step (1) has a deformation amount of 0.3 to 0.4.
7. The method according to claim 4, wherein the holding time in the step (2) is 5 to 60 minutes
8. The preparation method according to claim 4, wherein the heat preservation time of the aging treatment in the step (3) is 60 to 10000 minutes.
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