EP1438270A1 - Kostengünstige ferritmagnete mit verbesserten eigenschaften - Google Patents

Kostengünstige ferritmagnete mit verbesserten eigenschaften

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Publication number
EP1438270A1
EP1438270A1 EP02801367A EP02801367A EP1438270A1 EP 1438270 A1 EP1438270 A1 EP 1438270A1 EP 02801367 A EP02801367 A EP 02801367A EP 02801367 A EP02801367 A EP 02801367A EP 1438270 A1 EP1438270 A1 EP 1438270A1
Authority
EP
European Patent Office
Prior art keywords
equal
magnet
mixture
condition
typically
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02801367A
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English (en)
French (fr)
Inventor
Antoine Morel
Philippe Tenaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ugimag SA
Original Assignee
Ugimag SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ugimag SA filed Critical Ugimag SA
Publication of EP1438270A1 publication Critical patent/EP1438270A1/de
Withdrawn legal-status Critical Current

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    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
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    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
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Definitions

  • the invention relates to the field of magnets of the hexagonal ferrite type comprising the magnetoplumbite phase M.
  • Magnets of this type of formula are also known (M 1-x R x ) O • n [(Fe 12-y T y ) 2 O 3 ].
  • European application EP 0 964 411 A1 describes magnets in which: - M is an element chosen from Sr and / or Ba,
  • - R is an element belonging to rare earths
  • - T is an element chosen from Co, Mn, Ni and Zn, and with: - x ranging from 0.01 to 0.4,
  • European application EP 0 905 718 A1 describes magnets of this type of formula M ⁇ -X R X (Fe 12-y T y ) z O 1 in which:
  • - M is an element chosen from Sr, Ba, Ca and Pb, and essentially Sr
  • - R is an element belonging to rare earths or Bi, and essentially La
  • the manufacture of such magnets typically includes the following steps: a) forming a mixture of raw materials either by a wet process to form a dispersion, or by a dry process to form granules, b) calcining the mixture around 1250 ° C to form a clinker, or chamotte, comprising the magnetoplumbite phase sought, said mixture, either in the form of a dispersion or of granules, being introduced into a calcination oven, c) wet grinding of the clinker until an aqueous dispersion of particles with a particle size close to 1 ⁇ m, in the form of a paste of approximately 70% dry extract, d) the paste is concentrated and compressed under a orienting magnetic field of approximately 1 Tesla and under a pressure of 30 to 50 MPa of so as to obtain a green tablet, called "green compact" in English, anisotropic, and typically 87% dry extract, e) after drying and removal of the remaining water, sintering the tablet to green,
  • magnets of the ferrite type of the prior art typically magnets of the Sr ⁇ - x La x Fe 12 type .
  • y Co y O 1 are of two types:
  • the iron substitution element typically cobalt
  • the iron substitution element is an expensive product
  • Hk to take into account both the final magnetic properties and the square character of the magnetization and demagnetization curves.
  • the invention aims to obtain magnets with a global performance index GIP at least equal to 580, preferably at least equal to 585, or even at least equal to 590.
  • the ferrite magnet having the structure of the magnetoplumbite phase (hexaferrite of structure M) of formula M 1-X R X Fe 12 . y T y O 19 in which:
  • M designates at least one element chosen from the group consisting of: Sr, Ba, Ca and Pb,
  • - R denotes at least one element chosen by rare earths and Bi,
  • - T denotes at least one element chosen from Co, Mn, Ni, Zn, - 0.15 ⁇ x ⁇ 0.42
  • the research undertaken therefore aimed to greatly increase the square character hk, without further degrading the overall magnetic performance IP of the magnets, so as to obtain an overall performance index GIP at least equal to 580, and preferably at least equal to 585 , or even at least equal to 590.
  • the Applicant has first hypothesized that part of the Co element probably did not participate in the formation of the actual ferrite, and that this could lead to the transformation of initial Fe 3+ into Fe 2+ in ferrite.
  • the invention can allow, all other things being equal, both to reduce the content of element T of the ferrite magnet - element which is generally expensive, and to increase the overall performance of the ferrite magnet.
  • FIG. 3 is a graph showing the coefficients x on the abscissa and y on the ordinate (coefficients of the ferrite formula M 1-x R x Fe 12-y T y O 19 ) illustrating various fields of the invention, the main field being the lines:
  • Figures 4a and 4b are similar to Figure 3 and correspond to restricted areas:
  • FIG. 5a carries on the ordinate the remanent induction Br in mT.
  • HcJ coercive field
  • FIG. 6 illustrates an example of demagnetization curves for the tests Cl-1 in dotted lines and C3-1 in solid lines.
  • the coefficient ⁇ is taken at most equal to 0.90 so as to have simultaneously a significant reduction in the rate of the element T and an increase in the overall performance GIP, as observed in a surprising manner.
  • the applicant observed a lower limit for ⁇ 0.5 because of the degradation of the overall GIP performance.
  • the magnets of formula M 1-x R x Fe 12-y T y O 19 advantageously meet the following condition: 0.15 ⁇ x ⁇ 0.32.
  • Another more preferred subdomain corresponds to the following condition: 0.17 ⁇ x ⁇
  • ⁇ y / x ranges from 0.67 to 0.77 is particularly advantageous.
  • the most technically and economically interesting field is that defined by 0.17 ⁇ x ⁇ 0.22 and 0.67 ⁇ ⁇ 0.77.
  • the invention advantageously makes it possible to have ferrites with a low content of element T in which the coefficient y is at most equal to 0.16, or even at most equal to 0.15, while at the same time retaining a very high level of performance. overall.
  • ferrites according to the invention can be obtained under sintering conditions, in particular at a relatively low sintering temperature, and less than or equal to 1220 ° C and typically less than 1200 ° C, this which is economically advantageous.
  • the invention is not limited to this specific ferrite.
  • the atomic concentrations of the elements designated by T meet the condition [Co] / ([Co) + [Zn] + [Mn] + [Ni]> 30%, preferably> 50 % and even more preferably> 70%.
  • Another object of the invention is constituted by the use of a ferrite magnet according to the invention in an application requiring: - either a magnet having simultaneously a magnetic performance index IP greater than 590 mT and a high square character of the demagnetization curve, with typically a hjc ⁇ Hk / HcJ (%) ratio at least equal to 95%,
  • GIP general performance index
  • Another object of the invention consists of a method of manufacturing a magnet according to the invention in which: a) a mixture of precursors of the elements M, R, T and Fe is formed, corresponding to the stoichiometry of the formula M 1-x R x Fe 12-y T y O 19 with the conditions: 0.15 ⁇ x ⁇ 0.42 and 0.50 ⁇ - y / x ⁇ 0.90, b) the said mixture is calcined in temperature conditions and duration typically close to 1250 ° C.
  • a performance index IP Br + 0.5.
  • HcJ typically at least equal to 590 mT
  • Co 3 O 4 in the form of a powder of 0.96 m 2 / g of specific surface and an average diameter of the particles of 2.1 ⁇ m.
  • the powders were mixed in an aqueous mixer, the mixture was filtered, and then dried.
  • the powder obtained was put into the form of pellets with a density of 2.5 kg / dm 3 using water as a binder (moisture content of 14% by weight), the pellets being dried before calcination.
  • a clinker was obtained having the following properties:
  • the particles have an average diameter between 0.58 ⁇ m and 0.62 ⁇ m, and a BET specific surface area between 10.3 and 11.2 m 2 / g, so as to be able to make the measurements comparable of final properties of the magnets obtained.
  • the particles after grinding were subjected to a magnetic orienting field typically of IT and sintered at temperatures of: 1180 ° C, 1205 ° C, 1220 ° C or 1240 ° C. Results obtained as a function of the sintering temperature T ° C with a holding time of 25 min:

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  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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EP02801367A 2001-10-19 2002-10-14 Kostengünstige ferritmagnete mit verbesserten eigenschaften Withdrawn EP1438270A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0113542A FR2831317B1 (fr) 2001-10-19 2001-10-19 Aimants de type ferrite economiques et a proprietes ameliorees
FR0113542 2001-10-19
PCT/FR2002/003516 WO2003033432A1 (fr) 2001-10-19 2002-10-14 Aimants de type ferrite economiques et a proprietes ameliorees

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EP (1) EP1438270A1 (de)
JP (1) JP2005505944A (de)
KR (1) KR100845201B1 (de)
CN (1) CN100386288C (de)
BR (1) BR0213387A (de)
FR (1) FR2831317B1 (de)
MX (1) MXPA04003449A (de)
WO (1) WO2003033432A1 (de)

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US7758767B2 (en) 2004-09-10 2010-07-20 Neomax Co., Ltd. Oxide magnetic material and sintered magnet
WO2007060757A1 (ja) * 2005-11-25 2007-05-31 Hitachi Metals, Ltd. 酸化物磁性材料及びその製造方法、並びにフェライト焼結磁石及びその製造方法
US7919007B2 (en) * 2005-12-19 2011-04-05 Tdk Corporation Ferrite magnetic material
JP5316737B2 (ja) * 2006-01-11 2013-10-16 Ｔｄｋ株式会社 フェライト磁性材料
HUE029918T2 (en) * 2008-12-18 2017-04-28 Tridelta Hartferrite Gmbh Magnetically hard material
KR101082389B1 (ko) 2011-05-31 2011-11-11 쌍용머티리얼 주식회사 마그네토플럼바이트형 페라이트 자성재료 및 이로부터 유도된 세그멘트형 영구자석
CN103058641B (zh) * 2011-12-14 2014-04-23 南京梅山冶金发展有限公司 一种制备非稀土高磁性永磁铁氧体材料的方法
JP5650270B2 (ja) 2013-03-29 2015-01-07 株式会社リケン マグネトプランバイト型六方晶フェライト及びノイズ抑制シート
CN104003704B (zh) * 2014-02-27 2015-08-19 横店集团东磁股份有限公司 一种无镧钴永磁铁氧体的制备方法
CN104072124A (zh) * 2014-06-30 2014-10-01 中钢天源(马鞍山)通力磁材有限公司 一种直流变频电机用永磁铁氧体磁体的制备方法
CN107324406B (zh) * 2017-07-31 2019-09-24 电子科技大学 一种复合改性的锶铁氧体粉体的制备方法
JP7323221B2 (ja) * 2019-07-15 2023-08-08 漢陽大学校エリカ産学協力団 六角板状のフェライト構造体及びその製造方法
JP2021155317A (ja) * 2020-03-30 2021-10-07 Tdk株式会社 フェライト焼結磁石および回転電気機械
KR20220026316A (ko) * 2020-08-25 2022-03-04 현대자동차주식회사 GHz 대역의 전자파 흡수입자 및 이를 포함하는 전자파 흡수재
KR20220026315A (ko) * 2020-08-25 2022-03-04 현대자동차주식회사 GHz 대역의 전자파 흡수입자 및 이를 포함하는 전자파 흡수재
CN112299836A (zh) * 2020-11-25 2021-02-02 南通冠优达磁业有限公司 一种高频低损耗软磁铁氧体材料及制备方法
CN115849894B (zh) * 2022-11-07 2023-11-10 安徽龙磁科技股份有限公司 一种高磁特性永磁铁氧体材料及其制备方法

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JP2005505944A (ja) 2005-02-24
US20040251997A1 (en) 2004-12-16
BR0213387A (pt) 2004-12-21
KR100845201B1 (ko) 2008-07-10
FR2831317A1 (fr) 2003-04-25
WO2003033432A1 (fr) 2003-04-24
CN100386288C (zh) 2008-05-07
FR2831317B1 (fr) 2004-10-15
KR20050036879A (ko) 2005-04-20
MXPA04003449A (es) 2004-07-08
CN1571761A (zh) 2005-01-26

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