CN101275189A - 低氧含量的合金组合物 - Google Patents
低氧含量的合金组合物 Download PDFInfo
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Abstract
本发明涉及低氧含量的合金组合物。涉及一种包括Mn与选自Ga、In、Ni和Zn的一种元素结合的Mn合金的合金组合物。也包括Fe合金和Co合金,其中Fe或Co与Pt或Pd结合。所述的合金组合物在特定的组成范围内形成具有L10或L12型晶体结构的有序化合物。另外,所述的合金组合物的杂质如氧和硫的含量低,使其在磁记录应用中具有更好的性能。所述的合金组合物优选形成为用于薄膜应用领域的溅射靶。
Description
发明领域
本发明涉及低氧含量的合金组合物,更具体地,涉及具有磁记录应用中有用磁性的低氧含量的合金组合物。
背景技术
磁阻磁头(MR)和磁性随机存储器(MRAR)预期是未来几代垂直磁记录和手机存储应用中的关键技术。正在研究新的材料以改进提高存储面密度和降低存储芯片尺寸的设计。这些新的材料不仅必须具有专用于这些技术的磁性,而且它们也必须具有高纯度。
材料纯度对于用在磁性数据存储和MRAM应用中的薄膜材料的性能起着重要作用。例如,杂质如氧、氮、硫和碱性化合物改变薄膜材料的晶格结构,从而取代了晶格中的原子。这种对材料结构次序的影响降低了材料的磁性能,从而降低了在磁记录应用中的性能。另外,杂质如氧的存在可产生短的扩散路径通过薄膜材料进入磁性层。因此,需要鉴别和开发具有特定磁性能以及高纯度的薄膜材料。
发明概述
本发明包括一系列用于磁记录领域具有优良磁性的合金组合物。所述合金组合物在所要求保护的组成范围内形成具有L10或L12型晶体结构的有序化合物。另外,本发明的合金组合物杂质如氧和硫含量低,且在磁记录应用中具有更好的性能。合金组合物优选形成用于薄膜应用的溅射靶。
本发明的合金组合物包括Mn与选自Ga、In、Ni和Zn的一种元素结合的Mn合金。所述合金组合物也包括Fe合金和Co合金,其中Fe或Co与Pt或Pd结合。
本发明的合金组合物中氧含量为500ppm或更低,优选为100ppm或更低。另外,合金组合物中硫含量为100ppm或更低,优选为50ppm或更低。
为了能够快速理解本发明的内容,以上提供了本发明的概述。通过以下对本发明的详细描述将对本发明有更完整的理解。
附图说明
图1是刚铸好Ni40Mn at.%合金的光学显微图。
图2是刚铸好Ni30Mn at.%合金的光学显微图。
图3是刚铸好In50Mn at.%合金的SEM显微图。
图4是刚铸好Fe45Pt at.%有序合金的光学显微图。
发明内容
本发明人确认和开发了一系列具有优良磁性且杂质含量低的合金组合物。本发明的合金组合物形成具有L10或L12型晶体结构的有序化合物。另外,合金组合物的氧和硫含量显著降低。
表1总结了本发明合金组合物的相关组成和结构数据。具体地,表1鉴别了有序相符号、结构名称、所研究的相存在时的组成范围、以及所研究的相可与其它相类型共存时的组成范围。表1中所用的相符号从Binary Phase Diagrams,2nd Edition(Thaddeus B.Massalski,ed.)中的相图获得。
表1
合金体系X-Y | 有序相符号 | 结构名称 | 组成at.%Y | 组成范围at.%Y |
Mn-Ga | γ3 | L10 | 55-63 | 50-70 |
Mn-In | InMn3 | L10或L12 | 75 | 50-85 |
Mn-Ni | η′ | L10 | 47-55.5 | 44-60 |
Ni-Mn | γ′ | L12 | 15-29 | 10-30 |
Zn-Mn | α′ | L12 | 25-31 | 20-40 |
Zn-Mn | α1′ | L10 | 25-30 | 20-40 |
Fe-Pt | Fe3Pt | L12 | 16-33 | 16-35 |
Fe-Pt | FePt | L10 | 35-55 | 35-59 |
Fe-Pt | FePt3 | L12 | 57-79 | 57-83 |
Fe-Pd | FePd(a) | L10 | 48.5-60 | 30-63 |
Fe-Pd | FePd3(b) | L12 | 63-86 | 60-88 |
Co-Pt | CoPt(a) | L10 | 42-74 | 40-76 |
Co-Pt | CoPt3(b) | L12 | 75-88 | 75-90 |
Co-Pd | α″ | L10 | 48-52 | 30-58 |
Co-Pd | α′ | L12 | 60-90 | 58-94 |
表1中列出的第一组合金包括具有L10或L12晶体结构的Mn合金。这些Mn合金具有用于磁性数据存储的薄膜材料和MRAM应用中所需的反铁磁性。特别地,这些Mn合金在各向异性磁阻(AMR)和用于高密度记录的巨磁阻(GMR)自旋阀传感器中倍受关注。另外,这些Mn合金由于与Mn结合所用的合金组分比通常所用的那些组分如Pt、Pd、Ir或Rh价格低廉而受到关注。下文的实施例1和2分别描述了本发明的Mn-Ni合金和Mn-In合金。
实施例1:进行了三种Ni-Mn合金的系列熔融试验。每种试验所需的熔融装料组分如表2所示。用99.95%纯度的Ni球和99.9%纯度的Mn片来制备熔融装填组分。
表2
熔融装填组分 | 第一种Ni-Mn熔融试验 | 第二种Ni-Mn熔融试验 | 第三种Ni-Mn熔融试验 |
Ni给料(g) | 630.0 | 6477.5 | 4886.0 |
Mn给料(g) | 870.0 | 3583.1 | 2094.0 |
CaSi2给料(g) | 13.1 | 60.0 | 20.0 |
Ce给料(g) | 7.9 | 77.4 | 无 |
在第一种熔融实验中,合金块在MgO坩锅中直接固化。在第二种和第三种熔融试验中,合金被熔融并被浇铸到石墨模具中。石墨模具经BN喷淋,且在被安装到VIM单元室内之前在单独的加热炉中预热至500℉。在这三种熔融试验中,VIM单元室均被抽真空至约0.05mbar,以准备进行熔融操作。
三种熔融试验的熔融操作均通过对VIM单元施加5kW电压20分钟,并通过每5分钟增加5kW电压再保持20分钟来实现。对于第一种熔融试验,Mn片一旦熔融,便将VIM单元室回充入氩气至约40mbar的压力。对于第二种和第三种试验,随后在25分钟内将VIM单元室回充入氩气至500mbar,然后在37分钟内至700mbar。
从大块坯料制备合金样品以分析化学组成。制成块料后观察MgO坩埚和石墨模具,结果表明没有明显的腐蚀现象。图1和2分别为表征刚铸好Ni40Mn at.%合金和刚铸好Ni30Mn at.%合金微观结构的光学显微图。三种熔融试验中合金样品的化学分析结果如表3所示。
表3
Sippm | Cappm | Ceppm | Mgppm | Nappm | Kppm | Oppm | Cppm | Nppm | Sppm | MnWt.% | |
第一种熔融试验 | 4979 | 166 | 52 | 35 | / | / | 10 | 170 | 37 | 36 | 57.94 |
第二种熔融试验 | 655 | 3 | 49 | 78 | 18 | 0 | 20 | 139 | 28 | 10 | 32.28 |
第三种熔融试验 | 240 | / | 43 | 0 | / | 1 | 64 | 98 | 62 | 15 | 28.61 |
如表3所示,三种熔融合金均被充分脱氧,其氧含量均不超过100ppm。将第一种和第二种熔融试验的氧含量与第三种熔融试验的氧含量进行比较,结果表明Ce也有助于合金组合物的脱氧。另外,对于测得的硫含量约300ppm的Mn薄片,表3的数据表明CaSi2对合金融体的脱氧也起作用。在表3中,“/”表示对特定元素没有进行测量,“0”表示没有检测到特定元素。
实施2:使用2427克99.9%纯度的Mn薄片和5037克99.9%纯度的In棒进行熔融试验。除了Mn和In组分外,加入25克CaSi2和10克Ce作为脱氧剂。在VIM单元室内的MgO坩埚中,在0.07mbar分真空下将熔融填料预热至500℉。然后将VIM单元室回充入氩气至500mbar,通过向VIM单元施加5kW电压20分钟,并通过每5分钟增加5kW电压再进行20分钟,将熔融装料样品熔融。熔融装料然后被浇铸到石墨模具中。
图3是表征刚铸好In50Mn at.%合金微观结构的SEM显微图。该显微图表征的微观结构由三个相组成:浅的In基质、浅灰色相所示的(In,Mn)固熔体和深灰色区域所示的InMn3化合物。显微图中的黑点是气孔。分析刚铸好材料的化学组成,结果如表4所示。
表4
Sippm | Cuppm | Alppm | Nippm | Feppm | Oppm | Cppm | Nppm | Sppm | Mnat.% |
15 | 2 | 10 | 6 | 23 | 40 | 62 | 19 | 33 | 50.7 |
表1中所述的合金还包括Fe和Co合金。在这些合金中,Fe或Co与Pt或Pd结合形成合金组合物。这些合金组合物对使用垂直记录技术的未来几代记录介质很有意义,其容量可希望达到200GB或更高。这些合金组合物对形成磁性硬层特别有意义,因为其可获得高的各相异性常数(Kμ>107J.m-1)。下述实施例3公开了Fe-Pt合金组合物的例子。
实施例3:使用13.500千克99.9%纯度的Pt丸粒和4.724千克电解产生的99.97%纯度的铁薄片进行熔融试验。向熔融填料中加入91克(约0.50wt.%)CaSi2进行脱氧。将填料放置在具有Pt和Fe交替层且CaSi2均匀分布在各层间的坩埚中。将VIM单元室密封,抽真空至起始水平0.07mbar。然后向该室回充氩气,在熔融和铸造过程中保持500mbar的压力。熔融是通过向VIM单元施加5kW电压20分钟,然后每5分钟增加5kW另外进行20分钟而实现的。模具系统是8.00″宽,15.00″长和0.60″厚的石墨壳。
图4是表征刚铸好Fe45Pt at.%合金微观结构的光学显微图。微观结构由上述表1中所述的单相FePt的高孪生粒子构成。孪生粒子导致1300℃时(γFe,Pt)fcc固溶体转变成四方晶格FePt过程中晶格位错。分析刚铸好材料的化学组成,结果如表5所示。
表5
Alppm | Cuppm | Nippm | Sippm | Tappm | Auppm | Reppm | Oppm | Cppm | Nppm | Sppm | Fewt.% |
<5 | <5 | <5 | 90 | 23 | 200 | 515 | 34 | 27 | 4 | 10 | 25.77 |
前述实施例目的在于阐述本发明合金组合物的例子。这些实施例不是用来限制本发明的保护范围,而本发明的保护范围通过所附权利要求书来确定。
尽管前文已公开了本发明的最佳实施方式和/或其它实施例,但应当理解也可对其进行多种改变,且本发明的主题也可通过不同形式和实施例实现,且它们可用于多种领域,而本发明仅阐述了其中的一些。
Claims (11)
1.一种具有L10或L12晶体结构的Co合金组合物,其中所述的合金组合物含500ppm或更低的O和100ppm或更低的S。
2.如权利要求1的Co合金组合物,其中所述的合金组合物含100ppm或更低的O和50ppm或更低的S。
3.如权利要求1的Co合金组合物,其中所述的合金组合物包括60-24at.%的Co和40-76at.%的Pt。
4.如权利要求1的Co合金组合物,其中所述的合金组合物包括58-26at.%的Co和42-74at.%的Pt。
5.如权利要求1的Co合金组合物,其中所述的合金组合物包括25-10at.%的Co和75-90at.%的Pt。
6.如权利要求1的Co合金组合物,其中所述的合金组合物包括25-12at.%的Co和75-88at.%的Pt。
7.如权利要求1的Co合金组合物,其中所述的合金组合物包括70-42at.%的Co和30-58at.%的Pd。
8.如权利要求1的Co合金组合物,其中所述的合金组合物包括52-48at.%的Co和48-52at.%的Pd。
9.如权利要求1的Co合金组合物,其中所述的合金组合物包括42-6at.%的Co和58-94at.%的Pd。
10.如权利要求1的Co合金组合物,其中所述的合金组合物包括40-10at.%的Co和60-90at.%的Pd。
11.一种溅射靶,包括权利要求1-10中任一项的合金组合物。
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CN112301255B (zh) * | 2020-10-27 | 2021-07-30 | 上海交通大学 | 一种模具用高导热高强Co-Fe-Ni合金及其增材制造方法 |
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-
2004
- 2004-10-12 US US10/961,215 patent/US20060078457A1/en not_active Abandoned
-
2005
- 2005-05-10 SG SG200502943A patent/SG121929A1/en unknown
- 2005-05-10 SG SG200604323A patent/SG123796A1/en unknown
- 2005-05-10 SG SG200604324A patent/SG123797A1/en unknown
- 2005-05-10 SG SG200703741-9A patent/SG132681A1/en unknown
- 2005-05-10 SG SG200604322A patent/SG123795A1/en unknown
- 2005-05-10 SG SG200703743-5A patent/SG132682A1/en unknown
- 2005-05-10 SG SG200604320A patent/SG123794A1/en unknown
- 2005-05-11 EP EP06015557A patent/EP1724366A3/en not_active Withdrawn
- 2005-05-11 EP EP06015558A patent/EP1724368A3/en not_active Withdrawn
- 2005-05-11 EP EP05252881A patent/EP1647605A3/en not_active Withdrawn
- 2005-05-11 EP EP06015555A patent/EP1724365A3/en not_active Withdrawn
- 2005-05-11 EP EP06015554A patent/EP1724367A3/en not_active Withdrawn
- 2005-05-11 EP EP06015556A patent/EP1728879A3/en not_active Withdrawn
- 2005-05-19 TW TW094116373A patent/TW200611983A/zh unknown
- 2005-05-27 CZ CZ20050342A patent/CZ2005342A3/cs unknown
- 2005-06-17 KR KR1020050052444A patent/KR20060046479A/ko active Search and Examination
- 2005-07-08 JP JP2005200691A patent/JP2006111963A/ja not_active Withdrawn
- 2005-07-08 CN CNA2008100031945A patent/CN101275189A/zh active Pending
- 2005-07-08 CN CN200510083509.8A patent/CN1760393A/zh active Pending
-
2006
- 2006-05-10 SG SG200604318A patent/SG123793A1/en unknown
-
2008
- 2008-03-03 KR KR1020080019558A patent/KR20080026580A/ko not_active Application Discontinuation
- 2008-03-03 KR KR1020080019559A patent/KR20080027473A/ko not_active Application Discontinuation
- 2008-03-03 KR KR1020080019556A patent/KR20080026578A/ko not_active Application Discontinuation
- 2008-03-03 KR KR1020080019557A patent/KR20080026579A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
KR20060046479A (ko) | 2006-05-17 |
EP1724367A3 (en) | 2010-02-17 |
SG121929A1 (en) | 2006-05-26 |
EP1728879A2 (en) | 2006-12-06 |
KR20080026579A (ko) | 2008-03-25 |
EP1724365A2 (en) | 2006-11-22 |
EP1724365A3 (en) | 2010-02-17 |
EP1728879A3 (en) | 2010-02-17 |
EP1724367A2 (en) | 2006-11-22 |
SG132682A1 (en) | 2007-06-28 |
JP2006111963A (ja) | 2006-04-27 |
SG123795A1 (en) | 2006-07-26 |
SG123793A1 (en) | 2006-07-26 |
TW200611983A (en) | 2006-04-16 |
SG123797A1 (en) | 2006-07-26 |
US20060078457A1 (en) | 2006-04-13 |
SG123794A1 (en) | 2006-07-26 |
CN1760393A (zh) | 2006-04-19 |
EP1724366A2 (en) | 2006-11-22 |
EP1724368A2 (en) | 2006-11-22 |
EP1724368A3 (en) | 2010-02-17 |
EP1647605A2 (en) | 2006-04-19 |
KR20080027473A (ko) | 2008-03-27 |
CZ2005342A3 (cs) | 2006-05-17 |
SG132681A1 (en) | 2007-06-28 |
SG123796A1 (en) | 2006-07-26 |
EP1647605A3 (en) | 2006-08-02 |
KR20080026580A (ko) | 2008-03-25 |
KR20080026578A (ko) | 2008-03-25 |
EP1724366A3 (en) | 2010-02-17 |
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