CN102548903B - ε-型氧化铁的矫顽力提高方法和ε-型氧化铁 - Google Patents
ε-型氧化铁的矫顽力提高方法和ε-型氧化铁 Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 21
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 85
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 238000006467 substitution reaction Methods 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 50
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 description 26
- 238000006073 displacement reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000003991 Rietveld refinement Methods 0.000 description 2
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical group [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003147 molecular marker Substances 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
本发明提供一种ε-型氧化铁颗粒的矫顽力提高方法和ε-型氧化铁。提供用其它元素置换该ε-型氧化铁的Fe位且该ε-型氧化铁中的D位的Fe未被其它元素置换的ε-型氧化铁的矫顽力提高方法和该ε-型氧化铁。
Description
技术领域
本发明涉及作为磁性材料的ε-型氧化铁的矫顽力提高方法和ε-型氧化铁。
背景技术
在磁性材料的领域中,伴随着例如对于磁记录的高密度化的要求,不断地进行着具有更高矫顽力的物质的探求。在这种情况下,从具有高矫顽力的物质的观点出发,提出了含有贵金属尤其是铂族元素作为主要构成要素的铁铂系磁性材料等。
然而,像该铁铂系磁性材料等那样含有大量铂族作为主要构成要素的材料在成本方面不利。而且,当需要大量使用以该铂族元素为主要构成要素的材料的情况下,还存在可能引起供给不稳定的问题。
为了消除上述不利、可能,期望提供即使使用铂族元素也仅使用少量、但具有高磁特性的磁性材料。
基于以上需求,本发明人等想到了ε-型氧化铁(ε-Fe2O3)这种磁性材料。本发明人等证实了虽然该ε-型氧化铁是氧化铁这种极端廉价的材料,但可以得到具有高达20kOe的矫顽力的磁性材料,这类罕见的磁特性在非专利文献1~3中被公开,在专利文献1~3中公开了通过将该ε-型氧化铁中的Fe置换为其它元素,从而可以进行磁特性的调整。
现有技术文献
专利文献
专利文献1:日本特开2007-269548号公报
专利文献2:日本特开2007-281410号公报
专利文献3:日本特开2008-060293号公报
非专利文献
非专利文献1:Jian Jin,Shinichi Ohkoshi and KazuhitoHashimoto ADVANCED MATERIALS Vol.16 No.1(2004)pp.48~51
非专利文献2:Jian Jin,Kazuhito Hashimoto and ShinichiOhkoshi JOURNAL OF MATERIALS CHIMISTRY 15(2005)pp.1067~1071
非专利文献3:Shunsuke Sakurai,Jian Jin,KazuhitoHashimoto and Shinichi Ohkoshi JOURNAL OF THE PHYSICALSOCIETY OF JAPAN Vol.74,No.7(2005)pp.1946~1949
发明内容
发明要解决的问题
如发明人等在专利文献1等中公开的那样,通常可以按照将ε-型氧化铁的Fe的一部分用镓、铟、铝等元素置换而减少该ε-型氧化铁的矫顽力的形式进行磁特性的控制。即,具有最高矫顽力的ε-型氧化铁系的磁性材料是Fe未被其它种类的元素置换的纯粹的ε-型氧化铁。
在此,认为如果可以向增大该ε-型氧化铁的矫顽力值的控制范围的方向扩展,就能够扩大该ε-型氧化铁的适用范围。事实上,对于电波吸收材料的电波吸收性能,确认到在构成该电波吸收材料的磁性材料的矫顽力值不同时,该电波吸收材料的电波吸收带域发生变化,但已知以往通过进行置换而矫顽力变小。即,从可以更容易地调整电波吸收带域这种观点出发,认为提供用于提高该ε-型氧化铁的矫顽力值的方法从工业方面看是有用的。然而,并没有找出提高该ε-型氧化铁颗粒的矫顽力的方法。
本发明是在上述情况下完成的,要解决的技术课题在于提供ε-型氧化铁颗粒的矫顽力提高方法和ε-型氧化铁。
用于解决问题的方案
本发明人等经过深入研究,结果想到了下述的方案从而解决了上述课题。
即,用于解决上述课题的第1方案为一种ε-型氧化铁的矫顽力提高方法,
其为提高ε-型氧化铁的矫顽力的方法,其中,将该ε-型氧化铁的Fe位用其它元素置换且该ε-型氧化铁中的D位的Fe未被该其它元素置换。
第2方案为第1方案所述的ε-型氧化铁的矫顽力提高方法,其中,该ε-型氧化铁中的A位的Fe也未被该其它元素置换。
第3方案为第1方案或第2方案所述的ε-型氧化铁的矫顽力提高方法,其中,所述其它元素为铂族元素。
第4方案为第1方案~第3方案中任一项所述的ε-型氧化铁的矫顽力提高方法,其中,所述其它元素为铑。
第5方案为一种ε-型氧化铁,其为ε-型氧化铁,其中,该ε-型氧化铁的Fe位被其它元素置换,且该ε-型氧化铁中的D位的Fe未被该其它元素置换。
第6方案为第5方案所述的ε-型氧化铁,其中,该ε-型氧化铁中的A位的Fe也未被该其它元素置换。
第7方案为第5方案或第6方案所述的ε-型氧化铁,其中,所述其它元素为铂族元素。
第8方案为第5方案~第7方案中任一项所述的ε-型氧化铁,其中,所述其它元素为铑。
发明的效果
根据本发明的ε-型氧化铁的矫顽力提高方法,可以将ε-型氧化铁的矫顽力提高至Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的矫顽力以上。
附图说明
图1是表示本发明的ε-型氧化铁的晶体结构的示意图。
图2是表示本发明的ε-型氧化铁的a轴的晶格长度与矫顽力的关系的图。(其中,将实施例1~3中的试样粉末标记为●、对照例1中的纯粹的ε-型氧化铁试样粉末标记为◇、比较例1~3中的镓置换试样粉末标记为□、比较例4~6中的铝置换试样粉末标记为△。)
图3是表示本发明中的ε-型氧化铁的b轴的晶格长度与矫顽力的关系的图(符号与图2中记载的内容相同。)。
图4是表示本发明中的ε-型氧化铁的c轴的晶格长度与矫顽力的关系的图(符号与图2中记载的内容相同。)。
图5是表示本发明中的ε-型氧化铁的晶格体积与矫顽力的关系的图(符号与图2中记载的内容相同。)。
具体实施方式
如上所述,将具有(ε-Fe2O3/Pna21)的晶体结构的ε-型氧化铁粉末的Fe位用其它元素置换时,该粉末所具有的矫顽力降低。在该情况下,本发明人等为了提高ε-型氧化铁磁性粉末的矫顽力进行了各种研究。
其结果,发现了将具有(ε-Fe2O3/Pna21)的晶体结构的ε-型氧化铁的Fe位用其它元素置换且该ε-型氧化铁中的D位的Fe未被其它元素置换这一突破性的方案。进一步发现,如果加上该ε-型氧化铁中的A位的Fe也未被其它元素置换的方案,则可以进一步提高矫顽力。而且,作为实现该方案的手段,发现了使用铂族元素作为该其它元素的方案。
(颗粒的构成)
图1是本发明的(ε-Fe2O3/Pna21)ε-型氧化铁的晶体结构的示意图。图1中,大黑球表示Fe位,小白球表示O位。而且在该晶体结构的示意图中,A~D位上的Fe位分别使用A~D的符号表示。
这里,通过利用Rietveld method的解析来测定A~D位上的Fe位是存在Fe原子、还是置换为其它元素。
本发明的ε-型氧化铁的特征在于,Fe位的一部分被其它元素置换,而该置换部位为B位和C位。即,在该ε-型氧化铁中,D位的Fe未被其它元素置换。进一步优选该ε-型氧化铁的A位的Fe也未被其它元素置换。
与此相对,根据现有的技术也已知,将Fe位的一部分置换为其它元素(3价的金属元素)时,主要是D位的Fe被置换。即,可以认为使ε-型氧化铁矫顽力降低的利用三价的元素的置换主要是由于D位的Fe被其它元素置换而产生的。
这里,本发明人等想到了,作为置换ε-型氧化铁的Fe位且不置换该ε-型氧化铁中的D位的Fe的元素,铂族元素是合适的。进而想到在该铂族元素中进一步优选为铑。
为了实现该方案,向ε-型氧化铁中添加的铂族元素相对于该ε-型氧化铁为2mol%以下的微量即可,因此从原料成本的观点出发也是优选的方案。
实施例
以下边参照实施例边具体说明本发明。但是本发明不限定于该实施例的范围。
(实施例1)
向Teflon(注册商标)制的烧瓶中装入25.5g三甲基溴化铵、715mL纯水、105mL乙醇、41mL 2,2’,2”-三乙醇胺,在60℃下搅拌使其溶解。其溶解后,进一步添加71mL四乙氧基硅烷,在大气中同样地在60℃下搅拌2小时。其搅拌后,分离并采集生成的沉淀。用乙醇洗涤该采集的沉淀,进而在大气中在600℃下焙烧1小时从而得到介孔二氧化硅。
准备溶解有1.25mmol硝酸铁(III)和0.02mmol硝酸铑的、甲醇占80质量%而其余部分为水的混合溶液(2.41mL)。将该混合溶液浸渍于0.70g所得到的介孔二氧化硅中从而得到含浸物。使所得到的含浸物干燥制成干燥物后,将该干燥物在1200℃下焙烧4小时,从而得到铑置换的ε-型氧化铁的介孔二氧化硅包覆物。
将所得到的铑置换的ε-型氧化铁的介孔二氧化硅包覆物加入浓度2mol/L的NaOH水溶液中,在70℃下搅拌24小时以进行二氧化硅的除去处理。在该二氧化硅的除去处理之后,进一步进行过滤、水洗、干燥,从而得到实施例1的试样粉末。
将得到的实施例1的试样粉末供于粉末X射线衍射(XRD:Rigaku制RINT2000、线源CuKα线、电压40kV、电流30mA)。于是,根据晶格的精密解析,衍射图案具有与ε-型氧化铁的晶体结构(斜方晶、空间群Pna21)对应的峰。从以上情况判明,实施例1的试样粉末以ε-型氧化铁的晶体结构为主相。该晶体的 晶格体积为
进而,在该实施例1的试样粉末中,与作为杂质晶体的α-Fe2O3的晶体结构(六方晶、空间群R-3c)对应的弱峰也被观察到,但没有确认到除这些以外的磁性晶体的峰。
利用Rietveld法对该实施例1的试样粉末测定了ε-型氧化铁的A~D位中的Fe的置换状态。结果A位和D位中没有确认到作为置换元素的铑。与此相对,确认到B位上1%、C位上6%的铑。
利用Quantum Design Japan,Inc.制的PPMS(物理特性测定系统)在施加磁场90kOe的条件下对该实施例1的试样粉末进行磁滞回线的测定。其结果,矫顽力Hc为23.0kOe(1830.3kA/m)、σs为17.9Am2/kg。该值超过了对照例的Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的矫顽力(Hc)21.8kOe(1734.8kA/m)。
上述解析结果和磁特性测定结果示于表1。
(实施例2、3)
硝酸铑的添加量在实施例2中为0.05mmol,实施例3中为0.08mmol,除此以外进行与实施例1相同的操作,得到实施例2、3的试样粉末。
对于所得到的实施例2、3的试样粉末也进行与实施例1相同的解析和磁特性测定。该解析结果和磁特性测定结果示于表1。
由表1可知,将ε-型氧化铁的Fe用铑置换的情况下,A位和D位的Fe未被置换,而B位和C位的Fe被置换。
若观察磁特性,则实施例2、3的试样粉末均超过对照例的Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的矫顽力(Hc)。
(对照例1)
不添加硝酸铑,除此以外进行与实施例1相同的操作,得到Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的对照例1的试样粉末。
对于得到的对照例1的试样粉末,也进行与实施例1相同的解析和磁特性测定。该解析结果和磁特性测定结果示于表1。
(比较例1~3)
简单说明比较例1~3中的镓置换的ε-型氧化铁的制造方法。(制造方法的详情参照日本特开2007-269548号公报)
首先,向纯水、正辛烷、1-丁醇的混合液中添加硝酸铁(III)9水合物、硝酸镓(III)n水合物、硝酸钡,并搅拌溶解。进而,作为表面活性剂添加十六烷基三甲基溴化铵,搅拌使其溶解而得到胶束溶液I。
接着,向25%氨水与纯水的混合液中加入正辛烷、1-丁醇并充分搅拌。向该混合溶液中加入作为表面活性剂的十六烷基三甲基溴化铵并使其溶解,从而得到胶束溶液II。
然后,向胶束I溶液中滴加并混合胶束溶液II,然后加入四乙氧基硅烷,继续搅拌,进行离心分离处理从而回收沉淀物。
使用氯仿与甲醇的混合溶液洗涤回收的沉淀物,进行干燥后,在大气气氛下进行1000℃4小时的热处理制备热处理粉末。
将该热处理粉末在NaOH水溶液中搅拌,进行二氧化硅的除去处理,然后过滤、水洗、干燥,从而得到比较例1~3的镓置换的ε-型氧化铁试样粉末。
此时,以达到表1所示的比的方式添加硝酸镓(III)n水合物。
对于得到的比较例1~3的试样粉末也进行与实施例1相同的解析和磁特性测定。该解析结果和磁特性测定结果示于表1。
由表1可知,将ε-型氧化铁的Fe用镓置换的情况下,A位和B位的Fe未被置换,而C位和D位的Fe被置换。
若观察磁特性,则比较例1~3的试样粉末均低于对照例的Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的矫顽力(Hc)。
(比较例4~6)
简单说明比较例4~6的铝置换的ε-型氧化铁的制造方法。(制造方法的详情参照日本特开2008-060293号公报)
首先,向纯水、正辛烷、1-丁醇的混合液中添加硝酸铁(III)9水合物、硝酸铝(III)9水合物,搅拌并使其溶解。进一步添加作为表面活性剂的十六烷基三甲基溴化铵,搅拌并使其溶解从而得到胶束溶液I。
接着,向25%氨水与纯水的混合液中加入正辛烷、1-丁醇并充分搅拌。向该混合溶液中加入作为表面活性剂的十六烷基三甲基溴化铵并使其溶解,从而得到胶束溶液II。
然后,向胶束I溶液中滴加并混合胶束溶液II,然后加入四乙氧基硅烷,继续搅拌,进行离心分离处理从而回收沉淀物。
使用氯仿与甲醇的混合溶液洗涤回收的沉淀物,进行干燥,然后在大气气氛下进行1150℃4小时的热处理制备热处理粉末。
将该热处理粉末在NaOH水溶液中搅拌,进行二氧化硅的除去处理后,进行过滤、水洗、干燥,从而得到比较例4~6的铝置换的ε-型氧化铁试样粉末。
此时,硝酸铝(III)9水合物的添加量分别以达到表1所示比的方式进行添加。
对于得到的比较例4~6的试样粉末也进行与实施例1相同的解析和磁特性测定。该解析结果和磁特性测定结果示于表1。
由表1可知,将ε-型氧化铁的Fe用铝置换的情况下,A~D位的Fe被置换。
若观察磁特性,则比较例4~6的试样粉末均低于对照例的Fe未被其它种类的元素置换的纯粹的ε-型氧化铁的矫顽力(Hc)。
[表1]
需要说明的是,表1中的“各位的置换比例”栏中的负的值实质上是0。
将ε-型氧化铁的Fe位用镓、铝这样的元素置换时,a轴~c轴的晶格直径存在变短的倾向、且晶格体积收缩,可见到以往的置换的颗粒中,伴随着元素的置换量的增加、矫顽力降低。
另一方面,本发明的试样中,将Fe位用铑置换的情况下,如图2~5中所示,可以看出b轴、c轴的晶格直径、晶体体积的收缩。然而,将Fe位用铑置换的情况下,判明不管该晶格的收缩发生与否、矫顽力都增加这种以往不曾具有的物理特性。
对于产生该现象的理由进行了深入研究,由表1可知,判明了对于实施例1~3的试样颗粒,被置换的Fe位偏向于B位和C位。确认了由于该偏向,实施例1~3的试样颗粒在D位和A位上没有发生置换。
认为由于这些特征,对于ε-型的氧化铁,通过用铑置换Fe位,可见到矫顽力的提高。
产业上的可利用性
本发明的磁性材料在高密度磁记录介质用途上是有用的。进而,认为本发明的磁性材料由于为氧化物因而具有作为材料的稳定性,并具有优异磁特性,因此可以用于电波吸收材料、纳米等级(nanoscale)/电子材料、永磁体材料、生物体分子标识剂、药剂载体等。
Claims (6)
1.一种ε-型氧化铁的矫顽力提高方法,其特征在于,
ε-型氧化铁的B位以及C位的Fe的一部分被铂族元素置换,且所述ε-型氧化铁中的D位的Fe未被所述铂族元素元素置换。
2.根据权利要求1所述的ε-型氧化铁的矫顽力提高方法,其特征在于,所述ε-型氧化铁中的A位的Fe也未被所述铂族元素置换。
3.根据权利要求1或2所述的ε-型氧化铁的矫顽力提高方法,其特征在于,所述铂族元素为铑。
4.一种ε-型氧化铁,其特征在于,ε-型氧化铁的B位以及C位的Fe的一部分被铂族元素,且所述ε-型氧化铁中的D位的Fe未被所述铂族元素置换。
5.根据权利要求4所述的ε-型氧化铁,其特征在于,所述ε-型氧化铁中的A位的Fe也未被所述铂族元素置换。
6.根据权利要求4或5所述的ε-型氧化铁,其特征在于,所述铂族元素为铑。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007281410A (ja) * | 2006-03-17 | 2007-10-25 | Univ Of Tokyo | 磁性材料並びにそれを用いたメモリーおよびセンサ |
JP2008100871A (ja) * | 2006-10-19 | 2008-05-01 | Univ Of Tokyo | ε酸化鉄の製法 |
CN101178965A (zh) * | 2006-08-31 | 2008-05-14 | 国立大学法人东京大学 | 磁性材料 |
CN101410331A (zh) * | 2006-03-31 | 2009-04-15 | 国立大学法人东京大学 | 磁性材料 |
CN101512686A (zh) * | 2006-09-01 | 2009-08-19 | 国立大学法人东京大学 | 电波吸收材料用磁性晶体和电波吸收体 |
JP2009206376A (ja) * | 2008-02-28 | 2009-09-10 | Univ Of Tokyo | 磁性材料並びにそれを用いた磁気メモリ、及び温度センサ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4979492B2 (ja) * | 2003-03-17 | 2012-07-18 | 国立大学法人大阪大学 | 貴金属・磁性金属酸化物複合微粒子およびその製造法 |
KR20050109586A (ko) * | 2003-03-17 | 2005-11-21 | 간사이 티.엘.오 가부시키가이샤 | 귀금속·자성 금속산화물 복합 미립자 및 그의 제조법 |
JP5124825B2 (ja) * | 2006-09-08 | 2013-01-23 | 国立大学法人 東京大学 | ε酸化鉄系の磁性材料 |
JP5130534B2 (ja) | 2006-09-08 | 2013-01-30 | 国立大学法人 東京大学 | 磁気特性を改善したε酸化鉄粉末 |
-
2010
- 2010-09-30 US US13/499,172 patent/US9458026B2/en active Active
- 2010-09-30 EP EP18197222.5A patent/EP3473599A1/en not_active Withdrawn
- 2010-09-30 JP JP2011534311A patent/JP5408593B2/ja not_active Expired - Fee Related
- 2010-09-30 CN CN201080043063.5A patent/CN102548903B/zh not_active Expired - Fee Related
- 2010-09-30 EP EP10820649.1A patent/EP2484638B1/en not_active Not-in-force
- 2010-09-30 WO PCT/JP2010/067094 patent/WO2011040534A1/ja active Application Filing
-
2016
- 2016-08-08 US US15/231,122 patent/US9633770B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007281410A (ja) * | 2006-03-17 | 2007-10-25 | Univ Of Tokyo | 磁性材料並びにそれを用いたメモリーおよびセンサ |
CN101410331A (zh) * | 2006-03-31 | 2009-04-15 | 国立大学法人东京大学 | 磁性材料 |
CN101178965A (zh) * | 2006-08-31 | 2008-05-14 | 国立大学法人东京大学 | 磁性材料 |
CN101512686A (zh) * | 2006-09-01 | 2009-08-19 | 国立大学法人东京大学 | 电波吸收材料用磁性晶体和电波吸收体 |
JP2008100871A (ja) * | 2006-10-19 | 2008-05-01 | Univ Of Tokyo | ε酸化鉄の製法 |
JP2009206376A (ja) * | 2008-02-28 | 2009-09-10 | Univ Of Tokyo | 磁性材料並びにそれを用いた磁気メモリ、及び温度センサ |
Non-Patent Citations (6)
Title |
---|
Formation of spherical and rod-shaped e-Fe2O3 nanocrystals with a large coercive field;Jian Jin et al.;《J. Mater. Chem.》;20050117;第15卷;1067-1071 * |
Giant Coercive Field of Nanometer-Sized Iron Oxide;Jian Jin et al.;《Advanced Materials》;20040105;第16卷(第1期);48-51 * |
Jian Jin et al..Formation of spherical and rod-shaped e-Fe2O3 nanocrystals with a large coercive field.《J. Mater. Chem.》.2005,第15卷1067-1071. |
Jian Jin et al..Giant Coercive Field of Nanometer-Sized Iron Oxide.《Advanced Materials》.2004,第16卷(第1期),48-51. |
Reorientation Phenomenon in a Magnetic Phase of ε-Fe2O3 Nanocrystal;Shunsuke SAKURAI et al.;《Journal of the Physical Society of Japan》;20050731;第74卷(第7期);1946-1949 * |
Shunsuke SAKURAI et al..Reorientation Phenomenon in a Magnetic Phase of ε-Fe2O3 Nanocrystal.《Journal of the Physical Society of Japan》.2005,第74卷(第7期),1946-1949. |
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US9633770B2 (en) | 2017-04-25 |
EP3473599A1 (en) | 2019-04-24 |
US20160343484A1 (en) | 2016-11-24 |
EP2484638A1 (en) | 2012-08-08 |
JPWO2011040534A1 (ja) | 2013-02-28 |
JP5408593B2 (ja) | 2014-02-05 |
EP2484638A4 (en) | 2015-09-02 |
US20120263642A1 (en) | 2012-10-18 |
WO2011040534A1 (ja) | 2011-04-07 |
CN102548903A (zh) | 2012-07-04 |
EP2484638B1 (en) | 2018-11-14 |
US9458026B2 (en) | 2016-10-04 |
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