CN117737604A - Super-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance and preparation method thereof - Google Patents
Super-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 132
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 87
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- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 10
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- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 9
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 2
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
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- Heat Treatment Of Steel (AREA)
Abstract
The application relates to the technical field of ferrite stainless steel preparation, in particular to an ultra-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance, which comprises the following elements: 0.2 to 0.3 percent of Y, less than or equal to 0.009 percent of C, less than or equal to 0.006 percent of N, less than or equal to 0.005 percent of O, less than or equal to 0.05 percent of S i, less than or equal to 0.02 percent of P, less than or equal to 0.008 percent of S, less than or equal to 0.05 percent of N i, 0.4 to 1 percent of Mn, 16 to 22 percent of Cr, 0.04 to 0.12 percent of Ce, 0.05 to 0.2 percent of Al, 0.05 to 0.3 percent of Ti, less than or equal to 0.02 percent of Cu, less than or equal to 0.02 percent of V, 0.04 to 0.2 percent of surface modified graphene alloy additive, and the balance of Fe. The ultra-pure ferrite stainless steel master alloy has good mechanical property and corrosion resistance, can replace 304 stainless steel to be used, has the advantages of relatively better electric conductivity and heat conductivity, has lower thermal expansion coefficient and has excellent processability.
Description
Technical Field
The application relates to the technical field of ferrite stainless steel preparation, in particular to an ultra-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance and a preparation method thereof.
Background
The stainless steel material has excellent comprehensive performance and is widely applied to various industries. With the continuous progress of technological means, according to different steel uses, various stainless steel materials with different brands of types are correspondingly developed, including martensitic stainless steel, austenitic stainless steel, ferritic stainless steel, alpha+gamma duplex stainless steel, precipitation hardening stainless steel and the like.
The 304 stainless steel, namely 18-8 stainless steel, has the advantages of excellent corrosion resistance, high heat-resistant use temperature, good processability, excellent weldability and the like, contains more than 18% of Cr and more than 8% of Ni in alloy element, is widely applied to industries such as petrochemical industry, metallurgical machinery, agriculture, ship parts, food industry and the like, and is the stainless steel material with the most wide application and the largest use amount in the world at present.
430 The (ferrite/medium chromium) stainless steel contains 16-18% of Cr, basically does not contain nickel metal (less than or equal to 0.05%), is less than or equal to 0.015% of C+N (ultra-pure), is less than or equal to 0.05% of C+N (high purity), has the advantages of good corrosion resistance, low production cost relative to 304 stainless steel, high heat conductivity, small thermal expansion coefficient, excellent processability, weldability and the like, can replace 304 stainless steel in some fields, and mainly comprises kitchen facilities, washing machines, automobile parts and the like.
The 430 stainless steel is compared with the 304 stainless steel: the corrosion resistance of 430 stainless steel in high temperature environment and corrosive medium is inferior to that of 304 stainless steel, which is a major problem limiting the application and development of 430 stainless steel. For this purpose, the applicant has developed an ultra-pure ferritic stainless steel master alloy for yttrium-containing heat resistance, which can replace 304 stainless steel, and a method for preparing the same.
Disclosure of Invention
In order to solve the technical problems in the background art, the application provides an ultra-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance and a preparation method thereof.
In a first aspect, the present application provides an ultra-pure ferritic stainless steel master alloy for yttrium-containing heat resistance, which is realized by the following technical scheme:
an ultra-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance consists of the following components in percentage by weight: y, C less than or equal to 0.009 percent of 0.2 to 0.3 percent, N less than or equal to 0.006 percent, O less than or equal to 0.005 percent, S i less than or equal to 0.05 percent, P less than or equal to 0.02 percent, S less than or equal to 0.008 percent, N i less than or equal to 0.05 percent, mn of 0.4 to 1.0 percent, cr of 12 to 18 percent, ce of 0.04 to 0.12 percent, al of 0.05 to 0.20 percent, T i of 0.05 to 0.30 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, and surface modified graphene alloy additive of 0.04 to 0.20 percent, and the balance of Fe; the surface modified graphene alloy additive comprises a graphene carrier and an interface modified overmetal element loaded on the surface of the graphene carrier; the interface modified metal-plated element is connected to the surface of the graphene carrier through a chemical bond in a single atom form; the interface modified metal-plated element mainly comprises at least one of Fe, cr, mn, Y, ce and T i.
The ultra-pure ferrite stainless steel master alloy has good mechanical property and corrosion resistance, can replace 304 stainless steel to be used, has relatively better advantages of electric conduction and heat conduction, lower thermal expansion coefficient and excellent processing property, and in addition, the ultra-pure ferrite stainless steel modified by the surface modified graphene alloy additive also has good lubricating property, wear resistance, antibacterial mildew resistance and biocompatibility, and has more obvious competitive advantage compared with 304 stainless steel.
Preferably, the interface modified overmetallization element mainly comprises Fe, cr, mn, Y and T i, and the mass ratio of Fe, cr, mn, Y and T i is (74-83): (16-22): (0.4-1.0): (0.2-0.3): (0.05-0.3).
By adopting the technical scheme, the compatibility of the surface modified graphene alloy additive and the matrix alloy can be improved, so that the mechanical property, corrosion resistance, electric conduction and heat conduction properties of the prepared yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy are ensured.
Preferably, the composition comprises the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, N i less than or equal to 0.05 percent, mn less than or equal to 0.48 percent to 0.64 percent, cr less than or equal to 12 percent to 15 percent, ce less than or equal to 0.05 percent to 0.06 percent, al less than or equal to 0.10 percent to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, and surface modified graphene alloy additive less than or equal to 0.05 percent to 0.10 percent, with the balance being Fe.
Preferably, the interface modified overmetallization element mainly comprises Fe, cr, mn, Y and T i in a mass ratio of 810:180:5:3:2.
Preferably, the tensile strength of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy is more than or equal to 480MPa, the yield strength is more than or equal to 205MPa, the elongation is more than or equal to 25%, the thermal conductivity is more than or equal to 30W/(m.K), and the resistivity is more than or equal to 2.5 x 10 6 Omega.m, thermal expansion coefficient less than or equal to 11 um/(m.K), hardness of 80-90HRB, and corrosion rate less than or equal to 0.05mm/a.
Preferably, the yttrium-containing heat-resistant ultra-pure ferritic stainless steel master alloy comprises the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 12.0 to 13.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.048 to 0.054 percent of surface modified graphene alloy additive, and the balance of Fe.
Preferably, the yttrium-containing heat-resistant ultra-pure ferritic stainless steel master alloy comprises the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 14.0 to 15.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.035 to 0.040 percent of surface modified graphene alloy additive, and the balance of Fe.
By adopting the technical scheme, the stainless steel can ensure that the stainless steel has the advantages of good mechanical property and corrosion resistance, relatively better electric conduction and heat conduction, lower thermal expansion coefficient and excellent processability, and can replace 304 stainless steel.
Preferably, the preparation method of the surface modified graphene alloy additive comprises the following steps:
preparing boron-nitrogen doped graphene;
preparing 0.05-0.5g/L of overplating metal salt water solution, wherein nitrate is ferric nitrate nonahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, cerium nitrate hexahydrate, yttrium nitrate hexahydrate and titanium acetylacetonate;
thirdly, mixing boron-nitrogen doped graphene with deionized water, and then performing ultrasonic dispersion to obtain a boron-nitrogen doped graphene aqueous solution, wherein the mass ratio of the boron-nitrogen doped graphene to the deionized water is (1-2): (100-400), adding an overmetallization salt water solution into the boron-nitrogen doped graphene water solution, wherein the mass ratio of the overmetallization content in the overmetallization salt water solution to the carrier boron-nitrogen doped graphene is 1: (10-50), dispersing for 0.5-2h by adopting ultrasonic, magnetically stirring for 20-24h, removing the solvent by rotary evaporation, and drying to obtain solid powder;
and fourthly, performing planetary ball milling on the obtained solid powder for 0.5-2h at a rotating speed of 50-80rpm, placing the powder obtained by ball milling in an air atmosphere condition, performing heat treatment at 600-800 ℃ for 2-4h, performing planetary ball milling on the cooled solid material, and performing ball milling for 0.5-1.0h at a rotating speed of 180-300rpm to obtain the surface modified graphene alloy additive with the average particle size of 200-500 nm.
The preparation method provided by the application is relatively simple, low in operation difficulty and convenient for realizing industrial production and manufacturing.
In a second aspect, the present application provides a method for preparing an ultra-pure ferritic stainless steel master alloy for yttrium-containing heat resistance, which is implemented by the following technical scheme:
the preparation method of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following steps:
s1, proportioning according to the component control requirement of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy;
simultaneously preparing a surface modified graphene alloy additive;
s2, drying the preparation raw materials in S1 at 100-150 ℃ for 1-4h;
s3, feeding according to the sequence of 50wt% of Fe, 50wt% of Cr, ti, ce, the rest 50wt% of Cr and the rest 50wt% of Fe, and carrying out power transmission melting under vacuum at a vacuum degree of <10 Pa;
s4, refining at 1570-1590 ℃ under vacuum degree of less than 1.0Pa, and refining at a temperature after melting;
s5, cooling to 1480-1520 ℃, adding Al, stirring, sampling and analyzing in front of the furnace, and trimming and supplementing materials according to the analysis result in front of the furnace;
s6, adjusting the temperature of molten steel to 1610-1630 ℃, keeping the temperature, and preparing a module; filling argon with 50000Pa, wrapping yttrium metal with pure iron skin, adding yttrium metal according to 80% yield, controlling addition according to 95% yield, adding manganese metal, controlling addition according to 95% yield, stirring for 1-2min, and rapidly casting to obtain yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy rod.
The preparation method provided by the application is relatively simple, low in operation difficulty and convenient for realizing industrial production and manufacturing.
Preferably, the chute or the diverter tray used for pouring in the step S6 does not pass through the filter screen, but is required to be provided with a slag stopping dam for stopping slag.
By adopting the technical scheme, the quality and the quality stability of the same batch of ultra-pure ferrite stainless steel master alloy can be ensured.
In summary, the present application has the following advantages:
1. the ultra-pure ferrite stainless steel master alloy has good mechanical property and corrosion resistance, can replace 304 stainless steel to be used, has the advantages of relatively better electric conductivity and heat conductivity, has lower thermal expansion coefficient and has excellent processability.
2. The preparation method provided by the application is relatively simple, low in operation difficulty and convenient for realizing industrial production and manufacturing.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this.
It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention. While the following terms are believed to be well understood by those of ordinary skill in the art, the following definitions are set forth to aid in the description of the presently disclosed subject matter.
As used herein, the term "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional unrecited elements or method steps. "comprising" is a technical term used in claim language to mean that the recited element is present, but other elements may be added and still form a construct or method within the scope of the recited claims.
Examples
An ultra-pure ferrite stainless steel master alloy containing yttrium and used for heat resistance consists of the following components in percentage by weight: y, C less than or equal to 0.009 percent of 0.2 to 0.3 percent, N less than or equal to 0.006 percent, O less than or equal to 0.005 percent, S i less than or equal to 0.05 percent, P less than or equal to 0.02 percent, S less than or equal to 0.008 percent, N i less than or equal to 0.05 percent, mn of 0.4 to 1.0 percent, cr of 12 to 18 percent, ce of 0.04 to 0.12 percent, al of 0.05 to 0.20 percent, T i of 0.05 to 0.30 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, and surface modified graphene alloy additive of 0.04 to 0.20 percent, with the balance being Fe.
Preferably, the ultra-pure ferritic stainless steel master alloy consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, N i less than or equal to 0.05 percent, mn less than or equal to 0.48 percent to 0.64 percent, cr less than or equal to 12 percent to 15 percent, ce less than or equal to 0.05 percent to 0.06 percent, al less than or equal to 0.10 percent to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, and surface modified graphene alloy additive less than or equal to 0.05 percent to 0.10 percent, with the balance being Fe.
Preferably, the ultra-pure ferritic stainless steel master alloy consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 12.0 to 13.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.048 to 0.054 percent of surface modified graphene alloy additive, and the balance of Fe.
Preferably, the ultra-pure ferritic stainless steel master alloy consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, S i less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 14.0 to 15.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, T i percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.035 to 0.040 percent of surface modified graphene alloy additive, and the balance of Fe.
The surface modified graphene alloy additive comprises a graphene carrier and an interface modified overmetallization element loaded on the surface of the graphene carrier. The interface modified metal-plated element is connected to the surface of the graphene carrier in a single-atom form through a chemical bond. The interface modified metal-plated element mainly comprises at least one of Fe, cr, mn, Y, ce and T i. Preferably, the interface modified overmetallization element mainly consists of Fe, cr, mn, Y, ti, and the mass ratio of Fe, cr, mn, Y, ti is (74-83): (16-22): (0.4-1.0): (0.2-0.3): (0.05-0.3). Further preferably, the interface-modified overmetallised element consists essentially of Fe, cr, mn, Y, T i in a mass ratio of 810:180:5:3:2.
The tensile strength of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy is more than or equal to 480MPa, the yield strength is more than or equal to 205MPa, the elongation is more than or equal to 25%, the thermal conductivity is more than or equal to 30W/(m.K), and the resistivity is more than or equal to 2.5 x 10 6 Omega.m, thermal expansion coefficient less than or equal to 11 um/(m.K), hardness of 80-90HRB, corrosion rate less than or equal to 0.05mm/a, and can be used for replacing 304 stainless steel.
The preparation method of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following steps:
s1, proportioning according to the component control requirement of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy;
and simultaneously preparing a surface modified graphene alloy additive:
s1.1, preparing boron-nitrogen doped graphene;
s1.2, preparing 0.05-0.5g/L of overmetallised salt water solution, wherein nitrate is ferric nitrate nonahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, cerium nitrate hexahydrate, yttrium nitrate hexahydrate and titanium acetylacetonate;
s1.3, mixing boron-nitrogen doped graphene with deionized water, and then performing ultrasonic dispersion to obtain a boron-nitrogen doped graphene aqueous solution, wherein the mass ratio of the boron-nitrogen doped graphene to the deionized water is (1-2): (100-400), adding an overmetallization salt water solution into the boron-nitrogen doped graphene water solution, wherein the mass ratio of the overmetallization content in the overmetallization salt water solution to the carrier boron-nitrogen doped graphene is 1: (10-50), dispersing for 0.5-2h by adopting ultrasonic, magnetically stirring for 20-24h, removing the solvent by rotary evaporation, and drying to obtain solid powder;
s1.4, performing planetary ball milling on the obtained solid powder for 0.5-2 hours at a rotating speed of 50-80rpm, placing the powder obtained by ball milling in an air atmosphere condition, performing heat treatment at 600-800 ℃ for 2-4 hours, performing planetary ball milling on the cooled solid material, and performing ball milling at a rotating speed of 180-300rpm for 0.5-1.0 hour to obtain the surface modified graphene alloy additive with an average particle size of 200-500 nm;
s2, drying the preparation raw materials in S1 at 100-150 ℃ for 1-4h;
s3, feeding according to the sequence of 50wt% of Fe, 50wt% of Cr, ti, ce, the rest 50wt% of Cr and the rest 50wt% of Fe, and carrying out power transmission melting under vacuum at a vacuum degree of <10 Pa;
s4, refining at 1570-1590 ℃ under vacuum degree of less than 1.0Pa, and refining at a temperature after melting;
s5, cooling to 1480-1520 ℃, adding Al, stirring, sampling and analyzing in front of the furnace, and trimming and supplementing materials according to the analysis result in front of the furnace;
s6, adjusting the temperature of molten steel to 1610-1630 ℃, keeping the temperature, and preparing a module; filling argon with 50000Pa, wrapping metal yttrium with pure iron skin, adding metal yttrium according to 80% yield, calculating and controlling, adding metal manganese according to 95% yield, adding surface modified graphene alloy additive according to 95% yield, calculating and controlling, stirring for 1-2min after adding, pouring quickly, and setting a chute or a splitter plate adopted for pouring without putting a filter screen, wherein slag blocking dam is needed to block slag, so that the yttrium-containing ultra-pure ferrite stainless steel master alloy rod for heat resistance can be prepared.
Example 1: an ultra-pure ferrite stainless steel master alloy (single element composition of ingredients) for yttrium-containing heat resistance consists of the following components in percentage by weight: 0.2% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, si 0.02%, P0.01%, S0.005%, 0.04% N i%, 0.6% Mn 12% Cr 0.04% Ce 0.12% A l%, 0.2% T i%, 0.016% Cu 0.014% V0.08% surface modified graphene alloy additive, and the balance Fe.
The preparation method of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following steps:
s1, proportioning according to the component control requirement of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy;
and simultaneously preparing a surface modified graphene alloy additive:
s1.1, preparing boron-nitrogen doped graphene: weighing 0.5g of graphene (fineness 7-12um, CAS:7782-42-5, from Shenzhen Tuling New Material Co., ltd.) and adding into mixed acid solution (prepared from 25mL of concentrated sulfuric acid and 75mL of concentrated nitric acid), manually pre-mixing and stirring with a glass rod for 1-2min, then performing ultrasonic dispersion for 30min, performing ultrasonic power 800W and ultrasonic frequency 44kHz, uniformly dispersing graphene, heating to 88-90 ℃, heating and refluxing for 2h to make the surface acidification treatment of graphene rich in oxygen-containing groups, weighing 200mg of prepared graphene subjected to the surface acidification treatment, performing ultrasonic dispersion in 100mL of deionized water, ultrasonic dispersing for 30min, ultrasonic power 400W and ultrasonic frequency 32kHz, then adding 0.4g boric acid and 2g melamine, ultrasonic dispersing for 30min, ultrasonic power 400W and ultrasonic frequency 32kHz, finally sealing the mixture in a customized 500mL high-pressure reaction kettle, heating to 180 ℃ at 3 ℃/min, pressurizing to 0.5MPa, maintaining at 180 ℃ for 12 hours, decompressing after heat treatment, opening the high-pressure reaction kettle, naturally cooling to room temperature, taking out a sample, washing three sides with ultrapure water, and drying at 80 ℃ for 4.0 hours to obtain the boron-nitrogen doped graphene carrier;
s1.2, preparing 0.2g/L of overmetallised salt water solution, wherein nitrate is ferric nitrate nonahydrate and chromium nitrate nonahydrate matched with tetrahydrate manganese nitrate, and the ratio of the iron content in the ferric nitrate nonahydrate to the chromium content in the chromium nitrate nonahydrate to the manganese content in the tetrahydrate manganese nitrate is 87:12:1;
s1.3, mixing 200mg of boron-nitrogen doped graphene prepared in S1.1 with 50mL of deionized water, dispersing by adopting ultrasonic to obtain boron-nitrogen doped graphene aqueous solution, carrying out ultrasonic power 400W and ultrasonic frequency 32kHz, adding the boron-nitrogen doped graphene aqueous solution into 0.2g/L of the overmetallization salt water solution prepared in S1.2 at the adding speed of 20mg/60S, wherein the mass ratio of the overmetallization metal content in the overmetallization salt water solution to the carrier boron-nitrogen doped graphene is 1:40, dispersing by adopting ultrasonic for 2h, carrying out magnetic stirring for 24h at 200rpm by adopting ultrasonic power 400W and ultrasonic frequency 32kHz, steaming to remove solvent, and drying to obtain solid powder;
s1.4, carrying out planetary ball milling on the obtained solid powder for 1.0h at a rotating speed of 60rpm, placing the powder obtained by ball milling under an air atmosphere condition, carrying out heat treatment at 640 ℃ for 4h, cooling the obtained solid material, carrying out planetary ball milling on the cooled solid material, and carrying out ball milling at a rotating speed of 240rpm for 0.5h to obtain the surface modified graphene alloy additive with the average particle size of 500 nm.
S2, drying the preparation raw materials in S1 at 120 ℃ for 4 hours;
s3, feeding according to the sequence of 50wt% of Fe, 50wt% of Cr, ti, ce, the rest 50wt% of Cr and the rest 50wt% of Fe, and carrying out power transmission melting under vacuum at a vacuum degree of <10 Pa;
s4, refining at 1585+/-2 ℃ under vacuum degree of less than 1.0Pa, and refining at a temperature after melting;
s5, cooling to 1500 ℃, adding Al, stirring, sampling and analyzing in front of the furnace, and trimming and feeding according to the front analysis result;
s6, adjusting the temperature of molten steel to 1625+/-2 ℃, keeping the temperature, and preparing a module; filling argon with 50000Pa, wrapping metal yttrium (purity 4N) and metal manganese (purity 4N) with pure iron skin, adding metal yttrium according to 80% yield calculation control, adding metal manganese according to 95% yield calculation control, adding surface modified graphene alloy additive according to 95% yield calculation control, stirring for 2min after adding for quick casting, pouring a chute adopted and adopting a slag stopping dam to stop slag, naturally cooling to 200-205 ℃ to obtain an ultra-pure ferrite stainless steel master alloy rod for yttrium-containing heat resistance, then carrying out solution treatment, heating to 880 ℃ at 10 ℃/min, preserving heat for 4h, naturally cooling to 180 ℃ for 2h, and naturally cooling to room temperature to obtain the finished product of the ultra-pure ferrite stainless steel master alloy rod for yttrium-containing heat resistance, which can be machined.
Example 2 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.25% Y, C% or less 0.006%, N0.002%, O0.002%, si 0.02%, P0.01%, S0.005%, mn 0.68%, cr 15%, ce 0.08%, al 0.15%, ti 0.18%, cu 0.016%, V0.014%, surface modified graphene alloy additive 0.035%, and Fe in balance.
Example 3 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: y, C-0.006%, N-0.002%, O-0.002%, si-0.02%, P-0.01%, S-0.005%, mn-0.8%, cr-18%, ce-0.06%, al-0.18%, ti-0.24%, cu-0.016%, V-0.014%, surface modified graphene alloy additive 0.03% and Fe in balance.
Example 4 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.24% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 054% Mn 13% Cr 0.06% Ce 0.14% Al 0.20% T i% Cu 0.016% V0.014% 0.05% surface modified graphene alloy additive, the balance Fe.
Example 5 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.24% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 062% Mn 12.4% Cr 0.06% Ce 0.16% A l%, 0.24% T i%, 0.016% Cu 0.014% V0.054% surface modified graphene alloy additive, and the balance Fe.
Example 6 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.24% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, mn 0.6%, cr 14%, ce 0.06%, al 0.15%, T i% 0.22%, cu 0.016%, V0.014%, surface modified graphene alloy additive 0.04%, and Fe in balance.
Example 7 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.24% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 0.6% Mn 14.6% Cr 0.06% Ce 0.16% Al 0.24% T i, 0.016% Cu 0.014% V0.04% surface modified graphene alloy additive, the balance Fe.
Example 8 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.28% of Y, C-0.006%, N-0.002%, O-0.002%, S i-0.02%, P-0.01%, S-0.005%, 0.54% of Mn, 12% of Cr, 0.08% of Ce, 0.16% of Al, 0.24% of T i%, 0.016% of Cu, 0.014% of V, 0.06% of surface modified graphene alloy additive and the balance of Fe.
Example 9 differs from example 1 in that: surface modified graphene alloy additives. Specifically, the preparation method of the surface modified graphene alloy additive is different in that: s1.2, preparing 0.2g/L of overmetalized saline solution, wherein nitrate is ferric nitrate nonahydrate, chromium nitrate nonahydrate, tetrahydrate manganese nitrate and yttrium nitrate hexahydrate, and the mass ratio of iron contained in the ferric nitrate nonahydrate to chromium contained in the chromium nitrate nonahydrate to manganese contained in the tetrahydrate manganese nitrate to yttrium contained in the yttrium nitrate hexahydrate is 86:12:1:1.
Example 10 differs from example 1 in that: surface modified graphene alloy additives. Specifically, the preparation method of the surface modified graphene alloy additive is different in that: s1.2, preparing 0.2g/L of overspray salt water solution, wherein nitrate is ferric nitrate nonahydrate, chromium nitrate nonahydrate, tetrahydrate manganese nitrate, yttrium nitrate hexahydrate and titanium acetylacetonate, and the mass ratio of iron contained in the ferric nitrate nonahydrate to chromium contained in the chromium nitrate nonahydrate to manganese contained in the tetrahydrate manganese nitrate hexahydrate to yttrium contained in the yttrium nitrate hexahydrate to titanium contained in the titanium acetylacetonate is 810:180:5:3:2.
Example 11 differs from example 10 in that: the mass ratio of iron contained in iron nitrate nonahydrate, chromium contained in chromium nitrate nonahydrate, manganese contained in manganese nitrate tetrahydrate, yttrium contained in yttrium nitrate hexahydrate, and titanium contained in titanium acetylacetonate was 750:240:5:3:2.
Example 12 differs from example 10 in that: the mass ratio of iron contained in iron nitrate nonahydrate, chromium contained in chromium nitrate nonahydrate, manganese contained in manganese nitrate tetrahydrate, yttrium contained in yttrium nitrate hexahydrate, and titanium contained in titanium acetylacetonate was 830:160:5:3:2.
Comparative example 1 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: y, C-0.006%, N-0.002%, O-0.002%, S i-0.02%, P-0.01%, S-0.005%, N i%, mn-0.6%, cr-12%, ce-0.04%, A l%, T i-0.2%, cu-0.016%, V-0.014%, graphene-0.08% and Fe-the rest. The graphene is prepared from graphene raw materials of Shenzhen Tuling New material Co., ltd, the fineness is 7-12um, CAS:7782-42-5, and obtaining finished graphene with an average particle size of 500nm after planetary ball milling.
Comparative example 2 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.2% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 0.04% N i%, 0.6% Mn, 10% Cr, 0.04% Ce, 0.12% A l, 0.2% T i, 0.016% Cu, 0.014% V, 0.08% surface modified graphene alloy additive, and the balance Fe.
Comparative example 3 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.2% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 0.04% N i%, 0.6% Mn, 20% Cr, 0.04% Ce, 0.12% A l, 0.2% T i, 0.016% Cu, 0.014% V, 0.05% surface modified graphene alloy additive, and the balance Fe.
Comparative example 4 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: less than or equal to 0.006% of C, less than or equal to 0.002% of N, less than or equal to 0.002% of O, less than or equal to 0.02% of S i, less than or equal to 0.01% of P, less than or equal to 0.005% of S, 0.04% of N i, 0.6% of Mn, 12% of Cr, 0.04% of Ce, 0.12% of Al, 0.2% of T i, 0.016% of Cu, 0.014% of V, 0.08% of surface modified graphene alloy additive, and the balance of Fe.
Comparative example 5 differs from example 1 in that: the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy comprises the following components in percentage by weight: 0.2% Y, C% or less than or equal to 0.006%, N0.002%, O0.002%, S i% or less than or equal to 0.02%, P0.01%, S0.005%, 0.04% N i%, 0.6% Mn, 12% Cr, 0.12% Al, 0.2% T i%, 0.016% Cu, 0.014% V, 0.08% surface modified graphene alloy additive, and the balance Fe.
Comparative example 6 differs from example 10 in that: surface modified graphene alloy additives. Specifically, the preparation method of the surface modified graphene alloy additive is different in that: s1.2, preparing 0.2g/L of overmetallised salt water solution, wherein nitrate is only ferric nitrate nonahydrate.
Performance test: tensile strength, yield strength and elongation were measured according to the method GB/T228.1-2010. The hardness HRB is measured by a portable hardness tester for HRB steel aluminum plate metal materials of a Lev hardness tester. The heat conductivity testing method comprises the following steps: and (3) measuring by adopting a DR-S thermal conductivity coefficient measuring instrument. The resistivity was measured according to the GB/T351-2019 resistivity measurement method for metallic materials. The coefficient of thermal expansion is determined according to GB/T3810.3-2016 measurement of the coefficient of thermal expansion and the difference between the coefficients of thermal expansion of metals and alloys.
Table 1 is a table of conventional test parameters for stainless steel in examples 1 to 12 and comparative examples 1 to 6
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 6 and the combination of table 1, compared with comparative example 2, in example 1, the mechanical strength of the ultrapure ferritic stainless steel master alloy prepared from the unmodified graphene material tends to decrease, and the electric conductivity and the heat conductivity are improved slightly.
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 6 and the combination of Table 1, when the addition amount of the surface-modified graphene alloy additive is 0.03 to 0.08% as compared with comparative examples 1 and 3, the Cr content in the ultrapure ferritic stainless steel master alloy is controlled to be 12 to 18% by weight, and the excessive Cr addition does not significantly improve the mechanical strength and the electric conductivity and the heat conductivity.
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 6 and the combination of table 1, the addition of the metal elements Y and Ce to the ultrapure ferritic stainless steel master alloy in examples 1 to 3 can improve the mechanical properties and the processability of the finished product, and the auxiliary synergy effect can be achieved when the alloy is compounded with the surface-modified graphene alloy additive.
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 6 and the combination of table 1, examples 1 to 3 and comparative example 6 show that the interface-modified plating metal element is mainly composed of at least one of Fe, cr, mn, Y, ce, T i and the compatibility of the surface-modified graphene alloy additive with the matrix alloy element, and can improve the mechanical strength and greatly improve the electrical conductivity and the thermal conductivity.
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 6 and the combination of table 1, examples 1 to 3 are superior to examples 4 to 8 in terms of the combination properties of the ultra-pure ferritic stainless steel master alloy, and the ultra-pure ferritic stainless steel master alloy in examples 2 to 3 and examples 6 to 7 is superior to the ultra-pure ferritic stainless steel master alloy in examples 4 to 5 in terms of the economic cost and substitution of 304 stainless steel.
As can be seen from the combination of examples 1-12 and comparative examples 1-6 and the combination of Table 1, compared with examples 9-12, the interface-modified plating metal element in the surface-modified graphene alloy additive is mainly composed of (74-83), (16-22), (0.4-1.0), (0.2-0.3) and (0.05-0.3) according to the mass ratio of (Fe, cr, mn, Y, T i), and the compatibility of the prepared surface-modified graphene alloy additive and the matrix alloy element is more excellent, so that the overall mechanical strength can be improved, and the electric conductivity and the heat conductivity of the surface-modified graphene alloy additive can be greatly improved.
Table 2 is a table of corrosion resistance test parameters of stainless steels in examples 1 to 3, example 10 and comparative examples 1 to 6
Remarks: the test standard is still GB/T24187-2023, and the corrosion resistance rate S1 of stainless steel is calculated by exposing the stainless steel for 2 months under the test condition 1 of 80 ℃ (temperature)/85 DEG (humidity). Test condition 2 the corrosion resistance rate S2 of the stainless steel was calculated by immersing in a 10% nitric acid solution and heating to 100 ℃ for 2 months of the exposure experiment. Test strip 3 is the corrosion resistance rate S3 of stainless steel calculated from a 2 month exposure test by immersing in a 5% sulfuric acid solution and heating to 100 ℃. Test control 430 stainless steel was used for the Bao-steel 430 stainless steel plate and 304 stainless steel was used for the Bao-steel 304 stainless steel plate.
It can be seen in combination with examples 1-3, 10 and comparative examples 1-6 and with tables 1-2 that the ultra-pure ferritic stainless steel master alloys of examples 1-3 and 10 are superior in corrosion resistance to conventional 430 unaccustomed and comparable 304 stainless steels.
As can be seen from the combination of examples 1-3, 10 and comparative examples 1-6 and the combination of tables 1-2, the comparison of examples 1-3 and comparative example 2 shows that the unmodified graphene material has limited improvement of corrosion resistance to the ultra-pure ferritic stainless steel master alloy, and the commercially available conventional graphene material cannot meet the actual alloy production requirements, while the surface modified graphene alloy additive overcomes the compatibility of the surface modified graphene alloy additive and the matrix alloy element, and can effectively improve the corrosion resistance.
In conclusion, the ultra-pure ferritic stainless steel master alloy has the advantages of good mechanical property, corrosion resistance, relatively better electric conduction and heat conduction properties, lower thermal expansion coefficient and excellent processability, and can be used for replacing 304 stainless steel. In addition, the ultra-pure ferrite stainless steel modified by the surface modified graphene alloy additive also has good lubricating property, wear resistance, antibacterial and mildew-proof properties and biocompatibility, and has more obvious competitive advantage compared with 304 stainless steel.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. An ultra-pure ferritic stainless steel master alloy containing yttrium for heat resistance, which is characterized in that: the composite material consists of the following components in percentage by weight: y, C less than or equal to 0.009 percent of 0.2 to 0.3 percent, N less than or equal to 0.006 percent, O less than or equal to 0.005 percent, si less than or equal to 0.05 percent, P less than or equal to 0.02 percent, S less than or equal to 0.008 percent, ni less than or equal to 0.05 percent, mn less than or equal to 0.4 to 1.0 percent, cr less than or equal to 12 to 18 percent, ce less than or equal to 0.04 to 0.12 percent, al less than or equal to 0.05 to 0.20 percent, ti less than or equal to 0.05 to 0.30 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.04 to 0.20 percent of surface modified graphene alloy additive, and the balance of Fe; the surface modified graphene alloy additive comprises a graphene carrier and an interface modified overmetal element loaded on the surface of the graphene carrier; the interface modified metal-plated element is connected to the surface of the graphene carrier through a chemical bond in a single atom form; the interface modified metal-plated element mainly comprises at least one of Fe and Cr matched Mn, Y, ce, ti.
2. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 1, wherein: the interface modified metal-plated element mainly comprises Fe, cr, mn, Y, ti, wherein the mass ratio of Fe, cr, mn, Y, ti is (74-83): (16-22): (0.4-1.0): (0.2-0.3): (0.05-0.3).
3. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 2, wherein: the composite material consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, si less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, ni less than or equal to 0.05 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 12 to 15 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, ti less than or equal to 0.16 to 0.24 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.05 to 0.10 percent of surface modified graphene alloy additive, and the balance of Fe.
4. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 3, wherein: the interface modified metal-plated element mainly comprises Fe, cr, mn, Y, ti in a mass ratio of 810:180:5:3:2.
5. An ultra-pure ferritic stainless steel master alloy for yttrium-containing heat resistance according to any one of claims 3 or 4, wherein: the tensile strength of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy is more than or equal to 480MPa, the yield strength is more than or equal to 205MPa, the elongation is more than or equal to 25%, the thermal conductivity is more than or equal to 30W/(m.K), and the resistivity is more than or equal to 2.5 x 10 6 Omega.m, thermal expansion coefficient less than or equal to 11 um/(m.K), hardness of 80-90HRB, and corrosion rate less than or equal to 0.05mm/a.
6. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 2, wherein: the composite material consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, si less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 12.0 to 13.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, ti less than or equal to 0.16 to 0.24 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.048 to 0.054 percent of surface modified graphene alloy additive, and the balance being Fe.
7. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 2, wherein: the composite material consists of the following components in percentage by weight: y, C less than or equal to 0.006 percent, N less than or equal to 0.002 percent, O less than or equal to 0.002 percent, si less than or equal to 0.02 percent, P less than or equal to 0.01 percent, S less than or equal to 0.005 percent, mn less than or equal to 0.48 to 0.64 percent, cr less than or equal to 14.0 to 15.0 percent, ce less than or equal to 0.05 to 0.06 percent, al less than or equal to 0.10 to 0.20 percent, ti less than or equal to 0.16 to 0.24 percent, cu less than or equal to 0.02 percent, V less than or equal to 0.02 percent, 0.035 to 0.040 percent of surface modified graphene alloy additive, and the balance of Fe.
8. An ultra-pure ferritic stainless steel master alloy for heat resistance with yttrium according to claim 1, wherein: the preparation method of the surface modified graphene alloy additive comprises the following steps:
preparing boron-nitrogen doped graphene;
preparing 0.05-0.5g/L of overplating metal salt water solution, wherein nitrate is ferric nitrate nonahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, cerium nitrate hexahydrate, yttrium nitrate hexahydrate and titanium acetylacetonate;
thirdly, mixing boron-nitrogen doped graphene with deionized water, and then performing ultrasonic dispersion to obtain a boron-nitrogen doped graphene aqueous solution, wherein the mass ratio of the boron-nitrogen doped graphene to the deionized water is (1-2): (100-400), adding an overmetallization salt water solution into the boron-nitrogen doped graphene water solution, wherein the mass ratio of the overmetallization content in the overmetallization salt water solution to the carrier boron-nitrogen doped graphene is 1: (10-50), dispersing for 0.5-2h by adopting ultrasonic, magnetically stirring for 20-24h, removing the solvent by rotary evaporation, and drying to obtain solid powder;
and fourthly, performing planetary ball milling on the obtained solid powder for 0.5-2h at a rotating speed of 50-80rpm, placing the powder obtained by ball milling in an air atmosphere condition, performing heat treatment at 600-800 ℃ for 2-4h, performing planetary ball milling on the cooled solid material, and performing ball milling for 0.5-1.0h at a rotating speed of 180-300rpm to obtain the surface modified graphene alloy additive with the average particle size of 200-500 nm.
9. A method for producing an ultra-pure ferritic stainless steel master alloy for yttrium-containing heat resistance according to any one of claims 1 to 8, characterized by: the method comprises the following steps:
s1, proportioning according to the component control requirement of the yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy;
simultaneously preparing a surface modified graphene alloy additive;
s2, drying the preparation raw materials in S1 at 100-150 ℃ for 1-4h;
s3, feeding according to the sequence of 50wt% of Fe, 50wt% of Cr, ti, ce, the rest 50wt% of Cr and the rest 50wt% of Fe, and carrying out power transmission melting under vacuum at a vacuum degree of <10 Pa;
s4, refining at 1570-1590 ℃ under vacuum degree of less than 1.0Pa, and refining at a temperature after melting;
s5, cooling to 1480-1520 ℃, adding Al, stirring, sampling and analyzing in front of the furnace, and trimming and supplementing materials according to the analysis result in front of the furnace;
s6, adjusting the temperature of molten steel to 1610-1630 ℃, keeping the temperature, and preparing a module; filling argon with 50000Pa, wrapping yttrium metal with pure iron skin, adding yttrium metal according to 80% yield, controlling addition according to 95% yield, adding manganese metal, controlling addition according to 95% yield, stirring for 1-2min, and rapidly casting to obtain yttrium-containing heat-resistant ultra-pure ferrite stainless steel master alloy rod.
10. The method for preparing the yttrium-containing heat-resistant ultra-pure ferritic stainless steel master alloy according to claim 9, wherein the method comprises the following steps: and S6, the chute or the flow distribution plate adopted by pouring does not pass through a filter screen, but a slag blocking dam is required to be arranged to block slag.
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