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CN107488788A - A kind of special slag system and its preparation and application for being used to produce 17 4PH steel ingots - Google Patents

A kind of special slag system and its preparation and application for being used to produce 17 4PH steel ingots Download PDF

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CN107488788A
CN107488788A CN201710637068.4A CN201710637068A CN107488788A CN 107488788 A CN107488788 A CN 107488788A CN 201710637068 A CN201710637068 A CN 201710637068A CN 107488788 A CN107488788 A CN 107488788A
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slag
slag system
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steel
ingot
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CN107488788B (en
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李万明
董君伟
姜周华
耿峰
耿一峰
臧喜民
邓鑫
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University of Science and Technology Liaoning USTL
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16Remelting metals
    • C22B9/18Electroslag remelting
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/076Use of slags or fluxes as treating agents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Manufacture And Refinement Of Metals (AREA)
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Abstract

一种用于生产17‑4PH钢锭的专用渣系,该专用渣系由下列重量百分比的成分组成:Al2O3:26~28%,CaO:25~27%,SiO2:4~5%,MgO:5~6%,余量为CaF2;其二元碱度CaO/SiO2为5~6.75;该专用渣系的熔化半球温度为1220~1250℃;0.402~0.434Ω•cm。在1500℃下的粘度为0.0352~0.0359 Pa•s。本发明的渣系熔点较低,电阻率较高,粘度随温度变化较小,高温塑性较好,碱度较高,氟化物含量低,化渣速度快,能够满足抽锭式电渣重熔法生产17‑4PH钢锭的要求,能够保证17‑4PH钢锭的内部质量和表面质量,并具有节能和环保的优点。

A special slag system for producing 17-4PH steel ingots, the special slag system is composed of the following components by weight percentage: Al 2 O 3 : 26~28%, CaO: 25~27%, SiO 2 : 4~5% , MgO: 5~6%, the balance is CaF 2 ; its binary basicity CaO/SiO 2 is 5~6.75; the melting hemisphere temperature of this special slag system is 1220~1250℃; 0.402~0.434Ω·cm. The viscosity at 1500°C is 0.0352~0.0359 Pa·s. The slag system of the present invention has low melting point, high resistivity, small viscosity change with temperature, good high-temperature plasticity, high alkalinity, low fluoride content, fast slag melting speed, and can meet the requirements of ingot-pulling electroslag remelting The requirements for the production of 17-4PH steel ingots by law can guarantee the internal quality and surface quality of 17-4PH steel ingots, and have the advantages of energy saving and environmental protection.

Description

一种用于生产17-4PH钢锭的专用渣系及其制备和使用方法A special slag system for producing 17-4PH steel ingot and its preparation and use method

技术领域technical field

本发明属于钢铁冶炼领域,具体涉及一种用于生产17-4PH钢锭的节能环保专用渣系及其制备和使用方法。The invention belongs to the field of iron and steel smelting, and in particular relates to a special energy-saving and environment-friendly slag system for producing 17-4PH steel ingots and a preparation and use method thereof.

背景技术Background technique

17-4PH合金是一种沉淀硬化型马氏体不锈钢,由于具有较强的耐压强度、耐腐蚀、抗辐射性能,被广泛应用于航天涡轮机叶片、海洋平台、直升机甲板、核燃料废物桶等重要领域。17-4PH alloy is a precipitation-hardening martensitic stainless steel. Due to its strong compressive strength, corrosion resistance and radiation resistance, it is widely used in aerospace turbine blades, offshore platforms, helicopter decks, nuclear fuel waste barrels, etc. field.

17-4PH合金的成分特点为含有较高的Cr、Cu、Ni、Nb等合金元素,其中的Cr含量为15.0%~17.5%,Ni含量为3%~5%,Cu含量为3%~5%,Nb含量为0.20%~0.45%。然而,由于17-4PH合金含有大量的Cu、Cr等合金元素导致该钢的粘度较大,在冶炼过程中的钢水流动性很差,这使得17-4PH钢锭的凝固质量较差,容易出现较严重的夹杂、缩孔、疏松、偏析等内部质量问题,而且也容易造成钢锭表面褶皱、渣沟等表面质量问题。鉴于该钢在冶炼过程中存在的难度,一般采用电渣重熔方法制备17-4PH钢锭,这是由于电渣重熔法可以实现浇注和凝固过程的分离,既可以对钢水进行二次精炼保证钢水的纯净度,又可以在水冷结晶器的强制冷却作用下保证钢锭的凝固组织致密性,同时电渣重熔过程中在钢锭和结晶器之间的渣皮可以起到较好的润滑作用,从而保证钢锭的表面质量。为了保证电渣重熔17-4PH合金时能够使钢锭具有优异的内部质量和表面质量,需要有适合于该钢种的专用预熔渣渣系,这种渣系需要满足熔点较低、粘度较低的特点。The composition of 17-4PH alloy is characterized by high content of Cr, Cu, Ni, Nb and other alloying elements, among which the Cr content is 15.0%~17.5%, the Ni content is 3%~5%, and the Cu content is 3%~5%. %, Nb content is 0.20%~0.45%. However, since the 17-4PH alloy contains a large amount of alloying elements such as Cu and Cr, the viscosity of the steel is relatively high, and the fluidity of the molten steel during the smelting process is very poor, which makes the solidification quality of the 17-4PH steel ingot poor and prone to cracking. Serious internal quality problems such as inclusions, shrinkage cavities, porosity, and segregation can easily cause surface quality problems such as surface wrinkles and slag grooves on the ingot. In view of the difficulty in the smelting process of this steel, the 17-4PH steel ingot is generally prepared by electroslag remelting method, which is because electroslag remelting method can realize the separation of pouring and solidification process, which can ensure the secondary refining of molten steel The purity of the molten steel can also ensure the compactness of the solidified structure of the steel ingot under the forced cooling of the water-cooled crystallizer. At the same time, the slag skin between the steel ingot and the crystallizer during the electroslag remelting process can play a better role in lubrication. Thereby ensuring the surface quality of the steel ingot. In order to ensure that the steel ingot has excellent internal quality and surface quality when electroslag remelting 17-4PH alloy, it is necessary to have a special pre-melted slag system suitable for this steel type. This slag system needs to meet the low melting point and high viscosity. low feature.

目前,生产钢材所需的渣系基本上均为Al2O3,CaO,SiO2,MgO和CaF2的组合,但是不同的配比适用于生产不同的钢锭。针对于电渣重熔法生产17-4PH合金时,常规的渣系配比电耗较高,电阻率较低,无法满足润滑功能,致使钢锭表面会出现结瘤、渣沟、重皮等表面质量缺陷,同时,传统渣系在一定温度范围内粘度随温度变化易产生突变,上述缺陷都会影响17-4PH钢锭的成本和质量。At present, the slag system required for steel production is basically a combination of Al 2 O 3 , CaO, SiO 2 , MgO and CaF 2 , but different ratios are suitable for the production of different steel ingots. For the production of 17-4PH alloy by the electroslag remelting method, the conventional slag system has high power consumption and low resistivity, which cannot meet the lubrication function, resulting in nodules, slag grooves, heavy skin and other surfaces on the surface of the steel ingot Quality defects. At the same time, the viscosity of traditional slag systems is prone to sudden changes with temperature changes within a certain temperature range. The above defects will affect the cost and quality of 17-4PH steel ingots.

因此,研制一种用于生产17-4PH钢锭的专用渣系及其制备和使用方法,使其满足节能、环保、低熔点、低粘度的特点,是目前亟待解决的问题。Therefore, it is an urgent problem to develop a special slag system for producing 17-4PH steel ingot and its preparation and use method, so that it can meet the characteristics of energy saving, environmental protection, low melting point and low viscosity.

发明内容Contents of the invention

针对冶炼17-4PH钢锭时存在的问题以及对渣系提出的要求,本发明的目的在于提供一种用于生产17-4PH钢锭的专用渣系及其制备和使用方法,该专用渣系具有低熔点、节能、流动性好的优点,通过调整渣系的成分,使渣系的熔点降低且电导率增大,粘度随温度的变化速率较小,并且具有优异的高温塑性。本发明在传统抽锭渣系(60%CaF2+20%CaO+20%Al2O3)的基础上,提高了CaO的比例,主要目的是为了降低渣的熔点,以达到节能降耗的目的;但CaO量增加后,熔渣容易吸收空气中的水分而使钢水增氢,因此也提高了MgO的比例,这是因为MgO熔化后会产生致密的薄膜,可以起到防止吸潮的作用;而MgO增加会使渣的粘度增大,流动性降低,为降低熔渣的粘度,提高了渣中的SiO2含量。SiO2的另一个作用是增加渣的润滑性能和高温强度,有利于抽锭工艺的顺利进行。与传统抽锭渣系相比较,本发明渣系中的CaF2含量较低,减少了冶炼过程中的氟化物挥发,降低了对环境的污染。In view of the problems existing in the smelting of 17-4PH steel ingots and the requirements for the slag system, the purpose of the present invention is to provide a special slag system for producing 17-4PH steel ingots and its preparation and use method. The special slag system has a low Melting point, energy saving, and good fluidity. By adjusting the composition of the slag system, the melting point of the slag system is reduced and the electrical conductivity is increased. The rate of change of viscosity with temperature is small, and it has excellent high-temperature plasticity. Based on the traditional ingot-drawing slag system (60%CaF 2 +20%CaO+20%Al 2 O 3 ), the present invention increases the proportion of CaO, the main purpose of which is to reduce the melting point of slag, so as to save energy and reduce consumption. Purpose; but after the amount of CaO increases, the slag easily absorbs moisture in the air to increase the hydrogenation of molten steel, so the proportion of MgO is also increased. This is because MgO will produce a dense film after melting, which can prevent moisture absorption. The increase of MgO will increase the viscosity of the slag and reduce the fluidity. In order to reduce the viscosity of the slag, the SiO 2 content in the slag is increased. Another function of SiO 2 is to increase the lubricity and high temperature strength of slag, which is conducive to the smooth progress of the ingot drawing process. Compared with the traditional ingot pumping slag system, the CaF 2 content in the slag system of the present invention is lower, which reduces fluoride volatilization in the smelting process and reduces environmental pollution.

本发明的目的是这样实现的:一种用于生产17-4PH钢锭的专用渣系,该专用渣系的成分按重量百分比为Al2O3:26~28%,CaO:25~27%,SiO2:4~5%,MgO:5~6%,CaF2含量为34~40%,二元碱度在5~6.75之间。The object of the present invention is achieved like this: a kind of special-purpose slag system for producing 17-4PH steel ingot, the composition of this special-purpose slag system is Al2O3 : 26 ~28%, CaO: 25~27%, SiO 2 : 4~5%, MgO: 5~6%, CaF 2 content 34~40%, binary alkalinity between 5~6.75.

优选的,该专用渣系由下列重量百分比的成分组成:Al2O3:26.2 %,CaO:25.7%,SiO2:4.89 %,MgO:5.2 %,余量为CaF2;渣的二元碱度CaO/SiO2为5.25。Preferably, the special slag is composed of the following components by weight percentage: Al 2 O 3 : 26.2%, CaO: 25.7%, SiO 2 : 4.89%, MgO: 5.2%, and the balance is CaF 2 ; The degree of CaO/SiO 2 is 5.25.

优选的,该专用渣系由下列重量百分比的成分组成:Al2O3:27.8%,CaO:26.9%,SiO2:4.1%,MgO:5.9%,余量为CaF2;渣的二元碱度CaO/SiO2为6.5。Preferably, the special slag is composed of the following components by weight percentage: Al 2 O 3 : 27.8%, CaO: 26.9%, SiO 2 : 4.1%, MgO: 5.9%, and the balance is CaF 2 ; The degree CaO/SiO 2 is 6.5.

该专用渣系的熔化半球温度为1220~1250℃。The melting hemisphere temperature of this special slag system is 1220~1250℃.

该专用渣系用于抽锭式电渣重熔法生产沉淀硬化型马氏体不锈钢17-4PH钢锭。The special slag is used to produce precipitation-hardening martensitic stainless steel 17-4PH steel ingot by ingot-pulling electroslag remelting method.

该专用渣系在1600℃的电阻率为0.402~0.434Ω•cm,在1500℃下的粘度为0.0352~0.0359 Pa•s。The specific slag system has a resistivity of 0.402~0.434Ω•cm at 1600°C and a viscosity of 0.0352~0.0359 Pa•s at 1500°C.

一种用于生产17-4PH钢锭的专用渣系的制备方法,该方制备法包括如下步骤:将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1560℃下熔炼40min以上。A method for preparing a special slag system for producing 17-4PH steel ingots, the preparation method includes the following steps: after mixing fluorite, quicklime, alumina, fused magnesia and silica in proportion, melting and stirring evenly, Melting at 1500~1560℃ for more than 40min.

然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为5~10mm,制成上述成分含量的用于生产17-4PH钢锭的专用渣系。Then pour it into a water-cooled slag tray made of steel plates, cool it to room temperature, and crush it to a particle size of 5-10mm to make a special slag system for the production of 17-4PH steel ingots with the above-mentioned composition content.

一种用于生产17-4PH钢锭的专用渣系的使用方法,该使用方法包括如下步骤:首先将本发明渣系的熔渣烘烤至800℃,并保温10h以上;在电渣重熔过程中,将烘烤过的专用渣系在化渣炉内升温至1600℃以上并熔清,然后精炼20min左右,将液态炉渣浇注到电渣炉的结晶器内,将待重熔的自耗电极插入结晶器中后通电,使自耗电极与炉渣接触形成通电回路,进行电渣重熔17-4PH的熔炼过程,待电极熔化后形成熔池后开始抽锭操作。A method for using a special slag system for producing 17-4PH steel ingots. The method includes the following steps: first, bake the molten slag of the slag system of the present invention to 800°C and keep it warm for more than 10 hours; In the process, the baked special slag is heated to above 1600°C in the slag melting furnace and melted, and then refined for about 20 minutes, the liquid slag is poured into the crystallizer of the electroslag furnace, and the self-consumed electricity to be remelted The electrode is inserted into the crystallizer and then energized, so that the consumable electrode contacts the slag to form a energized circuit, and the smelting process of electroslag remelting is carried out at 17-4PH. After the electrode is melted and a molten pool is formed, the ingot extraction operation starts.

经试验研究表明:当渣中含有26%~28%的Al2O3,CaO:25~27%,SiO2:4~5%,MgO:5~6%,CaF2:34~40%时,既可保证渣的电阻率值较高又可以使渣系熔点(即熔化半球温度)较低,粘度测定实验结果表明在该配比条件下得到的渣系为长渣,并且4~5% 的SiO2含量使熔渣具有较好的高温塑性和强度,在抽锭时不易破裂从而可以防止漏钢和漏渣事故的发生,而该渣系的高碱度特性抑制了SiO2的活度,可以防止易氧化元素的烧损。本渣系中CaF2的含量较低而Al2O3的含量较高,因此电阻率较高,有利于降低电耗;该渣系半球温度比ANF-6渣系(30% Al2O3,70%CaF2)低约150℃(ANF-6渣系的半球温度为1400℃左右);该渣系的粘度数据也优于传统的ANF-6渣,粘度随时间变化的过渡非常平缓,尤其是温度达到1400℃以上时,粘度随温度变化非常小,这种渣系可以使渣皮具有较稳定的摩擦系数和强度,从而保证渣皮厚度均匀且连续,改善电渣钢锭的表面质量,同时能够减少抽锭过程中由于渣皮摩擦力过大而导致漏渣和漏钢等现象。The experimental research shows that: when the slag contains 26%~28% Al 2 O 3 , CaO: 25~27%, SiO 2 : 4~5%, MgO: 5~6%, CaF 2 : 34~40% , which can not only ensure the high resistivity value of the slag, but also make the melting point of the slag system (that is, the temperature of the melting hemisphere) lower. The SiO 2 content makes the slag have good high-temperature plasticity and strength, and it is not easy to break when the ingot is drawn, so that steel breakout and slag leakage accidents can be prevented, and the high alkalinity of the slag system inhibits the activity of SiO 2 , can prevent the burning loss of easily oxidized elements. The content of CaF 2 in this slag series is low and the content of Al 2 O 3 is high, so the resistivity is high, which is beneficial to reduce power consumption; the hemispherical temperature of this slag series is lower than that of ANF - 6 , 70%CaF 2 ) is about 150°C lower (the hemispherical temperature of ANF-6 slag system is about 1400°C); the viscosity data of this slag system is also better than that of traditional ANF-6 slag, and the transition of viscosity with time is very smooth, Especially when the temperature reaches above 1400℃, the viscosity changes very little with the temperature. This kind of slag system can make the slag skin have a relatively stable friction coefficient and strength, so as to ensure the uniform and continuous thickness of the slag skin and improve the surface quality of the electroslag steel ingot. At the same time, it can reduce the phenomena of slag leakage and steel leakage caused by excessive slag skin friction during the ingot drawing process.

与现有技术相比,本发明具有如下技术效果。Compared with the prior art, the present invention has the following technical effects.

(1)由于CaO和SiO2含量均较高,本发明渣系具有较低的熔点,在相同温度下具有更好的流动性。(1) Due to the high content of CaO and SiO 2 , the slag system of the present invention has a lower melting point and better fluidity at the same temperature.

(2)具有“长渣”的特性和较好的高温强度,即在一定温度范围内渣系的粘度不随温度变化而产生突变,从而保证了良好的高温塑性,适用于抽锭式电渣重熔炉。(2) It has the characteristics of "long slag" and good high-temperature strength, that is, the viscosity of the slag system does not change suddenly with the change of temperature within a certain temperature range, thus ensuring good high-temperature plasticity, and is suitable for ingot-type electroslag gravity furnace.

(3)由于Al2O3含量较高,渣系的电阻率较高,同时熔点较低,化渣速度快,能够起到较好的节能效果。(3) Due to the high content of Al 2 O 3 , the resistivity of the slag system is high, and the melting point is low, and the slag melting speed is fast, which can have a good energy-saving effect.

(4)碱度较高,能够保证重熔过程中易氧化元素的稳定性。(4) The high alkalinity can ensure the stability of easily oxidized elements in the remelting process.

(5)氟化钙含量较低,属于低氟渣系,能够减少冶炼过程的氟化物挥发,减小对环境的危害。(5) The content of calcium fluoride is low, which belongs to the low-fluorine slag system, which can reduce the volatilization of fluoride in the smelting process and reduce the harm to the environment.

附图说明Description of drawings

图1为采用本发明实施例1的产品进行抽锭式电渣重熔制取电渣锭表面照片图。Figure 1 is a photo of the surface of an electroslag ingot produced by ingot-pulling electroslag remelting using the product of Example 1 of the present invention.

图2为采用传统实心锭抽锭渣系进行抽锭式电渣重熔制取的电渣锭表面照片图。Figure 2 is a photograph of the surface of an electroslag ingot produced by ingot-pulling electroslag remelting using a traditional solid ingot pumping slag system.

图3为本发明实施例中的渣系与传统抽锭渣系、传统ANF-6渣系的温度-粘度曲线对比图;图中S1为实施例1的产品,S2为实施例3的产品,S3为传统实心锭用抽锭渣系,ANF-6为传统70% CaF2+30% Al2O3渣系。Fig. 3 is the temperature-viscosity curve comparison chart of the slag system in the embodiment of the present invention and the traditional ingot pumping slag system and the traditional ANF-6 slag system; among the figure, S1 is the product of embodiment 1, and S2 is the product of embodiment 3, S3 is the traditional solid ingot pumping slag system, and ANF-6 is the traditional 70% CaF 2 +30% Al 2 O 3 slag system.

具体实施方式detailed description

本发明实施例中采用的萤石为重量纯度≥98%的高纯萤石块。The fluorite used in the embodiment of the present invention is a high-purity fluorite block with a weight purity ≥ 98%.

本发明实施例中采用的石灰中CaO的重量含量≥92%。The weight content of CaO in the lime used in the embodiment of the present invention is more than or equal to 92%.

本发明实施例中采用的工业氧化铝中Al2O3的重量纯度≥99%。The weight purity of Al 2 O 3 in the industrial alumina used in the examples of the present invention is ≥99%.

本发明实施例中采用的电熔镁砂中MgO的重量纯度≥98%。The weight purity of MgO in the fused magnesia used in the embodiment of the present invention is ≥98%.

本发明实施例中采用的硅石中SiO2的重量纯度≥98%。The weight purity of SiO2 in the silica used in the examples of the present invention is ≥98%.

实施例1。Example 1.

采用高纯萤石块、石灰、工业氧化铝粉、电熔镁砂和硅石为原料,将准备好的各原料混合后,采用电渣炉石墨电极化渣,物料全部熔化后继续精炼40分钟;然后浇铸到底部厚度为60mm的铸铁盘内,经冷却凝固至室温后,采用破碎机粉碎后,筛选出粒度为5~10mm的部分,获得用于抽锭式电渣重熔法生产沉淀硬化型马氏体不锈钢17-4PH钢锭的预熔渣,然后包装成10kg一袋,供抽锭式电渣炉使用。High-purity fluorite block, lime, industrial alumina powder, fused magnesia and silica are used as raw materials. After mixing the prepared raw materials, electroslag furnace graphite electrode is used to slag. After all the materials are melted, the refining is continued for 40 minutes; then casting into a cast iron plate with a bottom thickness of 60mm, cooled and solidified to room temperature, crushed by a crusher, and screened out the part with a particle size of 5-10mm to obtain precipitation-hardening martensitic powder for the production of precipitation-hardening martensitic powder by the ingot-type electroslag remelting method. The pre-melted slag of the stainless steel 17-4PH steel ingot is packaged into a 10kg bag for use in the ingot pumping electroslag furnace.

上述专用渣系由下列重量百分比的成分组成:Al2O3:26.2 %,CaO:25.7%,SiO2:4.89 %,MgO:5.2 %,余量为CaF2;渣的二元碱度CaO/SiO2为5.25。The above special slag is composed of the following components by weight percentage: Al 2 O 3 : 26.2%, CaO: 25.7%, SiO 2 : 4.89%, MgO: 5.2%, and the balance is CaF 2 ; the binary basicity of the slag is CaO/ SiO2 is 5.25.

采用上述预熔渣在东北大学特殊钢冶金研究所的300kg多功能电渣炉试验,首先将本发明渣系的熔渣烘烤至800℃,并保温10h以上;在电渣重熔过程中,将烘烤过的专用渣系在化渣炉内升温至1600℃以上并熔清,然后精炼20min左右,将液态炉渣浇注到电渣炉的结晶器内,将待重熔的自耗电极插入结晶器中后通电,使自耗电极与炉渣接触形成通电回路,进行电渣重熔17-4PH的熔炼过程,待电极熔化后形成熔池后开始抽锭操作。Using the above-mentioned pre-melted slag in the 300kg multifunctional electroslag furnace test of the Institute of Special Steel Metallurgy, Northeastern University, first bake the slag of the slag system of the present invention to 800 ° C, and keep it warm for more than 10 hours; during the electroslag remelting process, Heat the baked special slag system to above 1600°C in the slag melting furnace and melt it, then refine it for about 20 minutes, pour the liquid slag into the crystallizer of the electroslag furnace, insert the consumable electrode to be remelted After the crystallizer is energized, the consumable electrode and the slag are in contact to form a energized circuit, and the smelting process of electroslag remelting is carried out at 17-4PH. After the electrode is melted and a molten pool is formed, the ingot extraction operation starts.

电渣重熔时,预熔渣的用量以保证渣池高度为260~280mm计算,为240~260kg/炉钢,电压为63~68V,电流为18~20kA,熔化速率为800~970kg/h,采用的熔炼炉的控制拉速为10~12 mm/min;其中自耗电极是采用AOD炉工艺生产并经轧制制成,直径Φ160mm;制取的电渣锭尺寸为Φ450mm,端钢锭表面质量良好,无渣沟、结瘤、重皮、褶皱、夹渣等缺陷,非金属夹杂物总重量含量降低69%;制取的电渣锭表面照片如图1所示。During electroslag remelting, the amount of pre-melted slag is calculated to ensure that the height of the slag pool is 260~280mm, which is 240~260kg/furnace steel, the voltage is 63~68V, the current is 18~20kA, and the melting rate is 800~970kg/h , the controlled casting speed of the smelting furnace used is 10~12 mm/min; the consumable electrode is produced by AOD furnace and rolled, with a diameter of Φ160mm; the size of the prepared electroslag ingot is Φ450mm, and the end steel ingot The surface quality is good, without slag grooves, nodules, heavy skin, wrinkles, slag inclusions and other defects, and the total weight content of non-metallic inclusions is reduced by 69%. The surface photo of the prepared electroslag ingot is shown in Figure 1.

1、Al2O3含量的筛选过程。1. Screening process of Al 2 O 3 content.

以实施例1的含量为基准,固定CaO、SiO2、MgO的含量,加入不同含量(20~30%)的Al2O3,余量为CaF2,检测电阻率和半球温度,不同Al2O3含量下渣的物性参数见表1。Based on the content of Example 1, the content of CaO, SiO 2 , and MgO was fixed, and Al 2 O 3 with different content ( 20 ~30%) was added, and the balance was CaF 2 . The physical parameters of slag under O3 content are shown in Table 1.

结果显示,当Al2O3含量在26-28%时,电阻率和半球温度能达到生产17-4PH的要求。The results show that when the content of Al 2 O 3 is 26-28%, the resistivity and hemisphere temperature can meet the requirements of producing 17-4PH.

2、CaO含量的筛选。2. Screening of CaO content.

以实施例1的含量为基准,固定Al2O3、SiO2、MgO的含量,加入不同含量(20~30%)的CaO,余量为CaF2 ,检测电阻率和半球温度,不同CaO含量下渣的物性参数见表2。Based on the content of Example 1, the content of Al 2 O 3 , SiO 2 , and MgO was fixed, and CaO with different content (20~30%) was added, and the balance was CaF 2 . The physical parameters of the slag are shown in Table 2.

结果显示,当CaO含量在25-27%时,电阻率较高而熔化半球温度较低,能达满足冶炼17-4PH时的节能降耗的要求。The results show that when the CaO content is 25-27%, the resistivity is higher and the melting hemisphere temperature is lower, which can meet the requirements of energy saving and consumption reduction when smelting 17-4PH.

3、SiO2含量的筛选过程。3. The screening process of SiO 2 content.

以实施例1的含量为基准,固定Al2O3、CaO、MgO的含量,加入不同含量(2~6%)的SiO2,余量为CaF2 ,检测电阻率和半球温度,不同SiO2含量时的渣的物性参数见表3。Based on the content of Example 1, fix the content of Al 2 O 3 , CaO, and MgO, add SiO 2 with different content ( 2 ~6%), and the balance is CaF 2 , and detect the resistivity and hemispherical temperature. See Table 3 for the physical parameters of the slag at different concentrations.

结果显示,当SiO2含量在4-5%时,具有良好的高温塑性和强度,满足生产17-4PH的要求。The results show that when the SiO 2 content is 4-5%, it has good high-temperature plasticity and strength, which meets the requirements for the production of 17-4PH.

实施例2。Example 2.

采用上述实例1中冶炼的预熔渣电渣重熔0Cr17Ni4Cu4Nb钢(即17-4PH),在江苏某企业的1.5吨电渣炉进行生产。The pre-melted slag electroslag remelted 0Cr17Ni4Cu4Nb steel (namely 17-4PH) smelted in the above example 1 was used for production in a 1.5-ton electroslag furnace of an enterprise in Jiangsu.

本次电渣重熔时,将该预熔渣直接在电渣炉结晶器内,采用固渣起弧工艺,本次用渣量为30kg,化渣时间为30min。冶炼时电压为57V-58V , 电流为6800A-7500A,结晶器规格为Ф330mm,电极棒为中频炉+精炼炉工艺经锻造后的205mm方棒。实际重熔熔化700kg钢锭,熔化时间3小时。During the electroslag remelting this time, the pre-melted slag was directly placed in the crystallizer of the electroslag furnace, and the solid slag starting process was adopted. The amount of slag used this time was 30kg, and the slag melting time was 30min. During smelting, the voltage is 57V-58V, the current is 6800A-7500A, the crystallizer specification is Ф330mm, and the electrode rod is a 205mm square rod forged by intermediate frequency furnace + refining furnace process. The actual remelting melts a 700kg steel ingot, and the melting time is 3 hours.

生产完毕的电渣锭表面质量良好,无明显渣沟、结瘤等缺陷,S、P含量较低,与电极材料相比,电渣锭的非金属夹杂物含量降低约65%。The surface quality of the finished electroslag ingot is good, without obvious defects such as slag grooves and nodules, and the content of S and P is low. Compared with the electrode material, the content of non-metallic inclusions in the electroslag ingot is reduced by about 65%.

实施例3。Example 3.

将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1560℃下熔炼43min;然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为5~10mm,制成上述成分含量的用于生产17-4PH钢锭的专用渣系。获得用于抽锭式电渣重熔制取空心锭的低污染节能预熔渣,包装成20kg一袋,供电渣炉使用。Mix fluorite, quicklime, alumina, fused magnesia, and silica in proportion, melt and stir evenly, and melt at 1500~1560°C for 43 minutes; then pour it into a water-cooled slag pan made of steel plate, and cool to At room temperature, crush it to a particle size of 5-10mm to make a special slag system for the production of 17-4PH steel ingots with the above-mentioned composition content. Obtain low-pollution and energy-saving pre-melted slag for producing hollow ingots by ingot-pulling electroslag remelting, pack it into a 20kg bag, and use it in an electric slag furnace.

上述专用渣系由下列重量百分比的成分组成:Al2O3:27.8%,CaO:26.9%,SiO2:4.1%,MgO:5.9%配置,余量为CaF2;渣的二元碱度CaO/SiO2为6.5。The above-mentioned special slag is composed of the following components by weight percentage: Al 2 O 3 : 27.8%, CaO: 26.9%, SiO 2 : 4.1%, MgO: 5.9%, and the balance is CaF 2 ; the binary alkalinity of the slag is CaO /SiO 2 is 6.5.

采用上述预熔渣在安徽某企业生产电渣重熔17-4PH,化渣工艺为液渣启动,即石墨电极首先化渣,然后换金属电渣化钢。冶炼期间工艺为:电压:48V~52V;冶炼电流:13000-13500A。熔速控制在480kg/h~520kg/h。The above pre-melted slag was used to produce electroslag remelting 17-4PH in an enterprise in Anhui. The slag melting process was started with liquid slag, that is, the graphite electrode first melted slag, and then replaced the metal electroslag to melt steel. The process during smelting is: voltage: 48V-52V; smelting current: 13000-13500A. Melting speed is controlled at 480kg/h~520kg/h.

经实验,本渣系冶炼的电渣锭表面质量良好,无明显渣沟、结瘤等缺陷,S、P含量较低,与原始电极材料相比,电渣锭的A类非金属夹杂物含量降低约62%,B类非金属夹杂物含量降低约57%,C类非金属夹杂物含量降低约65%。According to experiments, the surface quality of electroslag ingots smelted by this slag system is good, without obvious defects such as slag grooves and nodules, and the content of S and P is low. Compared with the original electrode materials, the content of class A non-metallic inclusions in electroslag ingots The content of type B non-metallic inclusions is reduced by about 57%, and the content of type C non-metallic inclusions is reduced by about 65%.

对比例1。Comparative example 1.

将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1550℃下熔炼30min;然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为3~12mm,制成传统实心锭用抽锭渣系。Mix fluorite, quicklime, alumina, fused magnesia, and silica in proportion, melt and stir evenly, and smelt at 1500~1550°C for 30 minutes; then pour it into a water-cooled slag pan made of steel plate, and cool to At room temperature, it is crushed to a particle size of 3-12mm to make the ingot slag system for traditional solid ingots.

传统实心锭用抽锭渣系由下列重量百分比的成分组成:Al2O3:20%,CaO:19.8%,CaF2:59%配置,余量为SiO2The ingot slag system for traditional solid ingots is composed of the following components by weight percentage: Al 2 O 3 : 20%, CaO: 19.8%, CaF 2 : 59%, and the balance is SiO 2 .

将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1480~1570℃下熔炼35min;然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为1~10mm,制成ANF-6渣系。Mix fluorite, quicklime, alumina, fused magnesia, and silica in proportion, melt and stir evenly, and melt at 1480~1570°C for 35 minutes; then pour it into a water-cooled slag pan made of steel plate, and cool to At room temperature, crush it to a particle size of 1-10mm to make ANF-6 slag system.

ANF-6渣系由下列重量百分比的成分组成:Al2O3:29%,CaF2:70%配置,余量为SiO2ANF-6 slag is composed of the following components by weight percentage: Al 2 O 3 : 29%, CaF 2 : 70%, and the balance is SiO 2 .

实施例1、实施例3、传统实心锭用抽锭渣系(60%CaF2,20%Al2O3,20%CaO)、ANF-6(30% Al2O3,70%CaF2)的物性参数如表4所示,1300~1500℃范围内粘度如表5所示。Example 1, Example 3, Ingot Slag System for Traditional Solid Ingots (60%CaF 2 , 20%Al 2 O 3 , 20%CaO), ANF-6 (30% Al 2 O 3 , 70%CaF 2 ) The physical parameters are shown in Table 4, and the viscosity in the range of 1300~1500°C is shown in Table 5.

结果显示,实施例1和3,即本发明渣系的性能优于传统实心锭用抽锭渣系和ANF-6。The results show that the performance of Examples 1 and 3, that is, the slag system of the present invention is better than that of the traditional solid ingot slag system and ANF-6.

由上表可见,传统实心锭用抽锭渣系和ANF-6渣的粘度随温度变化较大,曲线见图3。采用传统实心锭用抽锭渣系(60%CaF2,20%Al2O3,20%CaO)重复上述试验,制取的电渣锭表面照片如图2所示。经生产实验发现,传统渣系冶炼的电渣锭表面质量较差,出现明显渣沟、结瘤等缺陷,非金属夹杂物总重量含量较高。It can be seen from the above table that the viscosity of traditional solid ingot pumping slag system and ANF-6 slag changes greatly with temperature, and the curve is shown in Figure 3. The above test was repeated using the traditional solid ingot pumping slag system (60%CaF 2 , 20%Al 2 O 3 , 20%CaO). The photo of the surface of the electroslag ingot produced is shown in Figure 2. The production experiment found that the surface quality of electroslag ingots smelted by traditional slag system is poor, with obvious defects such as slag grooves and nodules, and the total weight content of non-metallic inclusions is high.

对比例2。Comparative example 2.

将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1560℃下熔炼43min;然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为5~10mm,制成上述成分含量的用于生产17-4PH钢锭的专用渣系。获得用于抽锭式电渣重熔制取空心锭的低污染节能预熔渣,包装成20kg一袋,供电渣炉使用。Mix fluorite, quicklime, alumina, fused magnesia, and silica in proportion, melt and stir evenly, and melt at 1500~1560°C for 43 minutes; then pour it into a water-cooled slag pan made of steel plate, and cool to At room temperature, crush it to a particle size of 5-10mm to make a special slag system for the production of 17-4PH steel ingots with the above-mentioned composition content. Obtain low-pollution and energy-saving pre-melted slag for producing hollow ingots by ingot-pulling electroslag remelting, pack it into a 20kg bag, and use it in an electric slag furnace.

上述专用渣系由下列重量百分比的成分组成:Al2O3:27.7%,CaO:30%,SiO2:4.15%,MgO:5.9%配置,余量为CaF2;渣的二元碱度CaO/SiO2为7.2。The above special slag system is composed of the following components by weight percentage: Al 2 O 3 : 27.7%, CaO: 30%, SiO 2 : 4.15%, MgO: 5.9%, and the balance is CaF 2 ; the binary basicity of the slag is CaO /SiO 2 is 7.2.

采用上述预熔渣在安徽某企业生产电渣重熔17-4PH,化渣工艺为液渣启动,即石墨电极首先化渣,然后换金属电渣化钢。冶炼期间工艺为:电压:52V;冶炼电流:13000A。熔速控制在4.35kg/min。The above pre-melted slag was used to produce electroslag remelting 17-4PH in an enterprise in Anhui. The slag melting process was started with liquid slag, that is, the graphite electrode first melted slag, and then replaced the metal electroslag to melt steel. The process during smelting is: voltage: 52V; smelting current: 13000A. Melting speed is controlled at 4.35kg/min.

经实验,电渣锭中氢含量达到4.3ppm,而该钢的氢含量要求为3ppm以下,不满足质量要求。After experiments, the hydrogen content in the electroslag ingot reaches 4.3ppm, but the hydrogen content of the steel is required to be below 3ppm, which does not meet the quality requirements.

通过对比例2的对比,可以得出CaO含量高出本发明所限定的25%~27%时,会造成熔炼过程中发生较明显的吸潮现象,不利于钢中氢的去除。Through the comparison of Comparative Example 2, it can be concluded that when the CaO content is 25%-27% higher than the limit of the present invention, it will cause obvious moisture absorption during the smelting process, which is not conducive to the removal of hydrogen in the steel.

对比例3。Comparative example 3.

将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1560℃下熔炼43min;然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为5~10mm,制成上述成分含量的用于生产17-4PH钢锭的专用渣系。获得用于抽锭式电渣重熔制取空心锭的低污染节能预熔渣,包装成20kg一袋,供电渣炉使用。Mix fluorite, quicklime, alumina, fused magnesia, and silica in proportion, melt and stir evenly, and melt at 1500~1560°C for 43 minutes; then pour it into a water-cooled slag pan made of steel plate, and cool to At room temperature, crush it to a particle size of 5-10mm to make a special slag system for the production of 17-4PH steel ingots with the above-mentioned composition content. Obtain low-pollution and energy-saving pre-melted slag for producing hollow ingots by ingot-pulling electroslag remelting, pack it into a 20kg bag, and use it in an electric slag furnace.

上述专用渣系由下列重量百分比的成分组成:Al2O3:27.5%,CaO:20%,SiO2:4.12%,MgO:5.9%配置,余量为CaF2;渣的二元碱度CaO/SiO2为4.85。The above special slag system is composed of the following components by weight percentage: Al 2 O 3 : 27.5%, CaO: 20%, SiO 2 : 4.12%, MgO: 5.9%, and the balance is CaF 2 ; the binary basicity of the slag is CaO /SiO 2 is 4.85.

采用上述预熔渣在安徽某企业生产电渣重熔17-4PH,化渣工艺为液渣启动,即石墨电极首先化渣,然后换金属电渣化钢。冶炼期间工艺为:电压:52V;冶炼电流:13000A。熔速控制在4.35kg/min。The above pre-melted slag was used to produce electroslag remelting 17-4PH in an enterprise in Anhui. The slag melting process was started with liquid slag, that is, the graphite electrode first melted slag, and then replaced the metal electroslag to melt steel. The process during smelting is: voltage: 52V; smelting current: 13000A. Melting speed is controlled at 4.35kg/min.

对熔炼后的电渣锭进行实验分析,钢中A类非金属夹杂物降低45%左右,B类非金属夹杂物含量降低30%左右,C类非金属夹杂物含量降低约35%,去除夹杂物的效果明显低于本发明的渣系。The experimental analysis of the electroslag ingot after smelting shows that the A-type non-metallic inclusions in the steel are reduced by about 45%, the B-type non-metallic inclusions are reduced by about 30%, and the C-type non-metallic inclusions are reduced by about 35%. The effect of material is obviously lower than the slag system of the present invention.

通过对比例3的对比,可以得出CaO含量低于本发明所限定的25%~27%时,不利于钢中夹杂物的去除。Through the comparison of Comparative Example 3, it can be concluded that when the CaO content is lower than the 25%-27% defined in the present invention, it is not conducive to the removal of inclusions in the steel.

以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (6)

1.一种用于生产17-4PH钢锭的专用渣系,其特征在于该专用渣系由下列重量百分比的成分组成:Al2O3:26~28%,CaO:25~27%,SiO2:4~5%,MgO:5~6%,余量为CaF2,二元碱度在5~6.75之间。1. A special slag system for producing 17-4PH steel ingot, characterized in that the special slag system is composed of the following components by weight percentage: Al 2 O 3 : 26~28%, CaO: 25~27%, SiO 2 : 4~5%, MgO: 5~6%, the balance is CaF 2 , and the binary alkalinity is between 5~6.75. 2.根据权利要求1所述的一种用于生产17-4PH钢锭的专用渣系,其特征在于,其特征在于该专用渣系的熔化半球温度为1220~1250℃。2. A special slag system for producing 17-4PH steel ingot according to claim 1, characterized in that the melting hemispherical temperature of the special slag system is 1220~1250°C. 3.根据权利要求1所述的一种用于生产17-4PH钢锭的专用渣系,其特征在于,该专用渣系用于抽锭式电渣重熔法生产沉淀硬化型马氏体不锈钢17-4PH钢锭。3. A special slag system for producing 17-4PH steel ingots according to claim 1, characterized in that the special slag system is used for the production of precipitation-hardening martensitic stainless steel 17 by ingot-pulling electroslag remelting -4PH steel ingot. 4.根据权利要求1所述的一种用于生产17-4PH钢锭的专用渣系,其特征在于,该专用渣系在1600℃的电阻率为0.402~0.434Ω•cm,在1500℃下的粘度为0.0352~0.0359 Pa•s。4. A special slag system for producing 17-4PH steel ingots according to claim 1, characterized in that the special slag system has a resistivity of 0.402~0.434Ω·cm at 1600°C, and a resistivity of 0.434Ω·cm at 1500°C The viscosity is 0.0352~0.0359 Pa·s. 5.一种如权利要求1所述的用于生产17-4PH钢锭的专用渣系的制备方法,其特征在于,该方制备法包括如下步骤:将萤石、生石灰、氧化铝、电熔镁砂、硅石按比例混合后,熔化并搅拌均匀,在1500~1560℃下熔炼40min以上;5. a preparation method for producing the special-purpose slag system for producing 17-4PH steel ingot as claimed in claim 1, is characterized in that, this method preparation method comprises the steps: with fluorite, unslaked lime, aluminum oxide, fused magnesium Sand and silica are mixed in proportion, melted and stirred evenly, and smelted at 1500~1560°C for more than 40 minutes; 然后将其浇注到钢板制成的水冷渣盘内,冷却至室温,将其粉碎至粒度为5~10mm,制成上述成分含量的用于生产17-4PH钢锭的专用渣系。Then pour it into a water-cooled slag tray made of steel plates, cool it to room temperature, and crush it to a particle size of 5-10mm to make a special slag system for the production of 17-4PH steel ingots with the above-mentioned composition content. 6.一种如权利要求1所述的用于生产17-4PH钢锭的专用渣系的使用方法,其特征在于,该使用方法包括如下步骤:首先将本发明渣系的熔渣烘烤至800℃,并保温10h以上;在电渣重熔过程中,将烘烤过的专用渣系在化渣炉内升温至1600℃以上并熔清,然后精炼20min左右,将液态炉渣浇注到电渣炉的结晶器内,将待重熔的自耗电极插入结晶器中后通电,使自耗电极与炉渣接触形成通电回路,进行电渣重熔17-4PH的熔炼过程,待电极熔化后形成熔池后开始抽锭操作。6. a method for using the special slag system for producing 17-4PH steel ingot as claimed in claim 1, characterized in that, the method for use comprises the steps of: first baking the molten slag of the slag system of the present invention to 800 ℃, and keep warm for more than 10h; in the electroslag remelting process, the baked special slag system is heated to above 1600℃ in the slag melting furnace and melted, and then refined for about 20min, and the liquid slag is poured into the electroslag furnace In the crystallizer, insert the consumable electrode to be remelted into the crystallizer and then energize, so that the consumable electrode and the slag are in contact to form a energized circuit, and carry out the smelting process of electroslag remelting 17-4PH, and form after the electrode is melted The ingot extraction operation starts after the molten pool.
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