JPWO2011004791A1 - フェライト磁性材料 - Google Patents
フェライト磁性材料 Download PDFInfo
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- JPWO2011004791A1 JPWO2011004791A1 JP2011521908A JP2011521908A JPWO2011004791A1 JP WO2011004791 A1 JPWO2011004791 A1 JP WO2011004791A1 JP 2011521908 A JP2011521908 A JP 2011521908A JP 2011521908 A JP2011521908 A JP 2011521908A JP WO2011004791 A1 JPWO2011004791 A1 JP WO2011004791A1
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Abstract
Description
Ca1−w−x−yRwSrxBayFezMmO19 (1)
(式(1)中、Rは希土類元素(Yを含む)及びBiからなる群より選ばれる少なくとも1種の元素であってLaを少なくとも含み、Mは、Co、Mn、Mg、Ni、Cu及びZnからなる群より選ばれる少なくとも1種の元素であってCoを少なくとも含む。)
式(1)中、w、x、y、z及びmは、下記式(2)、(3)、(4)、(5)、(6)、(7)及び(8)を満たし、
0.25<w<0.65 (2)
0.01<x<0.45 (3)
0.0002<y<0.011 (4)
y<x (5)
8<z<11 (6)
1.0<w/m<2.5 (7)
0.017<m/z<0.065 (8)
副成分として少なくともSi成分を含み、このSi成分の総量が、主組成に対して0.1〜3質量%であり、且つ、Ca、R、Sr、Ba、Fe、M及びSiが、モル比で下記式(9)を満たす、ことを特徴とする。
1.5≦[(Ca+R+Sr+Ba)−(Fe+M)/12]/Si≦3.5 (9)
図1は、好適な実施形態のフェライト永久磁石を示す斜視図である。図1に示すフェライト永久磁石1(以下、単に「磁石1」と称する。)は、端面が円弧状となるように湾曲した形状を有しており、一般にアークセグメント形状、C形形状、瓦型形状、弓形形状等と呼ばれる形状を有している。この磁石1は、フェライト磁性材料の焼結体から構成された、フェライト焼結磁石である。
0.25<w<0.65 (2)
0.01<x<0.45 (3)
0.0002<y<0.011 (4)
y<x (5)
8<z<11 (6)
1.0<w/m<2.5 (7)
0.017<m/z<0.065 (8)
1.5≦[(Ca+R+Sr+Ba)−(Fe+M)/12]/Si≦3.5 (9)
1.5≦[(Ca+R+Sr+Ba)−(Fe+M)/12]/Si≦3.5 (9)
次に、上述したようなフェライト永久磁石の製造方法の好適な実施形態について説明する。以下の実施形態では、フェライト磁性材料からなるフェライト焼結磁石の製造方法の一例を示す。本実施形態では、フェライト焼結磁石は、配合工程、仮焼工程、粉砕工程、成形工程及び焼成工程を経て製造することができる。各工程については以下に説明する。
配合工程では、フェライト磁性材料の原料を配合して、原料組成物を得る。まず、フェライト磁性材料の原料としては、これを構成する元素のうちの1種又は2種以上を含む化合物(原料化合物)が挙げられる。原料化合物は、例えば粉末状のものが好適である。原料化合物としては、各元素の酸化物、又は焼成により酸化物となる化合物(炭酸塩、水酸化物、硝酸塩等)が挙げられる。例えばSrCO3、La(OH)3、Fe2O3、BaCO3、CaCO3及びCo3O4等が例示できる。原料化合物の粉末の平均粒径は、例えば、均質な配合を可能とする観点から、0.1〜2.0μm程度とすることが好ましい。
仮焼工程では、配合工程で得られた原料粉末を仮焼する。仮焼は、例えば、空気中等の酸化性雰囲気中で行うことが好ましい。仮焼の温度は、1100〜1400℃の温度範囲とすることが好ましく、1100〜1300℃がより好ましく、1100〜1250℃がさらに好ましい。仮焼の時間は、1秒間〜10時間とすることができ、1秒間〜3時間であると好ましい。仮焼により得られる仮焼体は、上述したような主相(M相)を70%以上含む。主相の一次粒子径は、好ましくは10μm以下であり、より好ましくは2μm以下である。
粉砕工程では、仮焼工程により顆粒状や塊状とされた仮焼体を粉砕し、再び粉末状にする。これにより、後述する成形工程での成形が容易となる。この粉砕工程では、上述したような配合工程で配合しなかった原料を添加してもよい(原料の後添加)。粉砕工程は、例えば、仮焼体を粗い粉末となるように粉砕(粗粉砕)した後、これを更に微細に粉砕する(微粉砕)、2段階の工程で行ってもよい。
成形工程では、粉砕工程後に得られた粉砕材(好ましくは微粉砕材)を、磁場中で成形して、成形体を得る。成形は、乾式成形及び湿式成形のいずれの方法でも行うことができる。磁気的配向度を高くする観点からは、湿式成形で行うことが好ましい。
焼成工程では、成形工程で得られた成形体を焼成して焼結体とする。これにより、上述したような、フェライト磁性材料の焼結体からなる磁石1が得られる。アークセグメント形状の磁石を製造する場合、焼成では、所定の中心角を有するように成形された成形体が収縮し、この際、一定の縮率比が生じる。これにより、得られる焼結体は、成形体よりも更に小さな中心角を有するものとなる。円弧が深い焼結体を得るためには、焼成時の縮率比は、1.0〜2.5であると好ましく、1.5〜2.5であるとより好ましい。
まず、フェライト磁性材料の主組成の原料として、酸化鉄(Fe2O3)、炭酸カルシウム(CaCO3)、炭酸ストロンチウム(SrCO3)、酸化コバルト(Co3O4)、炭酸バリウム(BaCO3)及び水酸化ランタン(La(OH)3)を準備し、これらの原料を、焼成後の主組成が以下の組成式となるように秤量した。また、Si成分として酸化ケイ素(SiO2)を、主組成に対して0.69質量%となるように準備した。
主組成の組成式:Ca1−w−x−yLawSrxBayFezComO19
実験例1で得られた各フェライト焼結磁石の円柱の上下面を加工した後、最大印加磁場755kA/m(12kOe)のB−Hトレーサを用い、これらのBr(mT)及びHcJ(kA/m)を求めるとともに、Brの90%になるときの外部磁界強度(Hk)を測定し、これに基づいてHk/HcJ(%)を求めた。
実験例2では、表2に示すように主組成の原子比率がそれぞれ異なるフェライト磁性材料が得られるように、複数の組み合わせの原料を準備したこと以外は、実施例1と同様にしてフェライト焼結磁石の製造を行った。この実験例2は、特にLa(w=0.1801〜0.6621)の原子比率を大きく変化させ、これに伴ってLa/Co(w/m=0.72〜2.65)が変化するようにして、サンプル2−1〜2−9の各種フェライト焼結磁石を製造したものである。
実験例3では、表3に示すように主組成の原子比率がそれぞれ異なるフェライト磁性材料が得られるように、複数の組み合わせの原料を準備したこと以外は、実施例1と同様にしてフェライト焼結磁石の製造を行った。この実験例3は、特にFe(z=7.80〜12.10)の原子比率を大きく変化させて、サンプル3−1〜3−10の各種フェライト焼結磁石を製造したものである。
実験例4では、表4に示すように主組成の原子比率がそれぞれ異なるフェライト磁性材料が得られるように、複数の組み合わせの原料を準備したこと以外は、実施例1と同様にしてフェライト焼結磁石の製造を行った。この実験例4は、特にCo(m=0.00〜0.70)の原子比率を大きく変化させ、これに伴ってCo/Fe(m/z=0.000〜0.076)及びLa/Co(w/m=0.564〜3.589)が変化するようにして、サンプル4−1〜4−7の各種フェライト焼結磁石を製造したものである。
実験例5では、表5に示すように主組成の原子比率がそれぞれ異なるフェライト磁性材料が得られるように、複数の組み合わせの原料を準備したこと以外は、実施例1と同様にしてフェライト焼結磁石の製造を行った。この実験例5は、特にBa(y=0.0002〜0.0150)の原子比率を大きく変化させて、サンプル5−1〜5−11の各種フェライト焼結磁石を製造したものである。
実験例5で得られた各フェライト焼結磁石を用い、実験例1と同様にしてこれらのBr(mT)、HcJ(kA/m)及びHk/HcJ(%)を求めた。
実験例6では、表6に示す通り、フェライト焼結磁石を構成するフェライト磁性材料の構成元素の割合(モル%)がそれぞれ異なるように、複数の組み合わせの原料を準備したこと以外は、実施例1と同様にしてフェライト焼結磁石の製造を行った。各構成元素の割合(モル%)は、各元素のそれぞれ表6に示す酸化物に換算したときの含有量を、全体を100%として規格化した値である。この実験例6は、特にSi成分(SiO2)の含有量を大きく変化させ、これに伴って「[(Ca+R+Sr+Ba)−(Fe+M)/12]/Si」の値が変化するようにして、サンプル6−1〜6−5の各種フェライト焼結磁石を製造したものである。
まず、主組成におけるBaの原子比率(y)が、0.0002及び0.0045となるようにしたこと以外は、実施例1と同様にして円柱状のフェライト焼結磁石を作製した。これらについて、焼成時における成形体の収縮の割合を、厚み(shh(%)=100−(焼結体の厚み/成形体の厚み)×100)、及び直径(shΦ(%)=100−(焼結体の直径/成形体の直径)×100)をそれぞれ求め、これに基づいて焼結前後の縮率比(shh/shΦ:c軸方向/a軸方向)を算出した。
これとともに、これらと同様のフェライト磁性材料からなる、図1に示すアークセグメント型のフェライト焼結磁石をそれぞれ作製した。具体的には、各湿式成形用スラリーを得た後、アークセグメント形状が得られるように成形工程を行ったこと以外は、実験例1と同様にして、フェライト焼結磁石を得た。
目的とする焼結体の寸法を表8に示すように変えたこと以外は、実験例7と同様に2種類のフェライト磁性材料からなるフェライト焼結磁石の製造を行い、この際、同じ焼結体寸法を得るために必要となったそれぞれの成形体寸法を求めた。得られた結果を表8に示す。
目的とする焼結体の寸法を表9に示すように変えたこと以外は、実験例7と同様に2種類のフェライト磁性材料からなるフェライト焼結磁石の製造を行い、この際、同じ焼結体寸法を得るために必要となったそれぞれの成形体寸法を求めた。また、各フェライト磁性材料を用いた焼結体の製造をそれぞれ10000回行い、そのうち焼結体にクラックが生じた回数を数えるとともに、成形工程において、湿式成形用スラリーを金型に充填するのに要した平均時間を求めた。得られた結果を表9に示す。
Claims (3)
- 六方晶構造を有するフェライト相からなる主相を有するフェライト磁性材料であって、
下記式(1)で表される主組成を有し、
Ca1−w−x−yRwSrxBayFezMmO19 (1)
(式(1)中、Rは希土類元素(Yを含む)及びBiからなる群より選ばれる少なくとも1種の元素であってLaを少なくとも含み、Mは、Co、Mn、Mg、Ni、Cu及びZnからなる群より選ばれる少なくとも1種の元素であってCoを少なくとも含む。)
前記式(1)中、w、x、y、z及びmは、下記式(2)、(3)、(4)、(5)、(6)、(7)及び(8)を満たし、
0.25<w<0.65 (2)
0.01<x<0.45 (3)
0.0002<y<0.011 (4)
y<x (5)
8<z<11 (6)
1.0<w/m<2.5 (7)
0.017<m/z<0.065 (8)
副成分として少なくともSi成分を含み、該Si成分の総量が、前記主組成に対して0.1〜3質量%であり、且つ、
Ca、R、Sr、Ba、Fe、M及びSiのモル比が、下記式(9)を満たす、1.5≦[(Ca+R+Sr+Ba)−(Fe+M)/12]/Si≦3.5 (9)
ことを特徴とするフェライト磁性材料。 - 請求項1記載のフェライト磁性材料からなり、アークセグメント形状を有し、且つ当該形状の中心角が30°以上である、ことを特徴とする磁石。
- 前記中心角が60°以上である、ことを特徴とする請求項2記載の磁石。
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US11118140B2 (en) | 2014-08-29 | 2021-09-14 | Ecolab Usa Inc. | Solid rinse aid composition comprising polyacrylic acid |
US11624043B2 (en) | 2014-08-29 | 2023-04-11 | Ecolab Usa Inc. | Solid rinse aid composition comprising polyacrylic acid |
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JP5626211B2 (ja) | 2014-11-19 |
KR20140114057A (ko) | 2014-09-25 |
EP2452928B1 (en) | 2016-09-07 |
EP2452928A1 (en) | 2012-05-16 |
US9272955B2 (en) | 2016-03-01 |
CN102471162B (zh) | 2016-05-04 |
EP2452928A4 (en) | 2013-01-30 |
KR20120041744A (ko) | 2012-05-02 |
EP3150567A1 (en) | 2017-04-05 |
US20120161910A1 (en) | 2012-06-28 |
WO2011004791A1 (ja) | 2011-01-13 |
CN102471162A (zh) | 2012-05-23 |
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