CN113388788A - MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel - Google Patents
MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel Download PDFInfo
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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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- 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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
Abstract
The invention discloses MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel which comprises the following components in percentage by weight: c0.1 to 0.2 wt% of a strong carbide forming element M, 0.6 to 2.3 wt% of the balance Fe; wherein the molar ratio of the strong carbide forming elements M to C is 1: 1.0 to 1.55. The material comprises Fe, C and M, wherein C and M form MC carbide, and Fe and M form Fe2An M-Laves phase; by adjusting the ratio of M/C to 1.0-1.55, MC carbide and Fe are precipitated simultaneously from the alloy2The content of solid solution elements in the alloy is reduced to the maximum extent by the M-Laves phase, so that the material has high thermal conductivity and hardness; meanwhile, through reducing the content of C, the condition that the die steel cracks during 3D printing can be reduced through practical verification, so that the alloy has good 3D printing process performance.
Description
Technical Field
The invention relates to the technical field of die steel, in particular to MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel.
Background
The heat conductivity of the material is a determining factor of the cooling effect of the die steel and is also a key physical property of the die material, and the heat conductivity is related to whether rapid forming can be carried out or not and the production efficiency is improved. For example, the die material adopted by the domestic existing hot stamping production line is usually H13 steel, the heat conductivity is only 25W/m.K, the stamping beat is slow, only 2-3 stamping parts can be obtained per minute, and the high-heat-conductivity die material adopted abroad can obtain 6-7 stamping parts per minute at the stamping beat, so that the stamping beat can be accelerated by a larger heat conductivity coefficient, and the production efficiency is obviously improved. In the field of injection molds, in order to solve the problem that the cooling time of a traditional injection mold is long in the injection molding production process, common improvement methods are to improve the design of a mold water channel by adding a water-insulating sheet, adding a heat-conducting needle, shortening the length of a cooling water channel and the like; in recent years, with the development of additive manufacturing technology, more and more attention has been paid to manufacturing conformal cooling water channel injection molds based on 3D printing technology. However, the thermal conductivity of 3D printing plastic die steel such as CX and MS1 in the market is usually below 20W/m · K, and although the conformal cooling water channel is adopted, the inherent characteristics of the material have the limitation of "ceiling" for improving the cooling efficiency, and are disadvantageous for shortening the production cycle of the product, reducing the warp deformation and speeding up the delivery time of the product.
On the other hand, although a great deal of research is carried out on the development of high thermal conductivity die steel and the thermal conductivity of the die steel is successfully improved greatly, such as SDCM-S developed in Japan and HTCS-130 developed by Spanish, the thermal conductivity of the SDCM-S and the HTCS-130 at 100C can reach 47W/m.K and 60W/m.K respectively, the die steel has high C content, so that the die steel tends to form large internal stress during 3D printing, and finally serious deformation or cracking phenomena occur. In summary, it is difficult for the existing die steel to have both high thermal conductivity and printing performance.
Disclosure of Invention
In order to solve the problem that the thermal conductivity and the 3D printing performance of the existing die steel cannot be obtained at the same time, the invention aims to provide the MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel, the printing performance of the alloy is improved by reducing the content of C, meanwhile, the molar ratio of C to carbide forming elements is adjusted to improve the thermal conductivity and the hardness of the alloy, and finally, the thermal conductivity of the designed die steel is more than or equal to 40W/m.K, the hardness is more than or equal to 40HRC, and the 3D printing process performance is achieved, so that the die steel with both high thermal conductivity and printing performance is developed.
The purpose of the invention is realized by adopting the following technical scheme:
the MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel comprises the following components in percentage by weight: 0.1-0.2 wt% of C, a strong carbide forming element M, and the balance Fe; wherein the molar ratio of the strong carbide forming elements M to C is 1: 1.0 to 1.55.
C forms MC carbide with M, but since the C content is reduced, it is necessary to add higher M, Fe and M form Fe2The M-Laves phase is used for improving the hardness of the additive. In designing the composition of the die steel, in order to make the alloy have high thermal conductivity, 3D printing process performance and hardness, it is necessary to make MCCarbide and Fe2Since M-Laves precipitates in the same manner, the ratio M/C is kept between 1.0 and 1.55. Because the less solute atoms that are solutionized in the matrix, the higher the thermal conductivity of the alloy when it is fully precipitation strengthened.
Further, the MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel further comprises Cr and/or Mo, wherein the Cr accounts for 0-2 wt% and the Mo accounts for 0-2 wt%. Cr is a main element for providing corrosion resistance in stainless steel, and the corrosion resistance of the alloy can be improved by adding a certain content of Cr; however, the thermal conductivity of the alloy is obviously reduced due to the excessively high Cr content, so that the Cr content is not more than 2 wt% in consideration of the corrosion resistance and the thermal conductivity of the alloy. Mo can improve the pitting corrosion resistance of stainless steel and also can improve the high-temperature softening resistance of the alloy, but excessively high Mo is dissolved in a matrix to reduce the thermal conductivity of the alloy, and the content of Mo is not more than 2 wt%.
Since Fe, Cr, Mo and M all belong to carbide forming elements and all have an unfilled d electron layer, the more the d electron layer is unfilled, the stronger the carbide forming ability is, i.e. the greater the affinity with carbon, and the more stable the carbide formed. The additive of the invention is composed entirely of carbide forming elements, and does not require the addition of a third element, and the reduction of the alloy thermal conductivity is minimal.
Further, the strong carbide forming element M is a combination of two or more of Nb, Ti, V, Ta, or Zr.
Still further, the strong carbide forming element M is one of Nb, Ti, V, Ta, or Zr.
Further, when the strong carbide forming element M is Nb, the mass ratio of Nb to the total mass is 0.01 to 1.2 wt%.
And further, when the strong carbide forming element M is Ti, the mass ratio of Ti to the total mass is 0.01-0.6 wt%.
Further, when the strong carbide forming element M is V, the mass ratio of V to the total mass is 0.01 to 0.65 wt%.
Still further, when the strong carbide forming element M is Ta, the mass ratio of Ta to the total mass is 0.01 to 0.23 wt%.
Further, when the strong carbide forming element M is Zr, the mass ratio of Zr to the total mass is 0.01 to 1.1 wt%.
Compared with the prior art, the invention has the beneficial effects that:
(1) the additive mainly comprises Fe, C and M which belong to carbide forming elements, wherein the M and the C can be combined to form MC carbide and also can be combined with the Fe to form Fe2M-Laves phase, in the presence of C, M forms M preferentially with C, and only after C is consumed by M will Fe form Fe2M-Laves phase, so M/C must be>1, but the thermal conductivity is reduced by too high M, so the invention adjusts the molar ratio relation of M and C of the strong carbide forming elements to be 1.0-1.55 so as to simultaneously precipitate MC carbide and Fe in the alloy2The M-Laves phase reduces the content of solid solution elements in the alloy to the maximum extent, so that the additive has high thermal conductivity (not less than 40W/m.K) and hardness (not less than 40HRC) at the same time; meanwhile, through reducing the content of C, the condition that the die steel cracks during 3D printing can be reduced through practical verification, so that the additive has good 3D printing process performance. Therefore, the alloy disclosed by the invention has high thermal conductivity, good additive manufacturing process performance and higher hardness, is expected to be used in the industries of injection molds and stamping molds, and remarkably improves the production efficiency and quality of 3D printed products.
(2) For the existing commercial 3D printing die steel, if C is not added, the thermal conductivity is greatly reduced and is below 20W/m.K, and in order to obtain a single martensite structure to improve the hardness of the die steel, the existing die steel needs to add a large amount of expensive austenite forming elements such as Co and Ni; the invention does not need to add a large amount of Mo and W to improve the strength of the additive, only adopts C to ensure the formation of a single martensite matrix, and greatly reduces the cost.
(3) Cr and Mo are also added, and because Fe, Cr, Mo and M all belong to carbide forming elements, the additive disclosed by the invention is composed of the carbide forming elements, a third element does not need to be added, and the reduction of the heat conductivity of the alloy is minimum. The reason is that most of alloy elements have certain solid solubility in Fe, the higher the content of solid-dissolved elements is, the lower the thermal conductivity of the alloy is, in the invention, the addition of M firstly forms MC carbide, but only the alloy strength of the MC carbide is lower, so that other precipitated phases are reinforced together, so that the addition of M is increased, and the excessive M after being combined with C continues to form Laves phase with Fe, thereby effectively improving the strength of the alloy. However, if other phases are formed for strengthening, two additional elements are required to be added, thereby lowering the thermal conductivity. Therefore, only M which is a carbide forming element as Fe is added, and other element types are not added, so that the influence on the thermal conductivity is minimum.
Drawings
FIG. 1 is a comparison graph of calculated thermal conductivity and experimentally measured thermal conductivity of JmatPro of examples 1-3 and comparative examples 1-2.
Detailed Description
The MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel comprises the following components in percentage by weight: 0.1 to 0.2 wt% of C, 1 to 2 wt% of Cr, 1 to 2 wt% of Mo, a strong carbide forming element M, and the balance Fe; wherein the molar ratio of the strong carbide forming elements M to C is 1: 1.0 to 1.55. Wherein, the strong carbide forming element M is one or more combined elements of Nb, Ti, V, Ta or Zr, preferably 2-3 element combinations. 0 to 1.2 wt% of Nb, 0 to 0.6 wt% of Ti, 0 to 0.65 wt% of V, 0 to 2.3 wt% of Ta and 0 to 1.1 wt% of Zr.
C forms MC carbide with M, but since the C content is reduced, it is necessary to add higher M and Fe, which form Fe2The M-Laves phase is used for improving the hardness of the additive. Since Fe, Cr, Mo and M all belong to carbide forming elements and all have an unfilled d electron layer, the more the d electron layer is unfilled, the stronger the carbide forming ability is, i.e. the greater the affinity with carbon, and the more stable the carbide formed.
In the conventional application range of die steel, metal takes electron heat conduction as a main mechanism, the thermal conductivity and the electrical conductivity obey Weldmann-Franz law, and electrons are blocked by atoms and various lattice defects which move thermally during the movement process, so that resistance to heat transportation is formed. Thermal resistance is the inverse of thermal conductivity and can be broken down into two parts: thermal resistance due to lattice vibration and thermal resistance due to impurity defects. Factors influencing the movement of free electrons influence the thermal conductivity of the alloy in terms of the physical nature of the thermal conductivity of the alloy, so that the thermal conductivity of the alloy is related to the structure (lattice type), composition, impurities, point defects and plane defects of the alloy. In addition, thermal conductivity is also related to the grain size of the alloy, and the larger the grain size, the fewer interfaces in the alloy, the less resistance to electron movement, and the higher the thermal conductivity.
For a specific system of materials, the lower the lattice defects and the smaller the lattice distortion, the higher the thermal conductivity of the alloy, i.e. when the alloy is completely in a precipitation strengthening mode, the lower the solute atoms dissolved in the matrix, the higher the thermal conductivity of the alloy, therefore, common die steel components are summarized, and the corresponding mole percentages of carbide forming elements and carbon are given, as shown in table 1. It is known that as the ratio of M/C is increased, that is, as the amount of alloying elements dissolved in the alloy increases, the thermal conductivity of the alloy decreases, and particularly in the case of a printable CX and MS1 alloy, the molar ratio of the alloying elements to C is 30 or more because C is substantially not present, and the thermal conductivity is only 15W/M · K. Therefore, the C content needs to be greatly reduced in the die steel.
TABLE 1 composition, thermal conductivity and 3D printing Process Performance of typical die steels
However, the reduction of the C content causes a significant decrease in the hardness of the die steel, thereby deteriorating wear resistance, so that it is necessary to introduce a second precipitation phase to increase the hardness of the alloy in addition to carbide strengthening in the high thermal conductivity additive manufacturing die steel. Thus, the present invention adds higher levels of M (M ═ one or more of Nb, Ti, V, Ta, or Zr) to form Fe2M-Laves phase because of Fe formation2Both the M-Laves phase and the MC carbide are carbide forming elements M (M ═ Nb, Ti, V, Ta, Zr), and no third element needs to be added, minimizing the decrease in the alloy thermal conductivity. Therefore, in designing the composition of the die steel, the alloy is used as a main componentHigh thermal conductivity, 3D printing process performance and hardness, and the MC carbide and Fe are required to be made2Since M-Laves precipitates in the same manner, the ratio M/C is kept between 1.0 and 1.55. Meanwhile, in order to take the corrosion resistance and the high-temperature tempering softening resistance of the alloy into consideration, a certain content of Cr and Mo needs to be added.
The role of the alloying elements in the high thermal conductivity additive manufacturing die steel is described below. (1) Cr is a main element for providing corrosion resistance in the stainless steel, and the corrosion resistance of the alloy can be improved by adding a certain content of Cr; however, the thermal conductivity of the alloy is remarkably reduced due to the excessively high Cr content, so that the Cr content in the alloy is 1-2 wt% in consideration of the corrosion resistance and the thermal conductivity of the alloy. (2) Mo: mo can improve the pitting corrosion resistance of stainless steel and also can improve the high-temperature softening resistance of the alloy, but the heat conductivity of the alloy can be reduced due to the fact that the Mo is excessively dissolved in the matrix, and therefore the Mo content is less than or equal to 2 wt%. (3) Strong carbide forming element M (Nb, Ti, V, Ta, Zr): the above five are MC and Fe2And when the M-Laves phase forming elements are added independently, the content of the five elements cannot be respectively higher than Nb and is less than or equal to 1.2, Ti and is less than or equal to 0.6, V is less than or equal to 0.65, Ta is less than or equal to 2.3, Zr is less than or equal to 1.1, 2-3 composite additions are preferred in the invention, and the molar ratio of M to C is 1.0-1.55.
The additive alloys of examples 1-16 and comparative example 1 were prepared by the following method: the composition elements are proportioned according to the mass percentage; and smelting the proportioned mixture for multiple times by using a non-consumable vacuum arc smelting furnace under the protection of Ar gas to obtain an alloy ingot with uniform components and the mass of about 40 g. Then quenching treatment of 1200 ℃/60min + water cooling is carried out on the alloy ingot, and tempering treatment of 600 ℃/120min + air cooling is carried out.
The additive alloy compositions of examples 1-12 are shown in Table 2 along with their thermal conductivity and hardness comparisons.
TABLE 2 additive alloy compositions of examples 1-12 and their thermal conductivity and hardness
As can be seen from table 2, examples 1 to 12 both have high thermal conductivity (not less than 40W/m · K) and hardness (not less than 40HRC), and at the same time, the alloy also has good 3D printing process performance by reducing the C content to 0.1 wt.%.
The thermal conductivity of the designed alloy was calculated using the JmatPro software, as shown in table 3 and fig. 1, with alloy # 1 in fig. 1 being a spanish developed HTCS-130, the calculated thermal conductivity being 62W/m · K, which is substantially consistent with the experimentally measured thermal conductivity of 60W/m · K, indicating that the JmatPro software can be used to predict the thermal conductivity of the alloy. Comparative example No. 2 is comparative example 1, i.e. no addition of Cr and Mo. Examples 3# to 5# are examples 13 to 15, respectively.
TABLE 3M and C alloy compositions, measured thermal conductivities, calculated thermal conductivities, and M/C data for HTCS-130, comparative example 1, and examples 13-15
As can be seen from Table 3, the molar ratio M/C in comparative example 1 was 1:1, the calculated thermal conductivity is 73W/m.K, and the actual thermal conductivity is 74W/m.K, which is 20% higher than that of the HTCS-130 which is commercially used at present, and the key point for ensuring the high thermal conductivity of the alloy is that the carbide forming element M/C (1: 1) (at.%) is kept in the die steel. However, as shown in fig. 1, neither comparative example 1 nor example 13 can be used for 3D printing. This is because the printing performance of the die steel is closely related to the C content, and when the C content is higher than 0.2 wt%, a cracking phenomenon occurs during the printing process, so that when the C content needs to be controlled to be lower than 0.1 wt%, the die material without cracks is expected to be prepared by adjusting the printing process parameters. However, the reduction of the C content causes a significant decrease in hardness of the die steel, thereby deteriorating wear resistance, so that Cr and Mo need to be added to the die steel in addition to carbide strengthening to increase the hardness of the alloy.
In summary, the present invention adjusts the molar ratio of M/C to 1.0-1.5 of the strong carbide forming elements M (Nb, Ti, V, Ta, Zr) to C, so as to precipitate the strong carbide forming elements M (M) and C simultaneouslyPrecipitation of MC carbide and Fe2The M-Laves phase reduces the content of solid solution elements in the alloy to the maximum extent, and after quenching and tempering heat treatment, the alloy has high thermal conductivity (not less than 40W/m.K) and hardness (not less than 40HRC) simultaneously; at the same time, by reducing the C content to 0.1 wt.%, the alloy also has good 3D printing process performance. Therefore, the alloy disclosed by the invention has high thermal conductivity, good additive manufacturing process performance and higher hardness, and is expected to be used in the industries of injection molds and stamping molds.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. The MC and Laves phase reinforced high-thermal-conductivity additive manufacturing die steel is characterized by comprising the following components in percentage by weight: 0.1-0.2 wt% of C, 0.6-2.3 wt% of strong carbide forming element M and the balance of Fe; wherein the molar ratio of the strong carbide forming elements M to C is 1: 1.0 to 1.55.
2. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 1, wherein the MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel further comprises Cr and/or Mo, wherein Cr is 0-2 wt% and Mo is 0-2 wt%.
3. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 1, wherein the strong carbide forming element M is one or a combination of two or more of Nb, Ti, V, Ta or Zr.
4. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 3, wherein when the strong carbide forming element M is Nb, the mass ratio of Nb to the total mass of the additive is 0.01-1.2 wt%.
5. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 3, wherein when the strong carbide forming element M is Ti, the mass ratio of Ti to the total mass of the additive is 0.01-0.6 wt%.
6. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 3, wherein when the strong carbide forming element M is V, the mass ratio of V to the total mass of the additive is 0.01-0.65 wt%.
7. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 3, wherein when the strong carbide forming element M is Ta, the mass ratio of Ta to the total mass of the additive is 0.01-0.23 wt%.
8. The MC and Laves phase strengthened high thermal conductivity additive manufacturing die steel according to claim 3, wherein when the strong carbide forming element M is Zr, the mass ratio of Zr to the total mass of the additive is 0.01-1.1 wt%.
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