WO2014191783A1 - Procédé de production d'acier micro-allié de pureté ultra-élevée contenant du soufre et ayant une incidence sur les procédés de resulfuration métallurgiques - Google Patents

Procédé de production d'acier micro-allié de pureté ultra-élevée contenant du soufre et ayant une incidence sur les procédés de resulfuration métallurgiques Download PDF

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Publication number
WO2014191783A1
WO2014191783A1 PCT/HU2014/000045 HU2014000045W WO2014191783A1 WO 2014191783 A1 WO2014191783 A1 WO 2014191783A1 HU 2014000045 W HU2014000045 W HU 2014000045W WO 2014191783 A1 WO2014191783 A1 WO 2014191783A1
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WO
WIPO (PCT)
Prior art keywords
steel
sulphur
slag
deoxidation
content
Prior art date
Application number
PCT/HU2014/000045
Other languages
English (en)
Inventor
László KISS
Oszkár GREGA
Original Assignee
Astra Mining Hungary Kft.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Astra Mining Hungary Kft. filed Critical Astra Mining Hungary Kft.
Publication of WO2014191783A1 publication Critical patent/WO2014191783A1/fr

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Classifications

    • 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
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/076—Use of slags or fluxes as treating agents
    • 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
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • 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
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/40—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
    • 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

Definitions

  • the technological process as defined in the invention is suitable for the production of high purity microalloyed steel containing sulphur with better machinability.
  • the new technological process first we produce an ultra-high purity (free from gas, inclusion and sulphur) liquid steel, and in this steel bath prepared as above the operations of resulphurization providing good cutting performance, which is further refined by laser melting on the surface, in order to obtain surface precision machining.
  • the sulphur content is an inevitable, generally harmful accompanying element of iron metallurgy products.
  • sulphur has a very favourable effect: thanks to the low melting point of MnS generated on crystal the cutting performance of steel becomes better, and through the sublimation property of sulphur supports the self-lubrication during usage of the manufactured product.
  • the distribution of MnS inclusions may be in the range of 10- ⁇ / ⁇ 2 , because above that level the quantity of surface defects increases.
  • JP- 9-031.522 determines the range of free O content positively affecting the formation of sulphides more rigorously in 100-200ppm, favourably in 120- 180ppm.
  • the sulphur is freely soluble in steel while it considerably does not dissolve in solid iron.
  • FeS and MnS are present.
  • the melting point of FeS is 1193 °C, whilst that of MnS is 1620 °C.
  • the problem is caused by the fact that the FeS forms an eutectic with iron with a melting point of 988 °C. Since the FeS essentially does not dissolve in iron crystals, at cooling the FeS concentrates in the melt among the iron crystals. This melt will chill when temperature reaches the temperature of eutectic crystallisation and occurs in the form of so called intercrystalline sulphide net. Given that this net is extremely rigid it causes the steel to be fragile.
  • the MnS forms rounded inclusions, which slightly affect the strength characteristic of steel, but in adequate quantity it is able to render the steel chips frangible.
  • the resulphurization process applied for traditional steel production is performed directly in kettle at steel tapping when micro alloying the sulphur by adding 99% purity sulphur powder.
  • the aim of the invention is to elaborate a sulphur microalloying method, which improves the cutting performance of high purity steel suitable for production meanwhile eliminating the above mentioned disadvantages.
  • Another aim of the process is to reduce the quantity of inclusions worsening the castability of steel with a technology obtaining high purity of steel to the extent to fully replace the Ca-inclusion modification technology inevitably applied by all the other patents, beside the considerable improvement of the quality properties of steel.
  • the cutting performance of steel provided by the technology defined in the invention can be further improved by introducing iron sulphide on the steel surface.
  • the most favourable method of application is to lay a sulphide net on the surface of steel profiles and to melt the surface with laser.
  • the invention is suitable for the production of high purity microalloyed steel containing sulphur, during which following an effective deoxidation the sulphur content of steel is first reduced below S ⁇ 0.005 %, then the sulphur content adequate to the prescribed concentration will be added to the pure steel by sulphur cored wire.
  • a melt shall be made in the steel manufacturing machine, in accordance with the chemical composition of steel and slag, the necessary metal alloying is performed during tapping with slag restraining, while subject to the carbon and active oxygen content, the liquid steel shall be pre-deoxidized with 0.7 - 1.1 kg/t Al and aluminate slag of a grain size of 2.0 - 2.5 kg/t, 10 mm.
  • Another advantageous application method of the process described in the invention is when in order to obtain an extra high purity, during the ladle metallurgical treatment referred to a steel ladle with a volumetric capacity of 80- 100 tons of steel, a clearing argon rinse with an intensity of 50 - 100 l/min or inductive mixing is performed.
  • the fourth advantageous application method of the process described in the invention is when during the ladle metallurgical treatment applying an aggregation and diffusion deoxidation by the dosage of Al-wire, the active oxygen level of steel is reduced below ⁇ 2 ppm and its sulphur content is reduced below 0.005%, and subject to the quality of steel to be produced an argon gas and/or inductive mixing and at a pressure lower than 3 torr, at least for 10 minutes under vacuum, carbon-deoxidation and gas elimination is performed.
  • the fifth advantageous application method of the process described in the invention is when the application of sulphur with a cored wire is performed right before issuing for casting, with a concentration adequate to the quality of steel.
  • the continuous casting is performed at an initial temperature 25°C higher than the liquidus temperature adequate to the composition of the produced steel, meanwhile the liquid steel is inducted in the crystal growth device in a closed system provided by protective tube, applying inductive mixing and casting powder.
  • the eighth advantageous application method of the process described in the invention is when the produced profiles are coated with a net made of steel wire with high sulphur content, and the surface is melted by laser.
  • the seventh advantageous application method of the process described in the invention is also when a net is applied with a gap width of 0.3 - 3 mm and a diagonal rate of 1.5 made of rhombus shaped gaps.
  • Figure 1 shows the graph of severed (middle) band of Jominy hardenability provided for the quality 42 CrMoS4B
  • the process defined in the invention can be known through the production of a tempered, premium quality, sulphur (and boron) microalloyed steel with a severed band of Jominy hardenability.
  • the matter of microalloying with sulphur is to perform an effective deoxidation and desulphurization before alloying.
  • the values S ⁇ 0,005 % and ⁇ [O] ⁇ 12 ppm shall be reached in the steel bath.
  • the carbonization material necessary for the production (calculated for 0,35% oxidation of carbon), the first rate of quicklime and the alloy metal FeMo calculated for the lower limit of prescription shall be added to the primary melting device, together with the waste charged into basket no I.
  • Melted steel is made by argon agitation during melting.
  • a steel and slag sample shall be tested in order to determine the chemical composition.
  • the liquid steel shall be pre-deoxidized with 0.7 - 1.1 kg/t Al and aluminate slag of a grain size of 2.0 - -2.5 kg/t, 10 mm.
  • the tapping is performed into a ladle suitable for lower argon treatment and evacuation, heated to a min. of 1000 °C.
  • the tapping is performed with slag restraining. After a slag-free tapping a slag correction and staged deoxidation is applied.
  • the new slag formation shall be started immediately by the dosage of fresh quicklime (CaO).
  • the new slag is melted by starting arc heating and argon (+ inductive) mixing, than a slag reduction is performed for diffusion deoxidation, by forming a synthetic slag by the application of a CaO + AI 2 O 3 + Almeai mixture of proportion 88: 19:1. This is followed by sample taking for the determination of slag composition, gas content and chemical characteristics.
  • the intensity of argon and/or inductive mixing is adjusted in a way that there will be no clean steel surface (the slag coverage shall be continuous).
  • the oxygen level of steel is reduced below 2 ppm.
  • the slag treatment shall be applied until the S content of the steel bath reaches the value of 0.005%.
  • a "soft argon rinse" for at least 15 minutes shall be performed, calculating for a steel ladle with a volumetric capacity of 80-100 tons of steel, with the intensity of 50 - 100 l/min for the adequate elimination of inclusions.
  • the evacuation shall be controlled in a way that the pressure should remain under 3 Hgmm for at least 10 minutes.
  • the melted steel is mixed with argon (and/or inductive agitator) at a very low intensity with continuously monitoring the movement of the bath and the slag, its surface Waving shall not exceed the amplitude of 200 mm.
  • a cleaning argon rinse shall be made for 5-8 minutes, and a microalloy corresponding to the specification for composition (Ti, B, Nb, V, Bi, etc.), and then - except the quality of tool and ball bearing inclusion modification is applied by adding Ca cored wire. Then the cleaning rinse with argon is repeated.
  • the steels produced with the resulphurization technology are manufactured in a closed system, applying magnetic agitator, through casting provided by protection against reoxidation, providing the following completions:
  • the casting in closed system is performed on a way that initial temperature of the steel casting is 25 °C higher than the liquidus temperature adequate to the composition of the manufactured steel, casting powder application shall be continuous and shall completely cover the surface of the steel mirror.
  • the dry casting powder prescribed for cast quality is applied continuously to the surface of the steel in the mould.
  • care shall be taken with sprinkled casting powder so that it shall reach the space around the immersion tube and corners of the mould, also paying attention to the surface of the casting powder to always stay black.
  • subsequent casting powder dose is immediately applied.
  • Casting powder is always selected for the given quality, instead of the common "powder grain sized” casting powder we apply "meal grain sized" powder as its quality is more adequate.
  • Adjustment of casting parameters (depending on section size: casting speed, magnetic mixing intensity, secondary cooling, etc.) is determined according to local circumstances. To avoid the pressure flakes of casted billets during cooling down a re-cooling with directed temperature shall be performed.
  • the inspection, qualification of the re-cooled billets consists of the followings:
  • the gas elimination is performed in all cases in evacuator device because of strict quality requirements.
  • the preparation of the steel is performed by injecting argon gas and/or inductive treatment instead of evacuation.
  • the procedure according to the invention can be also performed on the following technological route.
  • primary phase can also be performed in devices different from UHP furnace (e.g. LD converter) if this meets the requirements regarding the composition of steel produced at tapping.
  • UHP furnace e.g. LD converter
  • the moulds are placed on corrugated cardboard and a ceramic-magnetic plate with the clog serial number is placed on the inner wall of the moulds.
  • a heat resistant stocking reoxidative protection with argon ring is applied between the casting ladle and the shell.
  • a net made of steel wire of high iron-sulphide content is laid on the surface of the steel profile.
  • the iron-sulphide net has a gap width of 0.3 - 3 mm and is made with rhomboid holes with a diagonal rate of 1.5.
  • the surface of steel profile covered on this way is then melted so that the net will melt into the surface of the steel profile.
  • the rhomboid surface segments inside the net will become easy to cut while the solidity of the whole surface is held. Following the direction given by the shorter diagonals of the rhomboids of the net cutting will be easier while vertically to that direction the elasticity of the surface is only slightly decreased.
  • the application of the technology can involve the manufacturing of all kinds of quality and hardened steel where extremely high cleanliness, cored wire micro alloying technology and resulphurization and good castability are the primary tasks.
  • Quality characteristics of the manufactured steel products (stability, yield point, impact, hardenability, inclusion content, etc.) beside related standards are providing the more strict requirements (narrowed chemical composition and/or narrowed Jominy region, total oxygen content of max. 12 ppm, hydrogen content of max. 0.2 ppm, etc.) requested by the clients.
  • the sulphur content of the surface can be further increased so that it improves the cutting performance of the surface but does not influence the stability of the entire surface.

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

Abstract

L'invention concerne un procédé de fabrication d'un acier micro-allié au soufre de grande pureté. L'invention permet, après une désoxydation efficace, de réduire d'abord la teneur en soufre de l'acier à une valeur inférieure à S < 0,005 %, et à ajouter ensuite à l'acier pur la quantité de soufre adéquate par rapport à une concentration prescrite, par un fil fourré au soufre.
PCT/HU2014/000045 2013-05-27 2014-05-15 Procédé de production d'acier micro-allié de pureté ultra-élevée contenant du soufre et ayant une incidence sur les procédés de resulfuration métallurgiques WO2014191783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HUP1300336 2013-05-27
HU1300336A HUP1300336A2 (en) 2013-05-27 2013-05-27 Method for production of steel microalloyed with super clean sulfur and controlled sulfur addition affecting metalurgical characteristics

Publications (1)

Publication Number Publication Date
WO2014191783A1 true WO2014191783A1 (fr) 2014-12-04

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PCT/HU2014/000045 WO2014191783A1 (fr) 2013-05-27 2014-05-15 Procédé de production d'acier micro-allié de pureté ultra-élevée contenant du soufre et ayant une incidence sur les procédés de resulfuration métallurgiques

Country Status (2)

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HU (1) HUP1300336A2 (fr)
WO (1) WO2014191783A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106319135A (zh) * 2016-11-24 2017-01-11 新兴铸管股份有限公司 用于冶炼工艺防止C、Mn元素成分波动的方法
CN109457077A (zh) * 2018-11-05 2019-03-12 宝钢特钢韶关有限公司 一种控制非调质钢大尺寸夹杂物的制造方法
CN112036693A (zh) * 2020-07-28 2020-12-04 成都飞机工业（集团）有限责任公司 基于有限加权工序故障率的工序排序法
CN114807506A (zh) * 2022-04-20 2022-07-29 山西太钢不锈钢股份有限公司 一种车轮钢冶炼钢水增硫的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040223867A1 (en) * 2003-05-09 2004-11-11 Sanyo Special Steel Co., Ltd. Free machining steel for machine structural use having improved chip disposability
RU2261934C1 (ru) * 2004-06-11 2005-10-10 Открытое акционерное общество "Оскольский электрометаллургический комбинат" (ОАО "ОЭМК") Среднелегированная сталь повышенной обрабатываемости резанием
RU2262547C1 (ru) * 2004-06-29 2005-10-20 Открытое акционерное общество "Оскольский электрометаллургический комбинат" Среднеуглеродистая сталь повышенной обрабатываемости резанием
US20090169414A1 (en) * 2005-12-16 2009-07-02 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Low-carbon sulfur-containing free-cutting steel with excellent cuttability

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040223867A1 (en) * 2003-05-09 2004-11-11 Sanyo Special Steel Co., Ltd. Free machining steel for machine structural use having improved chip disposability
RU2261934C1 (ru) * 2004-06-11 2005-10-10 Открытое акционерное общество "Оскольский электрометаллургический комбинат" (ОАО "ОЭМК") Среднелегированная сталь повышенной обрабатываемости резанием
RU2262547C1 (ru) * 2004-06-29 2005-10-20 Открытое акционерное общество "Оскольский электрометаллургический комбинат" Среднеуглеродистая сталь повышенной обрабатываемости резанием
US20090169414A1 (en) * 2005-12-16 2009-07-02 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Low-carbon sulfur-containing free-cutting steel with excellent cuttability

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106319135A (zh) * 2016-11-24 2017-01-11 新兴铸管股份有限公司 用于冶炼工艺防止C、Mn元素成分波动的方法
CN109457077A (zh) * 2018-11-05 2019-03-12 宝钢特钢韶关有限公司 一种控制非调质钢大尺寸夹杂物的制造方法
CN112036693A (zh) * 2020-07-28 2020-12-04 成都飞机工业（集团）有限责任公司 基于有限加权工序故障率的工序排序法
CN112036693B (zh) * 2020-07-28 2022-04-08 成都飞机工业（集团）有限责任公司 基于有限加权工序故障率的工序排序法
CN114807506A (zh) * 2022-04-20 2022-07-29 山西太钢不锈钢股份有限公司 一种车轮钢冶炼钢水增硫的方法

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