CN110512122B - 一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金及其制备方法 - Google Patents
一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金及其制备方法 Download PDFInfo
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- CN110512122B CN110512122B CN201910814944.5A CN201910814944A CN110512122B CN 110512122 B CN110512122 B CN 110512122B CN 201910814944 A CN201910814944 A CN 201910814944A CN 110512122 B CN110512122 B CN 110512122B
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- 239000000956 alloy Substances 0.000 title claims abstract description 131
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 127
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 229910018566 Al—Si—Mg Inorganic materials 0.000 title claims abstract description 55
- 238000005266 casting Methods 0.000 title claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 97
- 239000000843 powder Substances 0.000 claims description 95
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound 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[Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 91
- 239000002245 particle Substances 0.000 claims description 76
- 239000011777 magnesium Substances 0.000 claims description 37
- 239000011856 silicon-based particle Substances 0.000 claims description 34
- 238000003723 Smelting Methods 0.000 claims description 33
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
Abstract
本发明涉及一种石墨烯复合稀土变质亚共晶Al‑Si‑Mg铸造合金及其制备方法，所述合金化学组分为：Si 4.5～10.5％，Mg 0.25～0.70％，Ce 0.21～1.21％，Ti 0.05～0.20％，Fe 0.04～0.25％，Cu 0.03～0.25％，Mn 0.03～0.25％，Cr 0.00～0.25％，Ni 0.00～0.10％，Zn 0.00～0.35％，Sn 0.00～0.15％，Zr 0.05～0.15％，Be 0.05～0.1％，Pb 0.05～0.1％，石墨烯0.001～0.005％，余量为Al。本发明通过添加变质元素Ce、改性元素Ti和微量石墨烯与其它金属元素配伍，采用真空熔融工艺，扩大了铸态Al‑Si‑Mg合金材料的应用范围。
Description
技术领域
本发明属于铸造铝合金技术领域，特别是涉及一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金及其制备方法。
背景技术
铝的密度小，塑性好，具备优良的导电性，表面有致密的氧化膜，抗腐蚀性好，回收成本低，是一种可反复使用的有色金属。铝及其合金制品在现代工业生产，日常生活用品等多个方面都显示出了其他金属材料无法代替的优点。铸造铝合金中一般所含合金元素种类多且含量高，合金组织中含有多种共晶体，具有良好的铸造性能、成型性能和力学性能，适用于铸造零件，广泛应用于航空、航天、汽车、机械等各行业。
在纯铝中加入其它金属，能制备成各种可供变形加工或铸造用的铝合金。Si作为铝合金中最重要的添加元素之一，Si的加入能提高合金的铸造性能，改善铝合金金属液的流动性，降低热裂倾向性，减少缩松和气孔夹杂，获得组织致密的铸件，提高铝合金的成型率，该类合金具有良好的抗蚀性，但目前国内牌号的铸造Al-Si-Mg系合金力学性能普遍较低，塑性差，如铸态ZL101合金，抗拉强度155MPa，伸长率2％，铸态ZL104合金，抗拉强度150MPa，伸长率2％，限制其在建筑及汽车领域的应用，
发明内容
本发明所要解决的技术问题是针对现有技术中存在的上述不足，提供一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金及其制备方法，该Al-Si-Mg铸造合金抗拉强度、屈服强度、延伸率都较现有Al-Si-Mg铸造合金得到显著提升，扩大Al-Si-Mg铸造合金材料应用领域。
为解决上述技术问题，本发明提供的技术方案是：
提供一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，所述合金按质量百分比计的化学组分为：
Si 4.5～10.5wt.％，
Mg 0.25～0.70wt.％，
Ce 0.21～1.21wt.％，
Ti 0.05～0.20wt.％，
Fe 0.04～0.25wt.％，
Cu 0.03～0.25wt.％，
Mn 0.03～0.25wt.％，
Cr 0.00～0.25wt.％，
Ni 0.00～0.10wt.％，
Zn 0.00～0.35wt.％，
Sn 0.00～0.15wt.％，
Zr 0.05～0.15wt.％，
Be 0.05～0.1wt.％，
Pb 0.05～0.1wt.％，
石墨烯0.001～0.005wt.％，
未指定的其它杂质元素：每种≤0.02wt.％，合计≤0.10wt.％，
余量为Al。
本发明还提供上述石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金的制备方法，具体步骤如下：
步骤1、按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce粉，Ti粉，Fe粉，Cu粉，Mn粉，Cr粉，Ni粉，Zn粉，Sn粉，Zr粉，Be粉，Pb粉，石墨烯；
步骤2、将称取的石墨烯平铺在铝箔上，滴入少量高纯度酒精，使石墨烯充分溶解于酒精中，加入步骤1称取的Si颗粒，搅拌均匀，使Si颗粒粘附石墨烯，待酒精挥发20～30s后折叠铝箔，得到包裹石墨烯与硅颗粒的铝箔；
步骤3、将1/4～1/3的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
步骤4、将熔炼坩埚放入熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至450～500Pa充当保护气体，打开加热电源，升温至700～720℃使铝颗粒熔化，待铝颗粒完全熔化，升高熔炼温度至740～750℃，不断晃动熔炼坩埚，加速合金熔液均匀化；
步骤5、停止加热，待合金熔液降温至630～650℃，带电将合金熔液浇铸于石墨模具中，得到石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金。
按上述方案，步骤2所述铝箔为0.1mm厚的工业纯铝，Al的纯度为99.7wt.％以上；所述硅颗粒为平均粒径为1～6mm的片状颗粒，Si的纯度为99.9wt.％以上；所述石墨烯粉末为单层石墨烯，x-y平面宽度最长为10μm，碳含量大于95.0％，氧含量小于2.50％；所述铝粒为Φ6*6mm的工业纯铝柱状颗粒，Al的纯度为99.7wt.％以上；所述镁粒为平均粒径1-6mm的纯镁颗粒，Mg的纯度为99.9wt.％以上，其他金属原料的平均粒径为1～10mm，纯度为99.5wt.％以上。
按上述方案，步骤4所述的熔炼炉为真空感应熔炼炉。
本发明还包括上述石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金在建筑领域方面的应用。
本发明还包括上述石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金在汽车轮毂方面的应用。
本发明合金中各主要组份的功能如下：
Si是铝合金中最重要的添加元素之一，Si的加入能提高合金的铸造性能，改善铝合金金属液的流动性，降低热裂倾向性，减少缩松和气孔夹杂，获得组织致密的铸件，提高合金成型率，该类合金具有良好的抗蚀性，中等强度，但塑性较低。Mg是铝硅合金中主要的强化元素，在铝硅合金中加入少量Mg元素，合金中出现Mg2Si强化相，热处理后，弥散分布的Mg2Si会显著提高合金抗拉强度，但为了保证合金塑性，铝硅合金中Mg的加入量一般不超过1wt.％。根据Al-Si二元相图，亚共晶铝硅合金中Si的含量一般在4-13wt.％之间，亚共晶铝硅合金平衡凝固处于(Al)+(Si)两相区内，由于实际凝固过程为非平衡凝固，其相组成是(Al)+Mg2Si+(Si)，共晶温度为550℃，该温度下(Al)能溶解的Mg为0.0-0.7wt.％，若Mg含量高于此范围，粗大Mg2Si无法固溶在铝基体中，最终分布在晶界，急剧降低合金的延伸率，本发明优选的Mg的用量为0.25～0.70wt.％。
稀土元素Ce与Al、Si元素易形成中间化合物(如：AlSiCe2，Al4Ce等)，这些化合物与初晶(Al)，共晶(Si)竞争生长，将板条状共晶(Si)变质为纤维状或颗粒状形貌，大力提高合金的力学性能；此外，Ce与Al、Si在晶界上形成的弥散分布AlSiCe2中间相，其体积杨氏弹性模量大于基体Al和共晶Si的杨氏模量，AlSiCe2相比铝基体具有更高的强度，在合金内部作为强化硬质相起到颗粒强化的作用，提高合金强度，为达到最佳变质效果，本发明优选的Ce的用量为0.21～1.21wt.％。
微量Ti元素，熔炼铸造过程中，弥散均匀分布的Ti元素在铝硅合金中充当异质形核核心，降低形核驱动力，增加形核率，促进更多初晶(Al)晶粒生成，细化初晶(Al)晶粒尺寸。Ti对合金中的铝基体进行改性，减小铝基体的尺寸，提高合金抗拉强度。
石墨烯具有高强度、高导电性能和高导热性能等超强的力学和功能特性，本发明充分利用石墨烯的高强高韧性能，石墨烯与铝基体形成良好的结合界面，有效阻止合金受力过程中的位错移动和裂纹扩展，提升合金强度的同时提高合金塑性，本发明通过添加微量石墨烯改进亚共晶Al-Si-Mg合金综合性能。
本发明的有益效果在于：
(1)本发明通过添加变质元素Ce、改性元素Ti和微量石墨烯与其它金属元素配合，采用真空熔融工艺，研制出一种铸态高强高韧Al-Si-Mg铸造铝合金材料，其铸态强度可超国标热处理态强度，完全可应用在汽车工业和建筑领域，扩大了铸态Al-Si-Mg合金材料的应用范围；
(2)本发明引入熔池方法，使原料在熔炼过程中因加热而熔化成池状，形成液态金属，加快热传导，提高材料制备效率；另外，通过电流的变化产生磁场的变化，变化的磁场作用于熔池，产生搅拌作用，促进液态金属均匀化，通过带电浇铸保证浇铸过程中合金液的恒温性，使得到的Al-Si-Mg铸造合金微观结构均一，整体性能优良。
附图说明：
图1为本发明对比例1制备的Al-Si-Mg铸造合金的500倍率下金相组织图；
图2为实施例1制备的亚共晶Al-Si-Mg合金的500倍率下金相组织图；
图3为对比例2制备的Al-Si-Mg铸造合金的500倍率下金相组织图；
图4为实施例2制备的亚共晶Al-Si-Mg合金的500倍率下金相组织图；
图5为对比例3制备的Al-Si-Mg铸造合金的500倍率下金相组织图；
图6为实施例3制备的亚共晶Al-Si-Mg合金的500倍率下金相组织图；
图7为对比例4制备的Al-Si-Mg铸造合金的500倍率下金相组织图；
图8为实施例4制备的亚共晶Al-Si-Mg合金的500倍率下金相组织图；
图9为对比例1和实施例1所制备的Al-Si-Mg铸造合金的性能柱状对比图；
图10为对比例2和实施例2所制备的Al-Si-Mg铸造合金的性能柱状对比图；
图11为对比例3和实施例3所制备的Al-Si-Mg铸造合金的性能柱状对比图；
图12为对比例4和实施例4所制备的Al-Si-Mg铸造合金的性能柱状对比图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图对本发明作进一步详细描述。
除非另有说明，下列实例中所使用的仪器，材料、试剂等均可通过常规商业手段获得。
为使本发明的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述。很显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。
本发明实施例所用铝箔为0.1mm厚的工业纯铝，Al的纯度为99.7wt.％以上；所用硅颗粒为平均粒径为1～6mm的片状颗粒，Si的纯度为99.9wt.％以上；所用石墨烯粉末为单层石墨烯，x-y平面宽度最长为10μm，碳含量大于95.0％，氧含量小于2.50％；所用铝粒为Φ6*6mm的工业纯铝柱状颗粒，Al的纯度为99.7wt.％以上；所用镁粒为平均粒径1-6mm的纯镁颗粒，Mg的纯度为99.9wt.％以上，其他金属原料的平均粒径为1～10mm，纯度为99.5wt.％以上。
实施例1
本实施例拟制备一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，其化学组分为：Si5.00wt.％，Mg 0.50wt.％，Ce 0.41wt.％，Ti 0.10wt.％，Fe 0.12wt.％，Cu0.10wt.％，Mn 0.03wt.％，Cr 0.03wt.％，Ni 0.03wt.％，Zn 0.20wt.％，Sn 0.10wt.％，Zr0.05wt.％，Be 0.05wt.％，Pb 0.05wt.％，石墨烯0.005wt.％；未指定的其它杂质元素：每种≤0.02wt.％，合计≤0.10wt.％，余量为Al。
具体制备方法如下：
(1)按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce粉，Ti粉，Fe粉，Cu粉，Mn粉，Cr粉，Ni粉，Zn粉，Sn粉，Zr粉，Be粉，Pb粉，石墨烯；
(2)将称取的石墨烯平铺在铝箔上，滴定少量高纯度酒精，使石墨烯充分溶解于酒精中，加入Si颗粒，搅拌均匀，待酒精挥发20～30s后折叠铝箔，包裹住粘附石墨烯的Si颗粒；
(3)将1/3的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
(4)将熔炼坩埚放入真空感应熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至500Pa充当保护气体，打开加热电源，升温至700℃使铝颗粒熔化形成熔池，利用熔池效应加快热传递，提高熔化速率；待铝颗粒完全熔化，升高熔炼温度至740℃，不断晃动熔炼坩埚，加速合金液的均匀化；
(5)停止加热，待合金液降温至650℃，带电将熔液浇铸于石墨模具中，获得铸造合金。
对比例1
一种Al-Si-Mg铸造合金，制备方法与实施例1相似，不同之处在于原料中未添加Ce、Ti和石墨烯，得到Al-5wt.％Si-0.5wt.％Mg的亚共晶Al-Si-Mg合金。
对比例1制备的Al-Si-Mg铸造合金500倍率下金相组织图如图1所示，可见未添加Ce、Ti和石墨烯合金微观组织中有：初生(Al)，二元共晶(Al)+(Si)组织和三元共晶(Al)+(Si)+Mg2Si组织。其中，初生(Al)相为粗大的树枝晶，共晶Mg2Si弥散分布于晶粒，共晶(Si)为粗大的板条状，与共晶(Al)结合分布在晶粒边界。而实施例1制备的Al-Si-Mg铸造合金500倍率下金相组织图如图2所示，合金微观组织中有：初生(Al)相，二元共晶(Al)+(Si)组织，三元共晶(Al)+(Si)+Mg2Si组织和四元共晶(Al)+(Si)+Mg2Si+AlSiCe2组织。添加变质稀土元素Ce、Ti和石墨烯后，弥散分布的变质元素Ti和石墨烯将合金中粗大的初生(Al)相变质为细小的等轴晶。通过稀土元素Ce的添加，合金中除了存在三元共晶反应，还发生四元共晶反应，四元共晶反应将合金中的共晶(Si)变质为细小的骨骼状或者颗粒状；此外，稀土元素Ce在合金中与Al，Si之间通过四元共晶反应生成AlSiCe2硬质相，其体积杨氏模量远高于基体(Al)相，通过颗粒强化，提高合金综合力学性能。变质前合金(对比例1)的抗拉强度、屈服强度和延伸率分别为173.71MPa、89.46MPa和2.10％，变质后(实施例1)分别提高到187.76MPa、104.35MPa和2.60％，提升比例分别为8.09％、16.64％和23.80％，柱状对比图见图9。
实施例2
本实施例拟制备一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，其化学组分为：Si 7.00wt.％，Mg 0.50wt.％，Ce 0.61wt.％，Ti 0.10wt.％，Fe 0.12wt.％，Cu0.10wt.％，Mn 0.03wt.％，Cr 0.03wt.％，Ni 0.03wt.％，Zn 0.20wt.％，Sn 0.10wt.％，Zr0.05wt.％，Be 0.05wt.％，Pb 0.05wt.％，石墨烯0.005wt.％；未指定的其它杂质元素：每种≤0.02wt.％，合计≤0.10wt.％，余量为Al。
具体制备方法如下：
(1)按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce粉，Ti粉，Fe粉，Cu粉，Mn粉，Cr粉，Ni粉，Zn粉，Sn粉，Zr粉，Be粉，Pb粉，石墨烯；
(2)将称取的石墨烯平铺在铝箔上，滴定少量高纯度酒精，使石墨烯充分溶解于酒精中，加入Si颗粒，搅拌均匀，待酒精挥发20～30s后折叠铝箔，包裹住粘附石墨烯的Si颗粒；
(3)将1/4的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外及其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
(4)将熔炼坩埚放入真空感应熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至500Pa充当保护气体，打开加热电源，升温至700℃使铝颗粒熔化形成熔池，利用熔池效应加快热传递，提高熔化速率；待铝颗粒完全熔化，升高熔炼温度至740℃，不断晃动熔炼坩埚，加速合金液的均匀化；
(5)待合金液降温至650℃，带电将熔液浇铸于石墨模具中，获得铸造合金。
对比例2
一种Al-Si-Mg铸造合金，制备方法与实施例2相似，不同之处在于原料中未添加Ce、Ti和石墨烯，得到Al-7wt.％Si-0.5wt.％Mg的亚共晶Al-Si-Mg合金。
对比例2制备的Al-Si-Mg铸造合金500倍率下金相组织图如图3所示，可见未添加Ce、Ti和石墨烯合金微观组织中有：初生(Al)，二元共晶(Al)+(Si)组织和三元共晶(Al)+(Si)+Mg2Si组织。其中，初生(Al)相为粗大的树枝晶，共晶Mg2Si弥散分布于晶粒，共晶(Si)为粗大的板条状，与共晶(Al)结合分布在晶粒边界。而实施例2制备的Al-Si-Mg铸造合金500倍率下金相组织图如图4所示，合金微观组织中有：初生(Al)相，二元共晶(Al)+(Si)组织，三元共晶(Al)+(Si)+Mg2Si组织和四元共晶(Al)+(Si)+Mg2Si+AlSiCe2组织。添加变质稀土元素Ce、Ti和石墨烯后，弥散分布的变质元素Ti和石墨烯将合金中粗大的初生(Al)相变质为细小的等轴晶。通过稀土元素Ce的添加，合金中除了存在三元共晶反应，还发生四元共晶反应，四元共晶反应将合金中的共晶(Si)变质为细小的骨骼状或者颗粒状；此外，稀土元素Ce在合金中与Al，Si之间通过四元共晶反应生成AlSiCe2硬质相，其体积杨氏模量远高于基体(Al)相，通过颗粒强化，提高合金综合力学性能。变质前合金(对比例2)的抗拉强度、屈服强度和延伸率分别为195.80MPa、99.42MPa和4.83％，变质后(实施例2)分别提高到207.52MPa、109.46MPa和6.90％，提升比例分别为5.98％、10.10％和42.86％，柱状对比图见图10。
实施例3
本实施例拟制备一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，其化学组分为：Si 7.00wt.％，Mg 0.60wt.％，Ce 0.83wt.％，Ti 0.10wt.％，Fe 0.12wt.％，Cu0.10wt.％，Mn 0.03wt.％，Cr 0.03wt.％，Ni 0.03wt.％，Zn 0.20wt.％，Sn 0.10wt.％，Zr0.05wt.％，Be 0.05wt.％，Pb 0.05wt.％，石墨烯0.005wt.％；未指定的其它杂质元素：每种≤0.02wt.％，合计≤0.10wt.％，余量为Al。
具体制备方法如下：
(1)按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce粉，Ti粉，Fe粉，Cu粉，Mn粉，Cr粉，Ni粉，Zn粉，Sn粉，Zr粉，Be粉，Pb粉，石墨烯；
(2)将称取的石墨烯平铺在铝箔上，滴定少量高纯度酒精，使石墨烯充分溶解于酒精中，加入Si颗粒，搅拌均匀，待酒精挥发20～30s后折叠铝箔，包裹住粘附石墨烯的Si颗粒；
(3)将1/3的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外及其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
(4)将熔炼坩埚放入真空感应熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至500Pa充当保护气体，打开加热电源，升温至700℃使铝颗粒熔化形成熔池，利用熔池效应加快热传递，提高熔化速率；待铝颗粒完全熔化，升高熔炼温度至740℃，不断晃动熔炼坩埚，加速合金液的均匀化；
(5)待合金液降温至650℃，带电将熔液浇铸于石墨模具中，获得铸造合金。
对比例3
一种Al-Si-Mg铸造合金，制备方法与实施例3相似，不同之处在于原料中未添加Ce、Ti和石墨烯，得到Al-7wt.％Si-0.6wt.％Mg的亚共晶Al-Si-Mg合金。
对比例3制备的Al-Si-Mg铸造合金500倍率下金相组织图如图5所示，可见未添加Ce、Ti和石墨烯合金微观组织中有：初生(Al)，二元共晶(Al)+(Si)组织和三元共晶(Al)+(Si)+Mg2Si组织。其中，初生(Al)相为粗大的树枝晶，共晶Mg2Si弥散分布于晶粒，共晶(Si)为粗大的板条状，与共晶(Al)结合分布在晶粒边界。而实施例3制备的Al-Si-Mg铸造合金500倍率下金相组织图如图6所示，合金微观组织中有：初生(Al)相，二元共晶(Al)+(Si)组织，三元共晶(Al)+(Si)+Mg2Si组织和四元共晶(Al)+(Si)+Mg2Si+AlSiCe2组织。添加变质稀土元素Ce、Ti和石墨烯后，弥散分布的变质元素Ti和石墨烯将合金中粗大的初生(Al)相变质为细小的等轴晶。通过稀土元素Ce的添加，合金中除了存在三元共晶反应，还发生四元共晶反应，四元共晶反应将合金中的共晶(Si)变质为细小的骨骼状或者颗粒状；此外，稀土元素Ce在合金中与Al，Si之间通过四元共晶反应生成AlSiCe2硬质相，其体积杨氏模量远高于基体(Al)相，通过颗粒强化，提高合金综合力学性能。变质前合金(对比例3)的抗拉强度、屈服强度和延伸率分别为203.64MPa、105.82MPa和4.64％，变质后(实施例3)分别提高到217.15MPa、117.57MPa和8.77％，提升比例分别为6.63％、11.10％和89.01％，柱状对比图见图11。
实施例4
本实施例拟制备一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，其化学组分为：Si 9.50wt.％，Mg 0.50wt.％，Ce 1.01wt.％，Ti 0.10wt.％，Fe 0.12wt.％，Cu0.10wt.％，Mn 0.03wt.％，Cr 0.03wt.％，Ni 0.03wt.％，Zn 0.20wt.％，Sn 0.10wt.％，Zr0.05wt.％，Be 0.05wt.％，Pb 0.05wt.％，石墨烯0.005wt.％；未指定的其它杂质元素：每种≤0.02wt.％，合计≤0.10wt.％，余量为Al。
具体制备方法如下：
(1)按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce粉，Ti粉，Fe粉，Cu粉，Mn粉，Cr粉，Ni粉，Zn粉，Sn粉，Zr粉，Be粉，Pb粉，石墨烯；
(2)将称取的石墨烯平铺在铝箔上，滴定少量高纯度酒精，使石墨烯充分溶解于酒精中，加入Si颗粒，搅拌均匀，待酒精挥发20～30s后折叠铝箔，包裹住粘附石墨烯的Si颗粒；
(3)将1/4的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入包裹石墨烯与硅颗粒的铝箔，接着将其它原料放入坩埚，之后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
(4)将熔炼坩埚放入真空感应熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至500Pa充当保护气体，打开加热电源，升温至700℃使铝颗粒熔化形成熔池，利用熔池效应加快热传递，提高熔化速率；待铝颗粒完全熔化，升高熔炼温度至740℃，不断晃动熔炼坩埚，加速合金液的均匀化；
(5)待合金液降温至650℃，带电将熔液浇铸于石墨模具中，获得铸造合金。
对比例4
一种Al-Si-Mg铸造合金，制备方法与实施例4相似，不同之处在于原料中未添加Ce、Ti和石墨烯，得到Al-9.5wt.％Si-0.5wt.％Mg的亚共晶Al-Si-Mg合金。
对比例4制备的Al-Si-Mg铸造合金500倍率下金相组织图如图7所示，可见未添加Ce、Ti和石墨烯合金微观组织中有：初生(Al)，二元共晶(Al)+(Si)组织和三元共晶(Al)+(Si)+Mg2Si组织。其中，初生(Al)相为粗大的树枝晶，共晶Mg2Si弥散分布于晶粒，共晶(Si)为粗大的板条状，与共晶(Al)结合分布在晶粒边界。而实施例4制备的Al-Si-Mg铸造合金500倍率下金相组织图如图8所示，合金微观组织中有：初生(Al)相，二元共晶(Al)+(Si)组织，三元共晶(Al)+(Si)+Mg2Si组织和四元共晶(Al)+(Si)+Mg2Si+AlSiCe2组织。添加变质稀土元素Ce、Ti和石墨烯后，弥散分布的变质元素Ti和石墨烯将合金中粗大的初生(Al)相变质为细小的等轴晶。通过稀土元素Ce的添加，合金中除了存在三元共晶反应，还发生四元共晶反应，四元共晶反应将合金中的共晶(Si)变质为细小的骨骼状或者颗粒状；此外，稀土元素Ce在合金中与Al，Si之间通过四元共晶反应生成AlSiCe2硬质相，其体积杨氏模量远高于基体(Al)相，通过颗粒强化，提高合金综合力学性能。变质前合金(对比例4)的抗拉强度、屈服强度和延伸率分别为210.48MPa、111.09MPa和5.23％，变质后(实施例4)分别提高到232.54MPa、125.56MPa和5.81％，提升比例分别为10.48％、13.03％和11.09％，柱状对比图见图12。
本说明书中的各个实施例均采用相关的方式描述，各个实施例之间相同相似的部分互相参见即可，每个实施例重点说明的都是与其他实施例的不同之处。尤其，对于系统实施例而言，由于其基本相似于方法实施例，所以描述的比较简单，相关之处参见方法实施例的部分说明即可。
以上所述仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。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，均包含在本发明的保护范围内。
Claims (6)
1.一种石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金，其特征在于，所述合金按质量百分比计的化学组分为：
Si 4.5~10.5 wt. %，
Mg 0.25~0.70 wt. %，
Ce 0.21~1.21 wt. %，
Ti 0.05~0.20 wt. %，
Fe 0.04~0.25wt. %，
Cu 0.03~0.25 wt. %，
Mn 0.03~0.25 wt. %，
Cr 0.03~0.25 wt. %，
Ni 0.03~0.10 wt. %，
Zn 0.00~0.35 wt. %，
Sn 0.00~0.15 wt. %，
Zr 0.05~0.15 wt. %，
Be 0.05~0.1 wt. %，
Pb 0.05~0.1 wt. %，
石墨烯0.001~0.005 wt.%，
未指定的其它杂质元素：每种≤0.02 wt.%，合计≤0.10 wt.%，
余量为Al；
其制备方法具体步骤如下：
步骤1、按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce 粉，Ti 粉，Fe粉，Cu 粉，Mn 粉，Cr 粉，Ni 粉，Zn 粉，Sn粉，Zr 粉，Be 粉，Pb 粉，石墨烯；
步骤2、将称取的石墨烯平铺在铝箔上，滴入少量高纯度酒精，使石墨烯充分溶解于酒精中，加入步骤1称取的Si颗粒，搅拌均匀，使Si颗粒粘附石墨烯，待酒精挥发20~30s后折叠铝箔，得到包裹石墨烯与硅颗粒的铝箔；
步骤3、将1/4~1/3的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
步骤4、将熔炼坩埚放入熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至450~500Pa充当保护气体，打开加热电源，升温至700~720℃使铝颗粒熔化，待铝颗粒完全熔化，升高熔炼温度至740~750℃，不断晃动熔炼坩埚，加速合金熔液均匀化；
步骤5、停止加热，待合金熔液降温至630~650℃，带电将合金熔液浇铸于石墨模具中，得到石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金。
2.一种权利要求1所述的石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金的制备方法，其特征在于，具体步骤如下：
步骤1、按照合金元素配比称取各组分原料：铝颗粒、Si颗粒，Mg粉，Ce 粉，Ti 粉，Fe粉，Cu 粉，Mn 粉，Cr 粉，Ni 粉，Zn 粉，Sn粉，Zr 粉，Be 粉，Pb 粉，石墨烯；
步骤2、将称取的石墨烯平铺在铝箔上，滴入少量高纯度酒精，使石墨烯充分溶解于酒精中，加入步骤1称取的Si颗粒，搅拌均匀，使Si颗粒粘附石墨烯，待酒精挥发20~30s后折叠铝箔，得到包裹石墨烯与硅颗粒的铝箔；
步骤3、将1/4~1/3的铝颗粒放入熔炼坩埚中，铺满坩埚底部，随后放入步骤2所得包裹石墨烯与硅颗粒的铝箔，接着将Al以外其它金属原料放入坩埚，最后放入剩余铝颗粒，使铝颗粒完全覆盖其它原料；
步骤4、将熔炼坩埚放入熔炼炉中，关闭熔炼炉门，抽真空后充入高纯氩气至450~500Pa充当保护气体，打开加热电源，升温至700~720℃使铝颗粒熔化，待铝颗粒完全熔化，升高熔炼温度至740~750℃，不断晃动熔炼坩埚，加速合金熔液均匀化；
步骤5、停止加热，待合金熔液降温至630~650℃，带电将合金熔液浇铸于石墨模具中，得到石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金。
3. 根据权利要求2所述的石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金的制备方法，其特征在于，步骤2所述铝箔为0.1mm厚的工业纯铝，Al的纯度为99.7 wt.%以上；所述硅颗粒为平均粒径为1~6mm的片状颗粒，Si的纯度为 99.9 wt.%以上；所述石墨烯粉末为单层石墨烯，x-y平面宽度最长为10μm，碳含量大于95.0%，氧含量小于2.50%；所述铝颗粒为Φ6*6mm的工业纯铝柱状颗粒，Al的纯度为99.7 wt.%以上；所述Mg粉为平均粒径1-6mm的纯镁颗粒，Mg的纯度为99.9 wt.%以上，其他金属原料的平均粒径为1~10mm，纯度为99.5 wt.%以上。
4.根据权利要求2所述的石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金的制备方法，其特征在于，步骤4所述的熔炼炉为真空感应熔炼炉。
5.一种权利要求1所述的石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金在建筑领域方面的应用。
6.一种权利要求1所述的石墨烯复合稀土变质亚共晶Al-Si-Mg铸造合金在汽车轮毂方面的应用。
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