AlMnSi系列锰合金制备技术研究
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摘要
锰产业是重庆市城口县的支柱产业,但随着社会的发展,该县的中小型企业生产的高能耗的低端粗级产品越来越缺乏市场竞争力,因此研发具有市场竞争力的高附加值锰合金系列新产品已迫在眉睫。
本课题的目标是研发以锰为基,Al含量分别在12～18%、30～40%,钛含量不小于3%,钒含量不小于2%的高附加值锰合金系列新产品,针对锰、硅、铝、钛、钒等元素熔点、密度差别大、固溶度低、烧损率高、收得率低、组织结构调控困难等,重点解决合金粉化,成分偏析、制备困难等技术难题。在总结国内外相关文献的基础上,结合本课题组前期实验,发现通过熔炼设备选取、熔炼及浇铸工艺控制、存放方式选择等方面可有效解决上述问题。
实验在单相中频感应炉(功率5000w,频率1000Hz,容量10Kg)中完成,通过实验得出以下结论:(1)采取“先加少量废铝→再加其它原料→再添加剩余废铝”的加料方式可提高铝的收得率,同时缩短熔炼时间。(2)将温度控制在1500～1700℃;升温速度控制在130～150℃/min;以硅锰合金为主要原料,熔炼时间控制在15～17min,而以混合矿为主要原料,熔炼时间控制在20～25min的效果较为理想。(3)碱度控制方面:在以硅锰合金为主要原料的熔炼实验中,碱度控制在3～4可有效降低合金中的磷含量;在以混合矿为主要原料的熔炼实验中,碱度控制在0.6～0.8之间可使锰、硅综合收得率较高。(4)本实验选用的具有一定精炼能力的、在KCl和NaCl中加入冰晶石而组成的粉状覆盖剂,使得合金元素的烧损降低,合金铸块中氧化物夹杂及气体导致的气孔较少。(5)浇铸时选用传热较快的扁平型铜铸模,在反应完全后大约2min开始浇铸,浇铸时保持外浇口充满,保持合金液流动平稳、不断流,获得了成分比较均匀的合金块。(6)干燥、密封的环境可使合金的保存时间延长。
本实验所炼合金经过成分分析、金相检测以及存放期的观察,发现合金成分比较均匀,结构比较致密,存放期较长,基本达到了预期目标。
Manganese industry is the pillar cornerstone industry at Chengkou, Chongqing, China. With the development of society, medium and small enterprises become more and more lack of market competitiveness because their products are inferior and consume high energy. Thereby, it is necessary to research and develop more competitive new type of manganese alloy imminently.
The goal of this topic is to research and develop new type manganese alloys which is manganese-based and include Al:12～18% or 30～40%;Ti≥3%;V≥2%. Considering the melting point, density differences, low solid solution, high rate of burning loss and low redemptory of the element such as manganese、silicon、aluminum、titanium and vanadium , the difficulties of adjusting organizational structure and so on, this paper focus on solving the alloys pulverization, segregation and the difficulties of technical problems. These problems were solved by choosing an effective solution , such as equipent selection, controlling melting and casting process, storage areas.
The primary equipment is single-phase IF induction furnace. Main parameters are power, 5000W, frequency, 1000Hz, capacity, 10kg. The following conclusions by a lot of experiments are: (1) This feeding process which is to take“a small quality of raw Al material→other materials→remaining Al material”can improve the yield of aluminum intake, and reduce the melting time.(2) The whole process temperature should be controlled between 1500~1700℃, warming speed be controlled between 130 to 150℃/min; the melting time of Silicon-manganese alloys material be controlled between 15～17min; the melting time of manganese ore material be controlled between 20～25 min. (3) Basicity control: In silicon-manganese alloys as the main raw materials of melting experiments, the ideal basicity is between 3～4 to reduce the phosphorus; In manganese ore as the main materials of melting process, the ideal basicity is between 0.6～0.8 to improve manganese and silicon retraction.(4) we select a powdered coverage include KCl、NaCl and cryolite with refining capacity. This coverage reduce the alloying elements burning, oxide block and air hole.(5) Selecting flat bronze with rapid heat transfer in casting process. Casting start about 2 minutes after smelting, keeping the gate full and a smooth and relative flow. Thus, the composition of the alloys will be more homogeneous. (6) To extend the preservation of the alloys, dry and sealed storage should be selected.
Through alloys component analysis, metallographic phase testing and preservation period observation, the alloys has homogeneous composition, dense structure and long storage term. The author achieved the expected goals.
本课题的目标是研发以锰为基,Al含量分别在12～18%、30～40%,钛含量不小于3%,钒含量不小于2%的高附加值锰合金系列新产品,针对锰、硅、铝、钛、钒等元素熔点、密度差别大、固溶度低、烧损率高、收得率低、组织结构调控困难等,重点解决合金粉化,成分偏析、制备困难等技术难题。在总结国内外相关文献的基础上,结合本课题组前期实验,发现通过熔炼设备选取、熔炼及浇铸工艺控制、存放方式选择等方面可有效解决上述问题。
实验在单相中频感应炉(功率5000w,频率1000Hz,容量10Kg)中完成,通过实验得出以下结论:(1)采取“先加少量废铝→再加其它原料→再添加剩余废铝”的加料方式可提高铝的收得率,同时缩短熔炼时间。(2)将温度控制在1500～1700℃;升温速度控制在130～150℃/min;以硅锰合金为主要原料,熔炼时间控制在15～17min,而以混合矿为主要原料,熔炼时间控制在20～25min的效果较为理想。(3)碱度控制方面:在以硅锰合金为主要原料的熔炼实验中,碱度控制在3～4可有效降低合金中的磷含量;在以混合矿为主要原料的熔炼实验中,碱度控制在0.6～0.8之间可使锰、硅综合收得率较高。(4)本实验选用的具有一定精炼能力的、在KCl和NaCl中加入冰晶石而组成的粉状覆盖剂,使得合金元素的烧损降低,合金铸块中氧化物夹杂及气体导致的气孔较少。(5)浇铸时选用传热较快的扁平型铜铸模,在反应完全后大约2min开始浇铸,浇铸时保持外浇口充满,保持合金液流动平稳、不断流,获得了成分比较均匀的合金块。(6)干燥、密封的环境可使合金的保存时间延长。
本实验所炼合金经过成分分析、金相检测以及存放期的观察,发现合金成分比较均匀,结构比较致密,存放期较长,基本达到了预期目标。
Manganese industry is the pillar cornerstone industry at Chengkou, Chongqing, China. With the development of society, medium and small enterprises become more and more lack of market competitiveness because their products are inferior and consume high energy. Thereby, it is necessary to research and develop more competitive new type of manganese alloy imminently.
The goal of this topic is to research and develop new type manganese alloys which is manganese-based and include Al:12～18% or 30～40%;Ti≥3%;V≥2%. Considering the melting point, density differences, low solid solution, high rate of burning loss and low redemptory of the element such as manganese、silicon、aluminum、titanium and vanadium , the difficulties of adjusting organizational structure and so on, this paper focus on solving the alloys pulverization, segregation and the difficulties of technical problems. These problems were solved by choosing an effective solution , such as equipent selection, controlling melting and casting process, storage areas.
The primary equipment is single-phase IF induction furnace. Main parameters are power, 5000W, frequency, 1000Hz, capacity, 10kg. The following conclusions by a lot of experiments are: (1) This feeding process which is to take“a small quality of raw Al material→other materials→remaining Al material”can improve the yield of aluminum intake, and reduce the melting time.(2) The whole process temperature should be controlled between 1500~1700℃, warming speed be controlled between 130 to 150℃/min; the melting time of Silicon-manganese alloys material be controlled between 15～17min; the melting time of manganese ore material be controlled between 20～25 min. (3) Basicity control: In silicon-manganese alloys as the main raw materials of melting experiments, the ideal basicity is between 3～4 to reduce the phosphorus; In manganese ore as the main materials of melting process, the ideal basicity is between 0.6～0.8 to improve manganese and silicon retraction.(4) we select a powdered coverage include KCl、NaCl and cryolite with refining capacity. This coverage reduce the alloying elements burning, oxide block and air hole.(5) Selecting flat bronze with rapid heat transfer in casting process. Casting start about 2 minutes after smelting, keeping the gate full and a smooth and relative flow. Thus, the composition of the alloys will be more homogeneous. (6) To extend the preservation of the alloys, dry and sealed storage should be selected.
Through alloys component analysis, metallographic phase testing and preservation period observation, the alloys has homogeneous composition, dense structure and long storage term. The author achieved the expected goals.
引文
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[3]杨志忠,李蒙姬.中国锰系铁合金的发展与思考[J] .铁合金,2005,171(2):42-47.
[4]赵跃萍,丁松,张金柱.金属锰渗氮及热力学分析[J] .贵州工业大学学报(自然科学版),2002,30(1):33-35.
[5] Poulalion A,Botte R.Nitrogen addition in steelmaking using nitriding ferroalloys [J] . Int Conf on High Nitrogen Steels-HNS88,1989,15(2):49-52.
[6]加西克M N.铁合金生产的理论和工艺[M] .张烽,译..北京:冶金工业出版社,1994.
[7]陈刚,陈鼎.锰在有色金属中的应用[J] .中国锰业,2003,21(1):34-37.
[8]徐增华.金属耐蚀材料[J].腐蚀与防护,2001,35(12):549.
[9]田荣璋.铜合金及其加工手册[M].湖南:中南大学出版,2002.
[10]张瑾等.矿用管接头Cu—Al—Mn记忆合金材料的研究[J].金属矿山,2001,18(7):39.
[11]唱鹤鸣等.感应炉熔炼与特种铸造技术[M] .北京:冶金工业出版社,2002.
[12]宋耀欣. SiAlFe铁合金自然粉化行为的研究[C] .北京:北京科技大学,2007.
[13]张怀嵩.复合脱氧剂在炼钢终脱氧中的应用[J] .工业加热, 2004,33(6):62-63.
[14] Marcolino Fernandes, Jose Carlos Piers. Investigation of the chemical composition of Nonmetallic inclusions utilizing ternary phase diagrams[J] .MaterialsCharacterization,2003,49(3):437-443.
[15]吴占贤,郭仕斌.复合脱氧剂的技术分析[J] .兵器材料科学与工程,1998,21(4):69-70.
[16] PAL and Robert S.BDGAN.Laboratory Scale Refining Studies on Low Carbon Aluminum Killed Steels Using Synthetic Fluxes [J] .ISIJ International,1994,24(2):140~145.
[17] Chakrarti O P,Das P K,Mukerji J .Grouth of Sic in reaction sintered SIC[J] .Mater Chem & Phy,2001,67(15):199-202.
[18] Ortiz A L,Sanchez-Bajo F,Cumbrera F L.X-ray powder diffraction analysis of a silicom carbide-based ceramic[J] .Material Letter,2001,49(7):137-145.
[19]柯建华.炼钢复合脱氧剂-铝锰铁合金的试制与应用研究[J] .中国锰业,1994,12(1):34.
[20] Uday B.复合脱氧剂铝锰铁替代纯铝预脱氧工艺试验[J] .炼钢,1998,27(4):16～19.
[21]И.Г.Bonkouu,铝锰硅铁合金的生产[J] .Metary,1987,41(3):2.
[22]С.Т.罗斯托夫采夫.冶金过程理论[J] .冶金工业出版社,1959,17(9):649.
[23]陈坤,黄正全.钙系复合脱氧剂应用试验[J].四川冶金,2007,29(1):9～11.
[24]张剑君.Al-Mg合金复合脱氧机理分析[J].柳钢科技.2007年泛珠三角11省(区)炼钢连铸学会论文专辑,2007:10～15.
[25] Lindon P H , Billington J C . Deoxidation of steelwith Ca—Si—A1and Mg—Si—AIalloys[J].Jour-nla ofIron and SteelInstitute,1969,207(3):340~347.
[26] Kusuhiro MUKAI , Qiyong HAN . Application of Barium - bearing Alloys in Steelmaking[J].IJ International.1999,39(7):625~636.
[27]陶启兆.硅铝钡复合合金作炼钢终脱氧剂的应用与研究[J].四川冶金,1995,28(1):33～39.
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