CN111375736B - Casting method of martensite precipitation hardening stainless steel - Google Patents
Casting method of martensite precipitation hardening stainless steel Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/043—Curved moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/111—Treating the molten metal by using protecting powders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
- B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
- B22D11/225—Controlling or regulating processes or operations for cooling cast stock or mould for secondary cooling
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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Abstract
The invention provides a casting method of martensite precipitation hardening stainless steel, which is carried out in a straight arc-shaped slab continuous casting machine and comprises the following steps: (1) molten steel in the tundish enters the crystallizer through the submerged nozzle, covering slag is added on the surface of the molten steel to prevent secondary oxidation, the molten steel is cooled for the first time under the action of cooling water of the crystallizer, the casting machine is started for withdrawal and straightening at the same time, and a blank shell runs in the casting machine at a certain withdrawal speed under the action of the withdrawal and straightening; (2) and the blank shell obtained by the primary cooling enters a secondary cooling area for secondary cooling. Compared with the traditional die casting method, the method of the invention has the advantages of high metal yield, low production cost and high production efficiency.
Description
Technical Field
The invention relates to the technical field of stainless steel smelting, in particular to a casting method of martensite precipitation hardening stainless steel.
Background
The martensite precipitation hardening stainless steel has good obdurability, the corrosion resistance in the atmosphere and weak corrosive medium is superior to that of ferrite steel and martensite steel, the martensite precipitation hardening stainless steel can bear certain cold processing, the martensite precipitation hardening stainless steel is easier to weld, and the application amount in the precipitation hardening stainless steel is the largest.
In the casting process, the cooling speed has a direct influence on the toughness of the martensite precipitation hardening steel, and the slow cooling can cause the segregation of carbides and nitrides along grain boundaries. The delta ferrite of the steel grade generates solidification segregation in the solidification process to cause uneven plasticity and toughness, so the cooling of the steel grade needs to be designed.
In addition, the martensite precipitation hardening steel has very high copper and molybdenum contents, so that the steel has extremely strong crack sensitivity, and is generally realized by die casting at present, and the die casting process has low metal yield, high production cost and unstable internal quality.
In general, there is currently no low-cost, high-efficiency casting method that can achieve high quality martensitic precipitation hardened steel.
Disclosure of Invention
Aiming at the defects, the invention provides a continuous casting production process of the martensitic precipitation hardening stainless steel, and the martensitic precipitation hardening stainless steel is successfully produced in a straight arc-shaped plate blank continuous casting machine.
The invention realizes the above purposes by the following technical scheme:
a casting method of a martensitic precipitation hardened stainless steel, said casting method being performed in a straight arc slab caster, comprising the steps of:
(1) molten steel in the tundish enters the crystallizer through the submerged nozzle, is cooled to form a solidified blank shell, and casting powder is added on the liquid level of the molten steel;
(2) and the blank shell obtained by the primary cooling enters a secondary cooling area for secondary cooling.
Further, the martensitic precipitation hardened stainless steel has the following composition:
c: less than or equal to 0.07%, Si: less than or equal to 0.70 percent, Mn: less than or equal to 1.00 percent, P: less than or equal to 0.030 percent, S: less than or equal to 0.030 percent, Cr: 13.00-14.50%, Ni: 5.00-5.80%, Mo: 1.30-1.800%, Cu: 1.30-1.800%, Nb: 0.25-0.45% and the balance of Fe element and inevitable impurities.
Further, in the step (1), the drawing speed of molten steel in the tundish entering the crystallizer through the submerged nozzle is 0.70-0.90 m/min.
Further, the mold flux comprises the following components: 32.3 to 38.3 percent of CaO and SiO2 26.4～32.4％、Al2O3 2.7～4.7％、Li2O 0.4～1.0％、Na210.1-15.9% of O, 7.4-12.2% of F and 3.2-4.6% of total carbon.
Further, the water content of the casting powder is less than or equal to 0.5 wt%, the melting point is 1005-1065 ℃, and the viscosity at 1300 ℃ is 0.3-1.1 Poise.
Further, the cooling water parameters of the crystallizer are as follows: the wide water flow is 2600-2800L/min, and the narrow water flow is 480-520L/min.
Further, when the molten steel is fed into a crystallizer at a casting speed, the superheat degree of the tundish molten steel is 20-35 ℃, the binary alkalinity R of a tundish covering agent is 1.00-1.20, and the insertion depth of a water gap is 135-155 mm.
Furthermore, the specific water amount of the secondary cooling area is 0.70-0.85L/kg.
Furthermore, the water amount of the secondary cooling area is 10-195L/min.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) according to the invention, the straight arc-shaped continuous casting machine is adopted to replace die casting to produce the martensite precipitation hardening stainless steel, so that the production efficiency is improved; the metal yield is greatly improved, and the production cost is reduced.
(2) According to the invention, the straight arc-shaped continuous casting machine is adopted to replace die casting to produce the martensite precipitation hardening stainless steel, and qualified precipitation hardening stainless steel continuous casting plate blanks are produced by optimizing process parameters, so that quality defects of cracks, slag inclusion, inclusion and the like of the casting blanks are effectively prevented, and steel leakage accidents are avoided.
Drawings
FIG. 1 is a schematic view of a straight arc slab caster.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
At present, martensite precipitation hardening stainless steel is mostly produced by die casting or electroslag remelting process, and has the problems of low production efficiency, low metal yield and the like. In view of these problems, the inventors of the present invention have studied the casting process of the martensitic precipitation hardening stainless steel, and have optimized the casting method, cooling method, parameter design, and the like, and finally creatively proposed a casting method of the martensitic precipitation hardening stainless steel.
The martensite precipitation hardening stainless steel has high copper and molybdenum content, so that the copper content in the steel is increased, a low-melting-point phase is easy to form, the low-melting-point phase is easy to aggregate in a crystal boundary, the steel has high crack sensitivity, the temperature is improperly controlled in the continuous casting bending straightening process, and cracks are easy to generate. The casting method of the martensitic precipitation hardening stainless steel of the invention is proposed through the design of the cooling process.
The martensitic precipitation hardening steel (or martensitic precipitation hardening stainless steel) is martensitic stainless steel with a carbon content of less than 0.1%, which is further strengthened by adding strengthening elements such as copper, molybdenum, niobium and the like to precipitate carbides and intermetallic compounds. In the present invention, the martensitic precipitation hardening steel has a composition of C: less than or equal to 0.07%, Si: less than or equal to 0.70 percent, Mn: less than or equal to 1.00 percent, P: less than or equal to 0.030%, S: less than or equal to 0.030%, Cr: 13.00 to 14.50%, Ni: 5.00-5.80%, Mo: 1.30-1.800%, Cu: 1.30-1.800%, Nb: 0.25-0.45%, and the balance of Fe element and inevitable impurities.
The casting method of the martensite precipitation hardening stainless steel is straight arc continuous casting, adopts a straight arc slab continuous casting machine, adopts a low drawing speed according to the characteristics of the martensite precipitation hardening stainless steel, and designs secondary cooling as weak cooling. The method comprises the following steps: (1) molten steel in the tundish enters the crystallizer through the submerged nozzle, is cooled to form a solidified blank shell, and casting powder is added on the liquid level of the molten steel; (2) and the blank shell after primary cooling enters a secondary cooling area for secondary cooling.
The straight arc-shaped slab caster adopted by the casting method of the martensitic precipitation hardening stainless steel is conventional equipment in the field, and in the actual application process, a person skilled in the art can reasonably select the slab caster according to actual needs, and details are not described herein.
Specifically, the casting method of the martensitic precipitation hardening stainless steel of the present invention will be explained with reference to fig. 1. The casting method of the martensitic precipitation hardening stainless steel of the present invention comprises the steps of:
(1) primary cooling
Molten steel in the tundish enters the crystallizer through the submerged nozzle, protective slag is added on the surface of the molten steel to prevent secondary oxidation, the molten steel is cooled once under the action of cooling water of the crystallizer, the casting machine is started to perform withdrawal and straightening simultaneously, and a blank shell runs in the casting machine at a certain withdrawal speed under the action of the withdrawal and straightening
Specifically, molten steel to be smelted is contained in a ladle 1. In smelting, molten steel having the following composition by weight is fed into the mold 3 of a straight arc-shaped slab caster, and in the process, specifically, the tundish 2 receives molten steel from the ladle 1 and distributes the molten steel to the mold 3:
c: less than or equal to 0.07%, Si: less than or equal to 0.70 percent, Mn: less than or equal to 1.00 percent, P: less than or equal to 0.030%, S: less than or equal to 0.030 percent, Cr: 13.00-14.50%, Ni: 5.00-5.80%, Mo: 1.30-1.80%, Cu: 1.30-1.80%, Nb: 0.25-0.45%, and the balance of Fe element and inevitable impurities.
Since the martensitic precipitation hardening stainless steel has a large alloy ratio, the speed at which a billet is run in a continuous casting machine, i.e., the drawing speed (simply referred to as "drawing speed"), is designed to be a low drawing speed. Specifically, the pulling speed is designed to be 0.70-0.90 m/min. And, this pull rate is used throughout the steady state casting of the martensitic precipitation hardened stainless steel. The inventor finds that under the condition of relatively low pulling speed, the residence time in the cooling area is relatively long, the cooling rate can be properly increased, the segregation of internal elements is improved, and the degree of the segregation of carbide and nitride along the grain boundary is reduced.
In the method, the superheat degree of the molten steel in the tundish 2 is 20-35 ℃, and the tundish covering agent has binary alkalinity (CaO/SiO)2) R is 1.00 to 1.20, for example 1.05. The tundish covering agent is added into the tundish 2 and covers the molten steel surface to isolate air, and mainly prevents the molten steel from secondary oxidation. Immersion waterThe depth of the insertion opening is 135-155 mm, the submerged nozzle is a passage for molten steel in the tundish 2 to enter the crystallizer 3, and the inventor finds that the nozzle mainly has great influence on the liquid level of the molten steel in the crystallizer, and the excessive depth or the excessive depth of the nozzle can have adverse effect on the surface quality of a casting blank, for example, slag entrapment can be generated.
The molten steel is once cooled in the mold 3. The setting of the parameters of the crystallizer is critical for the primary cooling of the molten steel. In the method of the present invention, preferably, the cooling water of the crystallizer 3 has a wide water flow rate of 2600 to 2800L/min (more preferably 2700L/min) and a narrow water flow rate of 480 to 520L/min (more preferably 500L/min).
The mold 3 is an important part of the continuous casting process, and is essentially a water-cooled copper mold, and for slab casting, 4 copper plates are usually combined (i.e. 2 narrow surfaces and 2 wide surfaces are combined, and the narrow surfaces are clamped by the two wide surfaces), and each copper plate is provided with a separate cooling water system. In the continuous casting production process, cooling water is introduced, so that the heat of the molten steel is taken away by the circulating cooling water to form a solidified initial shell. The water flow of the wide surface and the water flow of the narrow surface are required to be capable of taking away heat emitted when molten steel is solidified. The amount of cooling water required for heat release from the mold 3 is obtained from data such as the specific heat capacity of molten steel and solidification heat release. The inventor calculates the heat flux density according to the cooling water quantity to keep a relatively reasonable value, so that the possibility of occurrence of cracks of the casting blank is reduced. Other parameters relating to the crystalliser 3 belong to the generic data.
In the method of the present invention, it is preferable that the molten steel is protected with mold flux during primary cooling in the mold 3. The water content of the casting powder adopted by the method is less than or equal to 0.5 wt%, the melting point is 1005-1065 ℃, and the viscosity at 1300 ℃ is 0.3-1.1 Poise. The main chemical components (wt%) of the mold flux used in the method of the present invention are shown in the following table:
according to the inventionThe method adopts the covering slag and is mainly based on the following inventive concept: the martensite precipitation hardening stainless steel has low carbon content, high alloy content and low liquidus temperature, contains copper, is easy to form a low-melting-point phase and crack, and needs to control proper mold flux to transfer heat so as to reduce the crack generated in the solidification process. The covering slag is added on the liquid level of the molten steel in the crystallizer 3, and after the covering slag is melted to form liquid slag, the contact between the molten steel and air can be prevented, and the secondary oxidation of the molten steel can be prevented. The liquid slag flows between the wall of the crystallizer and the solidified blank shell, and the formed slag film can play a role in lubricating and controlling heat transfer, so that the surface of the casting blank is prevented from being bonded and generating crack defects. For the martensitic precipitation hardening stainless steel which is sensitive to cracks in the invention, the uniform heat transfer control is mainly carried out through the casting powder (the proper alkalinity is CaO/SiO)2) So as to ensure the uniform and stable growth of the casting blank shell and reduce the occurrence of cracks.
The molten steel is cooled and solidified once in the crystallizer 3 to form a blank shell, and then the next step is carried out.
(2) Secondary cooling
The molten steel is cooled and solidified once in the crystallizer 3 to form a blank shell, the blank shell is output from the crystallizer 3 at a pulling speed of 0.70-0.90 m/min and enters a secondary cooling area 4, and the secondary cooling area consists of a plurality of fan-shaped sections and comprises a cooling water system, a pulling and straightening system, a bending and straightening device and the like.
According to the characteristics of martensite precipitation hardening stainless steel, in order to ensure that no crack is generated in the straightening process, in the secondary cooling design, the surface temperature of a casting blank in a bending and straightening area is more than or equal to 900 ℃, and a relatively reasonable cooling mode is obtained through calculation according to relevant parameters of steel grades.
In the method, the specific water amount of the secondary cooling area 4 is 0.75-0.85L/kg, such as 0.80L/kg, and the specific water amount of the secondary cooling area is changed with the temperature of the molten steel and the drawing speed and also with the temperature of the casting blank at the same drawing speed.
In the method of the present invention, the cooling water in the secondary cooling zone 4 is configured to be 10 to 195L/min.
In one embodiment, for example, when the pulling rate is 0.75m/min, the secondary cooling water may be configured in the following manner:
in the secondary cooling area 4, electromagnetic stirring is adopted, the current is 1600-1700A, the frequency is 3.5Hz, and the reversing time is 20 seconds. The electromagnetic stirring parameters are designed according to the characteristics of steel grades, and the main purpose of the electromagnetic stirring parameters is to homogenize elements in the steel in the solidification process and reduce the segregation of the elements.
The cast slab obtained after the secondary cooling in the secondary cooling zone 4 may be subjected to a subsequent operation, such as rolling or the like.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
The specific parameters of the straight arc slab continuous casting machine adopted in the following embodiments are as follows:
the secondary cooling water in the secondary cooling area in each of the following examples was configured as follows:
the parameters of the mold flux used in the following examples were as follows: (wt%)
The relevant parameters of the crystallizer in the following examples are as follows:
wide water flow 2700L/min and narrow water flow 500L/min.
The superheat degree of the tundish molten steel is 20-35 ℃, and the tundish covering agent has binary alkalinity CaO/SiO2R ═ 1.05. The superheat degree of the tundish is the difference value between the molten steel temperature of the tundish and the liquidus line of the molten steel, is obtained by measuring the molten steel in the tundish in the actual process, and changes within a certain range in the casting process.
The immersion nozzle insertion depth is maintained at a substantially constant value during the continuous casting process.
Example one
The applicant company produces martensite precipitation hardening stainless steel slabs in a straight arc slab continuous casting machine in 2018 in 6 months (secret experiment), and produces 1 furnace steel, wherein the specification of the slabs is 200 multiplied by 1240 multiplied by Lmm. The process conditions were as follows:
components of molten steel
The actual components of the molten steel are as follows, and meet the national standard component requirements of steel grades.
| Element(s) | C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Nb | Fe |
| Actual value | 0.042 | 0.38 | 0.51 | 0.016 | 0.0011 | 13.82 | 5.36 | 1.39 | 1.37 | 0.29 | Remainder of |
② process temperature and pull rate control
| Tundish temperature 1 | |
Tundish temperature 3 | |
Tundish temperature 5 | Pulling speed |
| 1508 | 1505 | 1506 | 1502 | 1502 | 0.75 |
Thirdly, the special covering slag is used, the process slag condition is normal, the consumption is 0.52 kg/ton steel, and the thickness of liquid slag is 9 mm; the immersion type water gap is inserted with the depth of 140 mm;
fourthly, using a newly designed water meter for secondary cooling water, wherein the specific water quantity is 0.80L/kg;
measuring the surface temperature of the casting blank before straightening to 950 ℃ in a secondary cooling area to meet the temperature requirement before straightening;
sixthly, casting blank surface quality: and measuring the depth of the vibration mark on the surface of the casting blank, wherein the maximum depth of the vibration mark is less than or equal to 0.5mm, inspecting the surface of the casting blank, and the method has no defects of rolling slag, depression, cracks and the like and has good surface quality of the casting blank. The internal quality center porosity rating of the casting blank is grade 1 (rated according to the Mannesmann standard).
Example two
The applicant company produces martensite precipitation hardening stainless steel slabs in a straight arc slab continuous casting machine in 2019 in 4 months (secret experiment), and the continuous casting furnace 2 is produced at this time, wherein the specification of the slabs is 200 multiplied by 1240 multiplied by Lmm. The process conditions were as follows:
components of molten steel
The actual components of the molten steel of the two furnaces are as follows, and the requirements of national standard components of steel grades are met.
| Element(s) | C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Nb | Fe |
| Heat 1 | 0.042 | 0.38 | 0.51 | 0.016 | 0.0011 | 13.82 | 5.36 | 1.39 | 1.37 | 0.29 | Remainder of |
| |
0.038 | 0.41 | 0.53 | 0.015 | 0.001 | 13.76 | 5.32 | 1.41 | 1.36 | 0.30 | Remainder of |
② process temperature and pull rate control
| Index (I) | Tundish temperature 1 | |
Tundish temperature 3 | |
Tundish temperature 5 | Pulling speed |
| Heat 1 | 1509 | 1507 | 1507 | 1505 | 1505 | 0.75 |
| |
1504 | 1502 | 1501 | 1501 | 1499 | 0.75 |
Thirdly, the special covering slag is used, the process slag condition is normal, the slag consumption of the two furnaces of steel is 0.54 kg/ton and 0.50 kg/ton respectively, the thickness of the liquid slag is 9-11 mm, and the covering slag consumption and the liquid slag layer are stable; the immersion type water gap is inserted with the depth of 140 mm;
fourthly, the specific water quantity of the secondary cooling water is 0.80L/kg when the water meter is still used in the 1 st production;
measuring the temperature of the steel of the two furnaces before straightening in a secondary cooling area and a straightening area, wherein the measurement results are 955 ℃ and 943 ℃ respectively, and the temperature requirement before straightening is met;
sixthly, the surface quality of the two-furnace steel casting blank is good, and no obvious defect is visible to the naked eye.
Compared with the existing method (such as die casting), the casting method of the straight arc continuous casting has the main advantages of shortening the production flow, improving the metal yield, reducing the energy consumption, having high automation degree and the like. Specifically, the production of the continuous casting blank omits the working procedures of demoulding, die setting, steel ingot heating, blooming, cogging and the like; compared with the die casting metal, the yield of the continuous casting billet is improved by at least about 10 percent; continuous casting billets can be subjected to red-feeding hot charging, so that energy consumption is reduced; the method is realized by adopting a straight arc slab continuous casting machine, and can improve the labor productivity through automatic control.
The inventor of the invention optimally designs the process parameters of the casting method according to the characteristics of the martensite precipitation hardening stainless steel, thereby improving the surface quality of the casting blank. As proved in the above examples, the maximum depth of oscillation mark is less than or equal to 0.5mm when the depth of oscillation mark on the surface of the casting blank is measured, and the surface of the casting blank is inspected, and the defects such as rolling slag, dent, cracks and the like do not exist.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other substitutions, modifications, combinations, changes, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be construed as equivalents and included in the protection scope of the present invention.
Claims (1)
1. A casting method of a martensitic precipitation hardened stainless steel, characterized in that the casting method is performed in a straight arc shaped slab caster, comprising the steps of:
(1) molten steel in the tundish enters the crystallizer through an immersion nozzle, a solidified blank shell is formed by cooling, and covering slag is added on the liquid level of the molten steel;
(2) the blank shell obtained by the primary cooling enters a secondary cooling area for secondary cooling;
wherein the composition of the covering slag is as follows: 32.3 to 38.3 percent of CaO and SiO2 26.4～32.4％、Al2O32.7～4.7％、Li2O 0.4～1.0％、Na210.1-15.9% of O, 7.4-12.2% of F and 3.2-4.6% of total carbon, wherein the water content of the covering slag is less than or equal to 0.5 wt%, and the viscosity at 1300 ℃ is 0.3-1.1 Poise;
wherein the cooling water parameters of the crystallizer are as follows: wide water flow 2700L/min and narrow water flow 500L/min;
wherein, the insertion depth of the submerged nozzle is 140 mm;
the secondary cooling water in the secondary cooling area adopts the following configuration:
the adopted straight arc-shaped slab continuous casting machine has the parameters as follows:
the molten steel comprises the following components in percentage by weight: 0.042% of C, 0.38% of Si, 0.51% of Mn, 0.016% of P, 0.0011% of S, 13.82% of Cr, 5.36% of Ni, 1.39% of Mo, 1.37% of Cu, 0.29% of Nb and the balance of Fe;
in the step (2), the specific water amount of the secondary cooling area is 0.80L/kg; during the casting process, the casting speed was 0.75 m/min.
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