钛氟酸钾-木屑法制备Al-Ti-C母合金机制与显微组织研究
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摘要
采用X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)等研究了氟盐-木屑法制备的Al-Ti-C母合金的组织性能。结果表明:由氟盐-木屑与铝液反应制备的Al-Ti-C母合金的合成过程包含以下几个阶段。(1)铝与钛氟酸钾反应置换出的钛与铝反应生成钛铝化合物;(2)木屑在高温条件下发生脱水、碳化反应,裂解产物二氧化碳、碳与铝反应生成碳铝金属化合物,与钛反应生成钛碳化合物;(3)钛铝、碳铝、钛碳化合物组成具有细化作用的Al-Ti-C母合金。合金的物相为α(Al)、铝钛化合物与碳铝化合物组成的共晶组织,其中α(Al)相的平均晶粒尺寸为10～60μm。铝钛化合物为棒状、骨骼状共晶组织并沿晶界分布,晶内可见针片状Al_3Ti,颗粒状TiC相聚合成团块状分布。木屑裂解产物水、二氧化碳与铝反应生成氧化铝和氢以渣-气共生的形式聚集于晶界。
The microstructure and properties of Al-Ti-C master alloy prepared by fluorine salt and sawdust method were studied by X-ray diffraction(XRD), scanning electron microscope(SEM) and energy dispersive spectrometer(EDS).The results showed that the synthesis process of Al-Ti-C master alloy prepared by the reaction of K_2TiF_6-sawdust and aluminum liquid contained the following stages.(1) The titanium substituted by the reaction of aluminum and potassium fluotitanate reacted with aluminum to produce the titanium aluminum compounds.(2) The sawdust were dehydrated and carbonized under high temperature, and then cracking products-carbon dioxide and carbon reacted with aluminum to form carbon and aluminum compounds, and reacted with titanium to form titanium carbon compounds.(3) Titanium aluminum, carbon aluminum and titanium carbon compounds formed Al-Ti-C parent alloy with refining effect. The phase of the alloy was a eutectic structure composed of α(Al), aluminum and titanium compounds and carbon aluminum compounds, with α(Al) phase′s average grain size of 10～60 μm. The aluminum and titanium compounds were rod like, bone like eutectic and distributed along the grain boundary. The needle like Al_3Ti was found in the crystal, and the granular TiC aggregated to form a clump like distribution. Sawdust′s crackate-water, carbon dioxide reacted with aluminum to produce alumina and hydrogen at the grain boundary in the form of slag-gas symbiosis.
The microstructure and properties of Al-Ti-C master alloy prepared by fluorine salt and sawdust method were studied by X-ray diffraction(XRD), scanning electron microscope(SEM) and energy dispersive spectrometer(EDS).The results showed that the synthesis process of Al-Ti-C master alloy prepared by the reaction of K_2TiF_6-sawdust and aluminum liquid contained the following stages.(1) The titanium substituted by the reaction of aluminum and potassium fluotitanate reacted with aluminum to produce the titanium aluminum compounds.(2) The sawdust were dehydrated and carbonized under high temperature, and then cracking products-carbon dioxide and carbon reacted with aluminum to form carbon and aluminum compounds, and reacted with titanium to form titanium carbon compounds.(3) Titanium aluminum, carbon aluminum and titanium carbon compounds formed Al-Ti-C parent alloy with refining effect. The phase of the alloy was a eutectic structure composed of α(Al), aluminum and titanium compounds and carbon aluminum compounds, with α(Al) phase′s average grain size of 10～60 μm. The aluminum and titanium compounds were rod like, bone like eutectic and distributed along the grain boundary. The needle like Al_3Ti was found in the crystal, and the granular TiC aggregated to form a clump like distribution. Sawdust′s crackate-water, carbon dioxide reacted with aluminum to produce alumina and hydrogen at the grain boundary in the form of slag-gas symbiosis.
引文
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[19] Xu C X.Research on Synthesis and Grain-Refining Efficiency of Al-Ti-C Based Master Alloys [D].Taiyuan:Taiyuan University of Technology,2010.1.(许春香.Al-Ti-C基中间合金的合成及其细化效果研究 [D].太原:太原理工大学,2010.1.)
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[2] Cheng C X,Yang X J,He Y,Zhu Y B.Effect of Ce on the A356 aluminum alloy and its refining mechanism [J].Rare Metals,2018,42(11):1127.(程昌学,杨湘杰,何毅,朱永博.Ce对A356合金的影响及细化机制的研究 [J].稀有金属,2018,42(11):1127.)
[3] Wang P,Zhang R Y,Liu T L,Yang S,Han X W.Rsearch of Al-TiO2-C refiners by different titanium carbon ratio on refining and modifying performance of ZL101 alloy [J].Rare Metals,2018,42(7):743.(王鹏,张瑞英,刘天丽,杨森,韩小伟.不同钛碳比制备的Al-TiO2-C细化剂对ZL101细化变质效果研究 [J].稀有金属,2018,42(7):743.)
[4] Yao L J,Zhang H J,Wang Y B,Zhang Y J.Application of novel grain refiner in refinement of A356 alloy for wheel hub [J].Foundry Technology,2017,38(2):360.(姚利军,张海军,王悦博,张亦杰.新型晶粒细化剂在A356汽车轮毂铝合金中的应用研究 [J].铸造技术,2017,38(2):360.)
[5] Chen Y Y,Su Y J,Kong F T.Research progress in preparation of TiAl interemetallic based compound [J].Rare Metal Materials and Engineering,2014,43(3):757.(陈玉勇,苏勇君,孔凡涛.TiAl金属间化合物制备技术的研究进展 [J].稀有金属材料与工程,2014,43(3):757.)
[6] Pramod S L,Rao A P,Murty B S,Bakshi S R.Effect of Sc addition on the microstructure and wear properties of A356 alloy and A356-TiB2 in situ composite [J].Materials & Design,2015,78:85.
[7] Cai S Q,Li Y J,Yuan C H,Li X W,Xue L H.Effect of nano TiN/Ti refiner on as-cast and hot-working microstructure of commercial purity aluminum [J].Transactions of Nonferrous Metals Society of China,2013,23(7):1890.
[8] Wang F,Dong Q,Liu Z L,Taylor J,Easton M,Zhang M X.Crystallographic study of Al3Zr and Al3Nb as grain refiners for Al alloys [J].Transactions of Nonferrous Metals Society of China,2014,24(7):2034.
[9] Sreekumar V M,Eskin D G.A new Al-Zr-Ti master alloy for ultrasonic grain refinement of wrought and foundry aluminum alloys [J].JOM,2016,68(12):1.
[10] Sato H,Ota K,Furukawa M,Azuma M,Watanabe W,Zhang Z.Grain refinement of as-cast pure Al by cold-rolled Al-Ti alloy refiner [J].Materials Transactions,2013,54(9):1554.
[11] Zheng J W,Nai C S.Synthesis and refinement performance of the novel Al-Ti-B-RE master alloy grain refiner [J].Rare Metal Materials and Engineering,2015,44(12):2970.
[12] Zheng J W,Nai C S.Effect of the morphology and distribution of the second phases of Al-Ti-B-RE master alloys on refining commercially pure aluminum [J].Rare Metal Materials and Engineering,2015,44(6):1494.
[13] Ren J,Tao Q G,Ma Y.Manufacture of Al-Ti-B grain refiner by reaction of complex halide salts with molten aluminum in B2O3 alternative KBF4 [J].Chinese Journal of Rare Metals,2016,40(2):188.(任峻,陶钦贵,马颖.B2O3替代KBF4用氟盐法制备Al-Ti-B晶粒细化剂的研究 [J].稀有金属,2016,40(2):188.)
[14] Han X W,Zhang R,Wang P,Li Y H.Microstructure and refining performance of Al-TiO2-C refiners with different TiO2 contents [J].Chinese Journal of Rare Metals,2016,40(12):1226.(韩小伟,张瑞英,王鹏,李艳辉.TiO2含量对Al-TiO2-C细化剂组织及细化效果的影响 [J].稀有金属,2016,40(12):1226.)
[15] Huang Y C,Du Z Y,Xiao Z B,Yan X Y.Effect of Al-Ti-C and Al-Ti-B on microstructure and mechanical performance of 7050 aluminum alloy [J].Journal of Materials Engineering,2015,43(12):75.(黄元春,杜志勇,肖政兵,颜徐宇.Al-Ti-C和Al-Ti-B对7050铝合金微观组织与力学性能的影响 [J].材料工程,2015,43(12):75.)
[16] Zhuang H Y,Pan X M.Influence of irradiation parameters on microstructures of Al-Ti-C master alloys by laser-induced self-propagating high-temperature synthesis (SHS) [J].Rare Metal Materials and Engineering,2010,39(1):46.(庄洪宇,潘学民.辐照参数对激光引燃自蔓延合成Al-Ti-C中间合金的影响 [J].稀有金属材料与工程,2010,39(1):46.)
[17] Wang E Z,Liu X F.Grain reinement limit of commercial pure Al inoculated by Al-Ti-C(B) master alloys [J].China Foundry,2015,12(2):99.
[18] Huang J B,Tong H,Li W M,Wu D.Molecular dynamic simulation study on thermal decomposition mechanism of lignin [J].Materials Review,2012,26(20):138.(黄金保,童红,李伟民,伍丹.木质素热解机理的分子动力学模拟研究 [J].材料导报,2012,26(20):138.)
[19] Xu C X.Research on Synthesis and Grain-Refining Efficiency of Al-Ti-C Based Master Alloys [D].Taiyuan:Taiyuan University of Technology,2010.1.(许春香.Al-Ti-C基中间合金的合成及其细化效果研究 [D].太原:太原理工大学,2010.1.)
[20] Zhao F J,He Y D,Liu X Y,Li Z J,He M G.Study on the effect of interactions between sticks and high-temperature aluminum liquid on formation of hydrogen and alumina inclusions in liquid aluminum [J].Light Metals,2017,(1):31.(赵风君,贺永东,刘向阳,李志军,何茂刚.木条与高温铝液作用对铝液中形成氢和氧化铝夹杂的影响研究 [J].轻金属,2017,(1):31.)