CN113930581B - Modification treatment agent and method for controlling carbide of high-carbon wear-resistant cast steel - Google Patents

Modification treatment agent and method for controlling carbide of high-carbon wear-resistant cast steel Download PDF

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CN113930581B
CN113930581B CN202111183004.4A CN202111183004A CN113930581B CN 113930581 B CN113930581 B CN 113930581B CN 202111183004 A CN202111183004 A CN 202111183004A CN 113930581 B CN113930581 B CN 113930581B
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CN113930581A (en
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闫志杰
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Zhejiang Jiexiong New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • 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
    • 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
    • C21D1/26—Methods of annealing
    • 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
    • C21D1/26—Methods of annealing
    • C21D1/28—Normalising
    • 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
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • 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
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

The invention discloses a method for refining and passivating high-carbon wear-resistant cast carbide through melt modification treatment and controlling the morphology, size and distribution of the carbide by combining subsequent heat treatment, wherein the carbide control method comprises the following steps: induction furnace or electric furnace smelting → LF refining → wire feeding adding proper amount of melt modifier → casting pouring → casting annealing → casting quenching or normalizing → casting tempering; wherein: selectively carrying out LF refining according to the requirements of the cast steel refining process, and directly entering the next step if the LF refining is not required; adding a proper amount of melt modification agent through wire feeding after selective LF refining; the casting is subjected to heat treatment by adopting corresponding process parameters according to the components of cast steel. The method can effectively control the carbide of the high-carbon wear-resistant steel in the as-cast state, refine and passivate the as-cast carbide and improve the component segregation of the casting. After subsequent heat treatment, the nano-sized spherical carbide is dispersed and distributed on a steel matrix.

Description

Modification treatment agent and method for controlling carbide of high-carbon wear-resistant cast steel
Technical Field
The invention belongs to the field of steel smelting, relates to a modification treatment agent for controlling carbide of high-carbon wear-resistant cast steel, and particularly relates to a carbide control method of high-carbon wear-resistant cast steel with high hardness and good toughness and a modification treatment agent used by the method.
Background
Key parts such as hammerheads, grinding balls and lining plates of mining machinery, engineering machinery and the like need materials with good wear resistance and certain toughness. Cast steel and cast iron are wear-resistant materials which are most widely applied in mining machinery, and the materials have the characteristics of plastic performance and recyclability. Generally, the higher the hardness of the wear-resistant material, the better the wear resistance. High-chromium (23-35 wt%) white cast iron is a typical material of high-hardness (HRC 60) wear-resistant cast iron, but the defects of high cost, low toughness, difficult machining and the like limit engineering application. The low-alloy cast steel has the advantages of low cost, good toughness and the like, occupies a large specific weight in the field of wear-resistant materials, but has lower hardness and poorer wear resistance compared with high-chromium white cast iron.
In order to increase hardness and improve wear resistance, the development of wear-resistant cast steel is directed to increase the carbon content and to add high-hardness carbide-forming elements. For example, recently published domestic patents CN 104294156A, CN 111254273 a and the like disclose high carbon cast steel with carbon content exceeding 0.6 wt% for the production of high carbon wear resistant steel pipe and high carbon wear resistant steel ball. With the increase of the carbon content, the number of carbides in the cast steel is increased, the carbides are agglomerated and grown up, and large and even reticular carbides are formed. The large carbide contains alloy elements, so that the distribution of the alloy elements is uneven, the mechanical property of the cast steel is deteriorated, the hardness of the material is reduced, and the wear resistance is reduced. In order to improve the distribution of the cast steel carbides, the growth of the carbides is generally inhibited by increasing the cooling rate, but rapid cooling is difficult to achieve for large castings. Therefore, the carbide is refined by a high-temperature homogenization heat treatment process, so that the energy consumption is increased, the efficiency is low, and the cracking is easy to occur if the cooling speed is not well controlled.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to solve the key common technical problem of carbide control of high-carbon wear-resistant cast steel and provides a method for controlling the shape, size and distribution of carbide by combining modification treatment and subsequent heat treatment. According to the invention, a self-designed and prepared modifying treatment agent is added in the high-carbon cast steel smelting process by a wire feeding method, under the action of the modifying agent, the nucleation and growth behaviors of carbide in the molten steel solidification process are controlled, the growth of the carbide is inhibited while the nucleation rate of the carbide is improved, the carbide is refined and passivated in an as-cast state, the distribution of the carbide is more uniform, and a tissue and component basis is provided for further controlling the carbide in the subsequent heat treatment.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention discloses a method for controlling carbide of high-carbon wear-resistant cast steel by combining melt modification treatment with heat treatment, which comprises the following steps: smelting in induction furnace (or electric furnace) → LF refining (selectivity) → wire feeding with proper amount of melt modifier → casting pouring → casting annealing → casting quenching (normalizing) → casting tempering
Wherein:
smelting in an induction furnace (or an electric furnace), and selecting smelting modes such as the induction furnace, the electric furnace and the like according to specific production conditions;
LF refining (selectivity), namely, selectively adopting LF refining on the molten steel according to the refining process requirement and the production condition of a specific cast steel material;
adding a proper amount of melt alterant into the wire feeding, and adding a proper amount of alterant into the wire feeding mode according to the components of the specific cast steel;
casting, namely according to a specific casting process, slagging off and then casting and forming in various casting molds such as sand molds, metal molds, graphite molds and the like;
and (3) annealing, quenching (normalizing), tempering and the like of the casting, and selecting a normal heat treatment process according to specific cast steel components.
According to the control method provided by the invention, the LF refining (selectivity) comprises the following steps: and (3) selectively adopting LF refining according to the specific steel refining process requirement, and if the LF refining is adopted, adopting a refining slag system with the alkalinity of 4-9 and adding a proper amount of calcium. The refining slag system is composed of CaO and SiO 2 、Al 2 O 3 And MgO. If LF refining is not adopted, the step of adding a melt modifier is directly carried out.
According to the control method provided by the invention, the step of adding a proper amount of melt alterant into the thread feeding process comprises the following steps: and after the selective LF refining is finished, adding 5-20 kg/ton molten steel melt alterant according to the component characteristics of the cast steel. After the wire feeding is finished, argon is blown at the bottom of the furnace for stirring, the slag surface is slightly moved, the molten steel is not exposed, and the time is controlled to be 10-30 min; and if the argon blowing and stirring are carried out without the furnace bottom, the power is cut off and the stand is carried out for 5-20 min. The melt alterant comprises the following components in percentage by weight: 20-80% of rare earth (the content is not lower than 25%) ferrosilicon, 10-40% of aluminum-calcium alloy and other trace alloy elements M10-40%, wherein the trace elements M comprise the following elements in percentage by weight: 5 to 30% of Zr, 5 to 20% of W, 5 to 20% of Pb, 5 to 30% of Bi, 5 to 30% of Si, 2 to 20% of Co, and 0.1 to 1% of B.
Further preferably, the total weight percentage of the rare earth ferrosilicon and the aluminum calcium alloy is not less than 65 percent of the weight of the melt alterant.
The purpose of adding the melt alterant is to control the nucleation and growth behavior of carbide in the process of solidification of the molten steel in a casting mold, improve the nucleation rate of the carbide and inhibit the growth speed of the carbide, realize the refinement and passivation of the carbide in an as-cast state and promote the uniform distribution of the carbide in a matrix.
According to the carbide control method provided by the invention, the casting is annealed, is kept at the temperature of 800-1100 ℃ for a proper time, is cooled to 300 ℃ along with the furnace, and is then cooled by air.
According to the carbide control method provided by the invention, the casting is quenched (normalized), and is subjected to water quenching, oil quenching or air cooling after being kept at the temperature of 800-1100 ℃ for a proper time; if the normalizing process is adopted, only air cooling is adopted.
According to the carbide control method provided by the invention, the casting is tempered and air-cooled after heat preservation for a proper time at the temperature of 150-300 ℃.
The carbide control method provided by the invention has the beneficial effects that the carbide of the high-carbon wear-resistant steel in the as-cast state can be effectively controlled, and the composition segregation of the casting is improved while the as-cast carbide is refined and passivated. After the subsequent heat treatment, the spherical carbide with nanometer size is dispersed and distributed on the steel matrix.
The hardness of the high-carbon steel casting prepared by the carbide control method provided by the invention reaches HRC 58-65, the impact toughness is higher than that of high-chromium white cast iron, and the high-carbon steel casting is suitable for producing wear-resistant steel castings in the fields of mining machinery, engineering machinery, agricultural machinery, coal mine machinery and the like.
Drawings
FIG. 1 is an SEM photograph of a high carbon cast steel in example 1 of the present invention;
FIG. 2 is an SEM photograph of a high carbon cast steel not used in example 1 of the present invention;
FIG. 3 is an SEM photograph of a high-carbon cast steel according to example 2 of the present invention;
FIG. 4 is an SEM photograph of a high-carbon cast steel not used in example 2 of the present invention;
FIG. 5 is an SEM photograph of a high carbon cast steel in example 3 of the present invention;
fig. 6 is a SEM photograph of high carbon cast steel according to example 3 of the present invention.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The invention is further illustrated by the following description and the accompanying drawings.
Example 1
The high-carbon cast steel in the embodiment mainly comprises the following components: 0.8 percent of C, 4.5 percent of Cr, 0.5 percent of Mo and 0.5 percent of V. According to the method for controlling the carbide, the control of the carbide of the casting with the composition is implemented, and the method mainly comprises the following steps:
smelting 100kg of molten steel in an atmosphere environment by adopting a 100kg intermediate frequency furnace, and controlling the components to be on-line in an allowable range in consideration of the burning loss of alloy elements;
after complete melting and heat preservation for 5min, refining in a furnace, wherein the refining slag system comprises the following components in percentage by weight: 25% of CaO and 20% of SiO 2 、40％Al 2 O 3 15% MgO and the like;
after 20min of refining, adding a melt treatment agent into the wire feeding, wherein the melt treatment agent comprises the following components: 40% of rare earth ferrosilicon (the content of rare earth is 31%), 30% of aluminum-calcium alloy and other trace alloy elements M30%, wherein the trace elements M comprise the following raw materials in percentage by weight: 5% of Zr, 17% of W, 30% of Bi, 25.5% of Si, 2% of Co, 19.5% of Pb and 1% of B, and the addition amount of the melt processing agent is 1.0kg (10 kg/ton of molten steel); then, the power is cut off and the mixture is kept stand for 10 min;
heating to 1650 deg.C, removing slag, and pouring into metal mold to obtain steel casting.
Annealing the casting, keeping the temperature at 860 ℃ for 6 hours, cooling the casting to 300 ℃ along with the furnace, and then air-cooling the casting;
quenching the casting, and carrying out oil quenching after heat preservation for 1h at the temperature of 930 ℃;
tempering the casting, keeping the temperature at 200 ℃ for 4h, and then air-cooling
FIG. 1 is an SEM photograph of a casting subjected to the carbide control method, wherein spherical carbides with the size of 200-500 nm are uniformly dispersed and distributed in a tempered martensite matrix. The unmodified carbide is large in size, and the carbide is present in a coarse elongated form in some parts. The hardness of the casting is HRC 55-57, and the impact toughness is 4-8J/cm 2.
Example 2
The high-carbon cast steel in the embodiment mainly comprises the following components: 1.3 percent of C, 5.0 percent of Cr, 0.6 percent of Mo and 0.6 percent of V. According to the method for controlling the carbide, the control of the carbide of the component casting is implemented, and the method mainly comprises the following steps:
smelting 100kg of molten steel in a 100kg intermediate frequency furnace in an atmospheric environment, and controlling the components to be on-line within an allowable range in consideration of the burning loss of alloy elements;
after complete melting and heat preservation for 5min, refining in a furnace, wherein the refining slag system comprises the following components in percentage by weight: 25% of CaO and 20% of SiO 2 、40％Al 2 O 3 15% MgO and the like;
after refining for 20min, feeding the wire and adding a melt treating agent, wherein the melt treating agent comprises the following components: the alloy comprises 60% of rare earth ferrosilicon, 20% of aluminum-calcium alloy and other trace alloy elements M20%, wherein the trace elements M comprise the following raw materials in percentage by weight: 22.5% of Zr, 5% of W, 5% of Bi, 30% of Si, 20% of Co, 17% of Pb and 0.5% of B, and the addition amount of the melt processing agent is 1.2kg (12 kg/ton of molten steel); then, powering off and standing for 10 min;
heating to 1630 deg.C, removing slag, and pouring into metal mold to obtain steel casting.
Annealing the casting, keeping the temperature at 860 ℃ for 6 hours, cooling the casting to 300 ℃ along with the furnace, and then air-cooling the casting;
quenching the casting, and carrying out oil quenching after heat preservation for 1h at the temperature of 930 ℃;
tempering the casting, keeping the temperature at 200 ℃ for 4h, and then air-cooling
FIG. 3 is an SEM photograph of a casting subjected to the carbide control method, wherein spherical carbides with the size of 200-500 nm are uniformly dispersed and distributed in a tempered martensite matrix. The unmodified carbide is coarse, and the local carbide is distributed in bulk or even in a net shape. The hardness of the casting is HRC 58-60, and the impact toughness is 3-6J/cm 2.
Example 3
The high-carbon cast steel in the embodiment mainly comprises the following components: 1.7 percent of C, 4.5 percent of Cr, 0.5 percent of Mo and 0.6 percent of V. According to the method for controlling the carbide, the control of the carbide of the component casting is implemented, and the method mainly comprises the following steps:
smelting 100kg of molten steel in an atmosphere environment by adopting a 100kg intermediate frequency furnace, and controlling the components to be on-line in an allowable range in consideration of the burning loss of alloy elements;
after complete melting and heat preservation for 5min, refining in a furnace, wherein the refining slag system comprises the following components in percentage by weight: 25% of CaO and 20% of SiO 2 、40％Al 2 O 3 15% MgO and the like;
after refining for 20min, feeding the wire and adding a melt treating agent, wherein the melt treating agent comprises the following components: 50% of rare earth ferrosilicon, 25% of aluminum-calcium alloy and other trace alloy elements M25%, wherein the trace elements M comprise the following raw materials in percentage by weight: 30% of Zr, 20% of W, 24.4% of Bi, 5% of Si, 15.5% of Co, 5% of Pb and 0.1% of B, and the addition amount of the melt processing agent is 1.5kg (15 kg/ton molten steel); then, the power is cut off and the mixture is kept stand for 10 min;
heating to 1600 ℃, removing slag and pouring into a metal mold to obtain a steel casting.
Annealing the casting, keeping the temperature at 860 ℃ for 6 hours, cooling the casting to 300 ℃ along with the furnace, and then air-cooling the casting;
quenching the casting, and carrying out oil quenching after heat preservation for 1h at the temperature of 930 ℃;
tempering the casting, keeping the temperature at 200 ℃ for 4h, and then air-cooling
FIG. 5 is an SEM photograph of a casting after the carbide control method is implemented, and spherical carbides with the size of 200-800 nm are uniformly dispersed and distributed in a tempered martensite matrix. The carbide of the casting which is not subjected to the deterioration treatment is coarse, and the carbide of a partial area exists in a net shape and a long strip shape. The hardness of the casting is HRC 61-63, and the impact toughness is 2-4J/cm 2.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The melt modification agent for controlling the carbide of the high-carbon wear-resistant cast steel is characterized by comprising the following components in percentage by weight: 20-60% of rare earth ferrosilicon, 10-40% of aluminum-calcium alloy and other trace alloy elements M25-40%; the trace alloy element M consists of the following raw materials in percentage by weight: 5 to 30% of Zr, 5 to 20% of W, 5 to 20% of Pb, 5 to 30% of Bi, 5 to 30% of Si, 2 to 20% of Co, and 0.1 to 1% of B.
2. The agent for modifying a melt according to claim 1, wherein the rare-earth ferrosilicon contains not less than 25% of rare-earth elements.
3. The melt-modifying agent according to claim 1, wherein the total weight percentage of the rare earth ferrosilicon and the aluminum calcium alloy is not less than 65% of the weight of the melt-modifying agent.
4. A method for controlling the carbide of high-carbon wear-resistant cast steel is characterized by comprising the following steps: smelting in an induction furnace or an electric furnace → adding a proper amount of melt modification treatment agent into a wire → pouring a casting → annealing the casting → quenching or normalizing the casting → tempering the casting;
a melt-modifying agent is added to the steel wire, and the melt-modifying agent according to any one of claims 1 to 3 is added by wire feeding according to the components of the steel grade.
5. The method for controlling carbides in high-carbon, wear-resistant cast steel according to claim 4, wherein said wire-feeding addition of melt-deterioration agents comprises: feeding a melt modification treatment agent line of 5-20 kg/ton of molten steel; after wire feeding is finished, argon is blown to the bottom of the furnace for stirring, the slag surface is slightly moved, the molten steel is not exposed, and the time is controlled to be 10-30 min; or argon blowing and stirring are carried out without the furnace bottom after the wire feeding is finished, and the power is cut off and the stand is carried out for 5-20 min.
6. The method for controlling carbides of high-carbon, wear-resistant cast steel according to claim 4, wherein said casting is annealed: keeping the temperature at 800-1100 ℃ for a proper time, cooling the mixture to 300 ℃ along with the furnace, and then cooling the mixture in the air.
7. Method for controlling the carbides of high-carbon, wear-resistant, cast steel according to claim 4, characterized in that the quenching or normalizing of the casting: and (3) preserving the temperature at 800-1100 ℃ for a proper time, and then performing water quenching, oil quenching or air cooling.
8. The method for controlling carbides of high-carbon, wear-resistant cast steel according to claim 4, wherein said casting is tempered: keeping the temperature for a proper time at the temperature of 150-300 ℃ and then cooling in air.
9. A high-carbon wear-resistant cast steel prepared by the melt modification agent as set forth in any one of claims 1 to 3 or the method as set forth in any one of claims 4 to 8.
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