JPS61238901A - Ferromagnetic powder - Google Patents
Ferromagnetic powderInfo
- Publication number
- JPS61238901A JPS61238901A JP60079752A JP7975285A JPS61238901A JP S61238901 A JPS61238901 A JP S61238901A JP 60079752 A JP60079752 A JP 60079752A JP 7975285 A JP7975285 A JP 7975285A JP S61238901 A JPS61238901 A JP S61238901A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- saturation magnetization
- iron oxide
- raw material
- weight
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 76
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 51
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 26
- 230000005415 magnetization Effects 0.000 abstract description 41
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000011358 absorbing material Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明法は、飽和磁化が高く耐候性に優れた強磁性粉末
に関し、電波吸収材や電磁遮蔽材などに利用できるもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The method of the present invention relates to a ferromagnetic powder with high saturation magnetization and excellent weather resistance, and can be used in radio wave absorbing materials, electromagnetic shielding materials, and the like.
近年、強磁性粉末の用途分野の拡大はめざましいものが
あり、飽和磁化が高く耐候性に優れ、電波吸収材や電磁
遮蔽材など用途に応じた粉末の開発が盛んに行なわれて
いる０例えば電波障害を防止するために建材等に強磁性
粉末を混入した電磁吸収材あるいは電磁遮蔽材が強磁性
であることを利用した用途である。In recent years, the field of application of ferromagnetic powder has been expanding at a remarkable pace, and powders with high saturation magnetization and excellent weather resistance are being actively developed for various uses, such as radio wave absorbers and electromagnetic shielding materials. This application takes advantage of the ferromagnetic nature of electromagnetic absorbing materials or electromagnetic shielding materials that are made by mixing ferromagnetic powder into building materials to prevent damage.
電波吸収材等に用いる強磁性粉末が備えるべき要件は、
コストが低いこと、飽和磁化が高いこと、耐候性が優れ
ていること、そして１粒度が細かいことである。より具
体的には、
飽和磁化σＳ≧８０ ｅ ｍ ｕ ／ ｇ平均粒度≦８
０用ｍ程度
が要求される。The requirements that ferromagnetic powder used for radio wave absorbing materials etc. should have are as follows:
It has low cost, high saturation magnetization, excellent weather resistance, and small grain size. More specifically, saturation magnetization σS≧80 e mu / g average particle size≦8
0 m is required.
鉄（Ｆｅ）とマグネタイト（Ｆｅ３０４）は最も卑近で
元来コストの低い磁性材料であるが、これを細かい粉末
とした場合には次のような問題がある。Iron (Fe) and magnetite (Fe304) are the most common and inherently low-cost magnetic materials, but when they are made into fine powders, the following problems arise.
鉄粉は飽和磁化σＳが高く（理論値２１０ｅｍｕ／ｇ）
、種々の公知の方法によって微粉とすることができるが
、単純な機械粉砕法によっては、鉄に展延性があるため
に粉砕しにくく、水やガスを噴射するアトマイズ法によ
っては、粗粒が多くなるために微粉の歩留りが悪くなる
など、結局コスト高となってしまう。また、通常の環境
においても極めて錆びやすく、耐候性上使用に耐えない
ことが多い。Iron powder has high saturation magnetization σS (theoretical value 210 emu/g)
can be made into fine powder by various known methods, but simple mechanical grinding is difficult to grind due to the malleability of iron, and atomization, which involves injecting water or gas, produces many coarse particles. As a result, the yield of fine powder decreases, resulting in higher costs. Furthermore, it is extremely susceptible to rust even in normal environments, and is often unable to withstand use due to its weather resistance.
一方、マグネタイト粉は飽和磁化σＳがやや低い（理論
値９２ ｅ ｍ ｕ ／ ｇ ）ものの耐候性は良く、
また鉄粉に比べて脆いため機械粉砕によって効率良く微
粉とすることができるし、「粉体及び粉末冶金Ｊ Ｖｏ
ｌ、 ２６ 、 Ｎｏ−７、ｐ 、 ２３５〜２４３に
示されたいわゆる湿式法によって微粉を得ることができ
る。しかし、マグネタイト粉の飽和磁化σＳは、Ｆｅ３
Ｏ４の飽和磁化σＳ理論値が比較的低いため、わずかの
不純物が混入したり、成分が化学量論的な値からずれた
りすると、要求値飼料磁化σＳ≧ａｏｅｍｕ／ｇを満た
すことがむずかしくなる。そこで、どうしても高純度の
マグネタイト粉を使わなければならないが、そのために
は上記湿式法に頼ることになり、その工程が複雑なため
にコスト高にならざると得なかった。On the other hand, although magnetite powder has a slightly lower saturation magnetization σS (theoretical value 92 e mu / g), it has good weather resistance.
In addition, since it is more brittle than iron powder, it can be efficiently turned into fine powder by mechanical pulverization.
A fine powder can be obtained by the so-called wet method shown in 1, 26, No-7, p. 235-243. However, the saturation magnetization σS of magnetite powder is Fe3
Since the theoretical saturation magnetization σS of O4 is relatively low, if a small amount of impurity is mixed in or the components deviate from the stoichiometric value, it will be difficult to satisfy the required feed magnetization σS≧aoemu/g. Therefore, it is necessary to use highly purified magnetite powder, but for this purpose, the wet method described above has to be relied upon, and the process is complicated, resulting in high costs.
本発明者らは、これらの問題点を解決するため研究を重
ねた結果、飽和磁化が高く、耐候性が優れ、低コストで
製造することのできる強磁性粉末を開発した。As a result of repeated research to solve these problems, the present inventors have developed a ferromagnetic powder that has high saturation magnetization, excellent weather resistance, and can be manufactured at low cost.
本発明はこのような強磁性粉末を提供することを目的と
するものである。The object of the present invention is to provide such a ferromagnetic powder.
本発明の着服点は、
ｌ）酸化鉄であれば微粉化が容易であり、２）酸化鉄の
一部を金属鉄（Ｍ、Ｆｅ）で置きかえれば飽和磁化σＳ
が向上する、
３）その置きかえが一定範囲内であれば、耐候性の優れ
た粉末とすることができる、
ということにある。The impregnation point of the present invention is as follows: l) Iron oxide can be easily pulverized, and 2) If part of the iron oxide is replaced with metallic iron (M, Fe), the saturation magnetization σS can be reduced.
3) If the replacement is within a certain range, a powder with excellent weather resistance can be obtained.
すなわち、
（１）酸化鉄を原料とすること、
（２）平均粒径が１〜８０Ｂｍであること、（３）金属
鉄（Ｍ、Ｆｅ）含有量が１〜２５重量％であって、マグ
ネタイ） （Ｆｅ３０４）の含有量が
ｙ≧８７−２．２８ ｘ
ここにＸ＝金属鉄含有量（重量％）
ｙ＝マグネタイトの含有量（重量％）
であるような強磁性粉末は、電波吸収材等用としての要
件を十分溝たすものである。That is, (1) iron oxide is used as a raw material, (2) the average particle size is 1 to 80 Bm, and (3) the metallic iron (M, Fe) content is 1 to 25% by weight, and magnetite is ) The ferromagnetic powder whose content of (Fe304) is y≧87-2.28 This fully satisfies the requirements for use in other areas.
以下、本発明の構成を詳細に説明する。Hereinafter, the configuration of the present invention will be explained in detail.
第一に、酸化鉄を原料とする理由は次の通りである。本
発明に規定した粒径及び組成の強磁性粉末は、酸化鉄を
原料とする番゛王かに、金属鉄の機械粉砕やアトマイズ
により得られる鉄粉を原料としても製造することができ
る。一般に、同等粒度の粉末を得るために、粉化に要す
るコストは、金属鉄に対するより、酸化鉄に対する方が
ずっと低くて有利である。これは、酸化鉄が脆いために
、機械粉砕によって容易に粉化できるからである。機械
粉砕で比較的容易に可能な粒度は約ＩＪＬｍまでである
。First, the reason why iron oxide is used as a raw material is as follows. The ferromagnetic powder having the particle size and composition specified in the present invention can be produced not only from iron oxide as a raw material, but also from iron powder obtained by mechanically crushing or atomizing metal iron. In general, the cost of comminution is much lower and advantageous for iron oxides than for metallic iron to obtain powders of comparable particle size. This is because iron oxide is brittle and can be easily pulverized by mechanical crushing. Particle sizes that are relatively easily possible by mechanical grinding are up to about IJLm.
本発明者らは、このように粉化された酸化鉄を原料とし
て、Ｍ、ＦｅとＦｅ３Ｏ４が前記の量を含有する粉末を
作ると、高飽和磁化であるとともに、耐候性も優れてい
ることを見出したのである。従来、酸化鉄を還元して鉄
粉を製造することは公知であったが、Ｍ、Ｆｅ量を２５
重量％に制限し、残りを酸化鉄（マグネタイトなど）と
することは試みられなかった。その理由は、電波吸収材
のような用途が無かったことのほかに、仮に丁体が酸化
鉄であっても、一定量のＭ 、 Ｆ ｅを含有すればそ
の分耐候性が劣化するとの予想ないしは先入観があった
ことと考えられる。しかしながら、本発明者らの研究に
よれば、一定量以上のマグネタイトを含み、しかも一部
がＭ、Ｆｅとなっているような粉末を酸化鉄から作ると
、通常のマグネタイト粉末よりも飽和磁化が大きくなる
利点があり、しかも電波吸収材用として耐候性に問題が
無いのである。The present inventors have found that when a powder containing the above amounts of M, Fe, and Fe3O4 is produced using the powdered iron oxide as a raw material, it has high saturation magnetization and excellent weather resistance. They discovered this. Conventionally, it has been known to reduce iron oxide to produce iron powder, but when the amount of M and Fe is reduced to 25
No attempt has been made to limit it to % by weight and make the remainder iron oxide (such as magnetite). The reason for this is that there was no use for it as a radio wave absorber, and in addition to the fact that even if the material was made of iron oxide, it was predicted that if it contained a certain amount of M or Fe, its weather resistance would deteriorate accordingly. Or perhaps it was due to preconceived notions. However, according to the research of the present inventors, when a powder containing a certain amount or more of magnetite and a portion of which is M and Fe is made from iron oxide, the saturation magnetization is higher than that of ordinary magnetite powder. It has the advantage of being larger, and there is no problem with weather resistance when used as a radio wave absorbing material.
このような組成の粉末を酸化鉄から作るには。To make a powder of such a composition from iron oxide.
（ａ）ウスタイ） （Ｆｅｄ）の共析変態によりＭ 、
ＦｅとＦｅ３Ｏ４を生成させる、（ｂ）へマタイ）（Ｆ
ｅ２０３）の還元によりＭ 、 Ｆ ｅとＦｅ３Ｏ４を
生成さセル、（ｃ）’Ｆｅ５０＋の部分還元により、一
部をＭ、Ｆｅとする、
（ｄ）ｋ記（ａ）〜′（Ｃ）の組合せ、（ｅ）上記（ａ
）〜（ｄ）の何れかの別個の方法で作られた粉末を混合
して、所定のＭ 、 Ｆ ｅ及びＦｅ３Ｏ４含有量を得
る、
などの方法によって可能である。(a) Due to the eutectoid transformation of (Fed) M,
Generate Fe and Fe3O4, (b) Hematai) (F
A cell in which M, Fe and Fe3O4 are generated by reduction of e203), (c) Partial reduction of 'Fe50+ results in a part of M and Fe, (d) Combination of (a) to '(C) in k. , (e) above (a
) to (d) by mixing powders made by any of the separate methods to obtain predetermined M, Fe, and Fe3O4 contents.
本発明者らの実験によれば、後に実施例で示すように、
耐候性が良好であるためには、Ｍ 、 Ｆ ｅが２５重
量％以下で平均粒径が１ｇｍ以上であることが必要であ
る。Ｍ、Ｆｅが２５重量％を越えると、粉末の中のＭ
、 Ｆ ｅ部分が外気にさらされる機会が多くなり、酸
化が起こるために飽和磁化σＳが低下する。すなわち耐
候性が劣化する。また平均粒径が１ｇｍ未満であると、
粉末の比表面積が大きくなるため、この場合もＭ、Ｆｅ
が外気にさらされやすくなり、酸化が起こって耐候性が
劣化する。According to the experiments conducted by the present inventors, as shown in the examples later,
In order to have good weather resistance, it is necessary that M and Fe be 25% by weight or less and the average particle size be 1 gm or more. When M and Fe exceed 25% by weight, M in the powder
, the Fe portion is exposed to the outside air more often, and oxidation occurs, resulting in a decrease in saturation magnetization σS. In other words, weather resistance deteriorates. Moreover, when the average particle size is less than 1 gm,
Since the specific surface area of the powder increases, M, Fe
is more easily exposed to outside air, oxidation occurs and weather resistance deteriorates.
Ｍ 、 Ｆ ｅ量及び平均粒径を選べば耐候性が優れて
いるのは、Ｍ 、 Ｆ ｅ部分が酸化鉄部分によって外
気から保護されるためと考えられ、この点が、本発明法
による粉末が従来予測されるよりも耐候性が良い結果を
生んだ原因と思われる。The reason why weather resistance is excellent when the amount of M and Fe and the average particle size are selected is thought to be that the M and Fe parts are protected from the outside air by the iron oxide part. This is thought to be the reason why the weather resistance was better than previously predicted.
次に、電波吸収材等用の粉末としては、粉体性状も重要
である。すなわち、電波吸収材等は１通常強磁性粉末を
樹脂などに混合し、混練してシート状にノズルから押出
して製造されることが多い、そのためには、微粉である
ほど混線性や押出し性が良い０粒度が粗くなるとこれら
の性質が劣り、実施例で示すように平均粒径が８０ｐｍ
を超えたものは押出しが不可能となる。Next, powder properties are also important for powders for radio wave absorbers and the like. In other words, radio wave absorbing materials are often manufactured by mixing ferromagnetic powder with resin, kneading it, and extruding it into a sheet from a nozzle.For this purpose, the finer the powder, the better the crosstalk and extrudability. When the good 0 particle size becomes coarse, these properties become inferior, and as shown in the example, the average particle size is 80 pm.
Extrusion becomes impossible if it exceeds this range.
また、電波吸収材等用の粉末は飽和磁化σＳ≧８０ｅｍ
ｕ／ｇを必要とするが、そのためには一定量以上のＭ
、 Ｆ ｅ及びＦｅ３Ｏ４含有量が必要である。特にＭ
、 Ｆ ｅは理論的な飽和磁化（Ｉｓが約２ＬＯｅｍ
ｕ／ｇであッテ、Ｆｅ３Ｏ４の約９２ ｅ ｍ ｕ ／
ｇより格段に大きく、Ｍ 、 Ｆ ｅを含むことが１
本発明粉末が通常のマグネタイト粉末よりも飽和磁化σ
Ｓを高くしうるポイントとなる。実施例の飽和磁化σＳ
測定結果によると、Ｆｅ３Ｏ４を含む粉末の飽和磁化σ
Ｓは、Ｍ、ＦｅとＦｅ３Ｏ４の理論飽和磁化σＳ値を加
算したものにほぼ等しい、すなわち、Ｍ 、 Ｆ ｅが
Ｘ重量％、Ｆｅ３Ｏ４が７重量％であれば、飽和磁化σ
Ｓの予想値は、
２１０Ｘ （ｘ／１００）＋９２Ｘ （ｙ／１００）従
って、Ｆｅ３Ｏ４の一部をＭ 、 Ｆ ｅで置きかえ、
Ｍ 、 Ｆ ｅを１重量％だけ増やすと、飽和磁化σＳ
は約２ｅｍｕ／ｇ増加する。飽和磁化σＳの上昇量はＭ
、 Ｆ ｅの含有量に比例して増加するが、２ ｅ
ｍ ｕ ／ ｇ以下の上昇量は工業的な意味が小さいか
ら、Ｍ 、 Ｆ ｅは１重量％以上必要である。このよ
うにしてＭ、Ｆｅ量（Ｘ重量％）が定められると、粉末
の飽和磁化σＳを８０ ｅ ｍ ｕ ７ｇとするために
必要なＦｅ３Ｏ４量（７重量％）は、最小限
ｙ＝８７−２．２８ｘ（重量％）
である。In addition, the saturation magnetization σS≧80em of powder for radio wave absorbing materials, etc.
u/g, but for that purpose more than a certain amount of M
, Fe and Fe3O4 content are required. Especially M
, F e is the theoretical saturation magnetization (Is is about 2LOem
u/g, about 92 e m u/of Fe3O4
It is much larger than g, and it is 1 to include M and Fe.
The powder of the present invention has a higher saturation magnetization σ than normal magnetite powder.
This is a point where S can be increased. Saturation magnetization σS of the example
According to the measurement results, the saturation magnetization σ of powder containing Fe3O4
S is approximately equal to the sum of the theoretical saturation magnetization σS values of M, Fe and Fe3O4, that is, if M, Fe are X weight % and Fe3O4 is 7 weight %, the saturation magnetization σ
The expected value of S is 210X (x/100) + 92X (y/100) Therefore, replace part of Fe3O4 with M, Fe,
When M and Fe are increased by 1% by weight, the saturation magnetization σS
increases by about 2 emu/g. The amount of increase in saturation magnetization σS is M
, increases in proportion to the content of Fe, but 2 e
Since an increase of less than mu/g has little industrial significance, M and Fe are required to be at least 1% by weight. When the amount of M and Fe (X weight %) is determined in this way, the amount of Fe3O4 (7 weight %) required to make the saturation magnetization σS of the powder 80 e mu 7 g is the minimum amount y = 87- 2.28x (wt%).
このように、本発明による粉末はＭ、Ｆ ｅを増加させ
ることによって飽和磁化σＳを向上させ、同一不純物量
であれば従来のマグネタイト粉よりも大きな飽和磁化が
得られ、逆に同一飽和磁化σＳならば純度を落とし、コ
ストダウンすることができるのである。なお、規定した
量のＭ 、 Ｆ ｅ及びＦｅ３Ｏ４以外の残部は非磁性
の物質で良＜、Ｆｅｄ、Ｆｅ２０３またはその他の物質
であってもよく、特に＃１約は無い。As described above, the powder according to the present invention improves the saturation magnetization σS by increasing M and Fe, and with the same amount of impurities, a larger saturation magnetization can be obtained than the conventional magnetite powder, and conversely, the same saturation magnetization σS can be obtained. If so, it is possible to reduce purity and reduce costs. Note that the remainder other than the specified amounts of M, Fe, and Fe3O4 may be a nonmagnetic substance, Fed, Fe203, or other substances, and there is no #1 in particular.
以上、本発明の詳細を述べたが、数値限定の理由をまと
めると次のようになる。The details of the present invention have been described above, but the reasons for the numerical limitations are summarized as follows.
（１）平均粒径の下限 ：耐候性
（２）平均粒径の上限 ：混練押出性（３）Ｍ、Ｆ
ｅの下限 ：飽和磁化σＳ（４）Ｍ、Ｆｅの上限
：耐候性
（５）Ｆｅ３０４の下限 ：飽和磁化ｃ７．ｓさて１
本発明になる強磁性粉末を製造するための具体的な方法
を以下例示する。なお、実施例において、より具体的な
製造条件を述べることとする。(1) Lower limit of average particle size: Weather resistance (2) Upper limit of average particle size: Kneading and extrudability (3) M, F
Lower limit of e: Saturation magnetization σS(4)M, upper limit of Fe
: Weather resistance (5) Lower limit of Fe304 : Saturation magnetization c7. s Now 1
A specific method for producing the ferromagnetic powder according to the present invention will be exemplified below. In addition, more specific manufacturing conditions will be described in Examples.
まず原料としては、ミルスケールを用いるコトができる
。これは鉄鋼製品製造工程における副産物であり、Ｆｅ
Ｏを主成分としていて、注意深く入手すれば、純度の高
いものを選ぶことが可能である。ミルスケールは脆いか
ら１機械粉砕によって所定の粒度に粉砕することができ
る。さらに細かいものは、空気分級法による分級や、集
塵採取によって得られる。First, mill scale can be used as a raw material. This is a byproduct in the steel product manufacturing process, and Fe
The main component is O, and if you carefully obtain it, it is possible to select one with high purity. Since mill scale is brittle, it can be ground to a predetermined particle size by one mechanical grinding. Even finer particles can be obtained by classification using the air classification method or by dust collection.
次にＦｅＯを主成分とする粉末を熱処理し、Ｆｅ３Ｏ４
とＭ−Ｆｅに変態させる。Ｍ、Ｆｅを生成させるために
は、通常弱還元性の雰囲気が必要となる。従って、Ｎ２
ガスにＨ２ガスを添加した雰囲気で加熱するのが一法で
ある。そのほか。Next, the powder containing FeO as the main component is heat-treated to produce Fe3O4
and metamorphose into M-Fe. In order to generate M and Fe, a weakly reducing atmosphere is usually required. Therefore, N2
One method is to heat in an atmosphere in which H2 gas is added to the gas. others.
ＣＯガスや固体Ｃ（コークスなど）を還元剤として用い
ることができる。また、粉末の耐候性を改善するために
、はじめに還元性雰囲気、次に中性または弱酸化性の雰
囲気を用いることもある。CO gas or solid C (such as coke) can be used as a reducing agent. Additionally, in order to improve the weather resistance of the powder, a reducing atmosphere may be used first and then a neutral or weakly oxidizing atmosphere.
熱処理温度は、粉末の焼結凝集が過度にならぬようにす
るためと、ウスタイトの分解変態を促進するために、５
６０℃以下で行うのが良い。The heat treatment temperature was set at 5.5% to prevent excessive sintering agglomeration of the powder and to promote decomposition transformation of wustite.
It is best to do this at a temperature below 60°C.
５６０℃はウスタイトの共析変態温度である。560°C is the eutectoid transformation temperature of wustite.
こうして所望のＭ、Ｆｅ、Ｆｅ３０４含有量をもつ粉末
ができるが、熱処理中に粉末が焼結・凝集した場合は、
粉砕工程を加えたり、または何らかの分級工程を加える
ことがある。In this way, a powder with the desired M, Fe, and Fe304 contents is produced, but if the powder sinters and agglomerates during heat treatment,
A grinding step or some sorting step may be added.
なお、粉末中ｃ７）Ｍ、Ｆｅ、Ｆｅ３０４などの分析は
次のように行うのが良い、まず、鉄鋼分析で通常使われ
る湿式分析法によってＭ 、 Ｆ ｅとＴ、Ｆｅを分析
する９次に、Ｘ線回折を用いＦｅｄ、Ｆｅ３０４．Ｆｅ
２０３ ｃ７）重量比を定量する。これらの値と、湿式
分析による非金属鉄量とから、Ｆｅ０１Ｆｅ３０４、Ｆ
ｅ２Ｏ３の絶対量が求まる０本明細書に記された分析値
はこの方法によるものである。In addition, analysis of c7) M, Fe, Fe304, etc. in powder should be carried out as follows. First, analyze M, Fe, T, and Fe using the wet analysis method normally used in steel analysis. , Fed, Fe304. using X-ray diffraction. Fe
203 c7) Determine the weight ratio. From these values and the amount of nonmetallic iron determined by wet analysis, Fe01Fe304, F
The analytical values described in this specification for determining the absolute amount of e2O3 are based on this method.
また、平均粒度は、累積重量粒度分布が５０％になる粒
度、いわゆるメジアン径である０粒度分布測定法として
は、粗い粉末についてはふるい分は法、細かい粉末につ
いてはマイクロトラック法や沈降法を使用することがで
きるが、本明細書の数値はマイクロトラック法によるも
のである。The average particle size is the particle size at which the cumulative weight particle size distribution is 50%, the so-called median diameter.As for particle size distribution measurement methods, the sieve method is used for coarse powders, and the microtrack method and sedimentation method are used for fine powders. However, the numbers herein are from the Microtrack method.
実施例１
ミルスケールを振動ボールミルで１０時間粉砕し、空気
分級によって粗粉をカットして、平均粒径８． Ｏルｍ
の微粉を得た。Example 1 Mill scale was ground in a vibrating ball mill for 10 hours, coarse powder was cut by air classification, and the average particle size was 8. Orm
A fine powder was obtained.
この微粉は Ｔ、Ｆｅニア３．９重量％ であり、不純物としては、 ５ｉ０２：０．２２重量％、 ＭｎＯ：０．３５重量％ Ｐ：０−０１重量％、 Ｓ：０．０１重量％、 ＣａＯ：０．０５重量％ を含んでいた。This fine powder T, Fe nia 3.9% by weight And as impurities, 5i02: 0.22% by weight, MnO: 0.35% by weight P: 0-01% by weight, S: 0.01% by weight, CaO: 0.05% by weight It contained.
熱処理のための粉末容器として、スチールウールを加工
して、内法が５０ｍｍ立方の立方体容器を作成した。ス
チールウールの厚みは約５ｍｍであった。粉末を容器に
充填したのち、スチールウール製の蓋をし、容器ごとコ
ークスの中に埋めた。コークスは２〜１０ｍｍに篩分け
した範囲のものを用いたため、被処理粉末とコークスと
はスチールウールで接触が防がれ、しかも、スチールウ
ール容器は通気性があるため、コークスとともに容器を
加熱することにより、容器内を還元性雰囲気とすること
ができた。加熱は５００℃で９時間行なった。As a powder container for heat treatment, a cubic container with an internal dimension of 50 mm was prepared by processing steel wool. The thickness of the steel wool was about 5 mm. After filling the powder into a container, the container was covered with a steel wool lid and buried in coke. Because the coke used was one that had been sieved to a size of 2 to 10 mm, the steel wool prevented contact between the powder to be treated and the coke, and since the steel wool container was breathable, the container was heated together with the coke. This made it possible to create a reducing atmosphere inside the container. Heating was performed at 500°C for 9 hours.
熱処理後の粉末はほとんど凝集していなかったため、そ
のまま以後の測定旋供した。その結果、Ｍ、Ｆｅ：９．
７重量％、
Ｆｅ３０４ ： ８６．３重量％、
Ｆ ｅ Ｏ： ２−１重量％、
Ｆｅ２Ｏ３≦０．１［ｔ％
であり、その他の不純物は原料ミルケース粉とほぼ同等
であった。平均粒度は８．２ ｇ ｍであった。Since the powder after heat treatment was hardly agglomerated, it was used for subsequent measurements as it was. As a result, M, Fe: 9.
7% by weight, Fe304: 86.3% by weight, FeO: 2-1% by weight, Fe2O3≦0.1 [t%], and other impurities were almost the same as the raw material millcase powder. The average particle size was 8.2 g m.
この粉末の飽和磁化σＳを求めるため、振動試料型磁化
測定装置を用い、磁界１０ｋＯｅ（キロエルステッド）
のもとで測定した結果、飽和磁化ｃ ｓ ＝ ９７．９
ｅ ｍ ｕ ／ ｇと高い値を得た。In order to determine the saturation magnetization σS of this powder, a vibrating sample type magnetization measuring device was used, and a magnetic field of 10 kOe (kiloersted) was used.
As a result of measurement under , saturation magnetization c s = 97.9
A high value of emu/g was obtained.
次に、粉末の耐候性を調べるため、粉末１０ｇをアルミ
ナの皿にのせ、湿度９５％、温度５０℃のもとで、３０
日間放置し、再び飽和磁化σＳを測定した。その結果、
飽和磁化σＳ比（放置後／放置前）は９９．２％であり
、実用」−問題無い耐候性を示した。Next, to examine the weather resistance of the powder, 10 g of the powder was placed on an alumina plate and heated for 30 minutes at a humidity of 95% and a temperature of 50°C.
After leaving it for a day, the saturation magnetization σS was measured again. the result,
The saturation magnetization σS ratio (after being left to stand/before being left to stand) was 99.2%, indicating good weather resistance for practical use.
さらに、粉末を液状エポキシ樹脂と混合し、押し出し性
を調べた０重量比で粉末８０に対し、樹脂２０の混合割
合とし、ビーカー中でスプーンを用いて混合したのち、
内径１０ｍｍのピストン（注射器）に長さ約３０ｍｍに
充填し、２ ｍ ｍ径の穴から手動で押し出したところ
、閉塞は起こらずに全昔押し出された。Furthermore, the powder was mixed with a liquid epoxy resin and the extrudability was examined.The mixing ratio was 80 parts of the powder to 20 parts of the resin, and the mixture was mixed using a spoon in a beaker.
When a piston (syringe) with an inner diameter of 10 mm was filled to a length of about 30 mm and manually pushed out through a 2 mm diameter hole, the solution was completely pushed out without any blockage.
実施例２
次の実施例では、主にＭ 、 Ｆ ｅ量の影響を調べた
。原料は実施例１と同じミルスケールの微粉とし、これ
をアルミナのトレーに２００ｇのせ、管状炉で熱処理し
た。加熱は５００℃とし、最初の２時間はＮ２ ＋Ｈ２
ガス中、残りの８時間はＮ２ガス中で、合計１０時間保
持した。でき上がった粉末を乳鉢ですりつぶし、３２５
メツシユの篩で篩分けし、篩下歩留りを求めた。−３２
５メツシユノ粉末につき、Ｍ、Ｆｅ、Ｆｅ３Ｏ４の分析
、平均粒度および飽和磁化σＳの測定、また、実施例１
と同様の耐候性試験（飽和磁化σＳ比）と押出し試験を
行なった。第１表に、加熱初期のＮ２量と特性との関係
を示す。Example 2 In the next example, the influence of the amounts of M and Fe was mainly investigated. The raw material was the same mill scale fine powder as in Example 1, and 200 g of this was placed on an alumina tray and heat treated in a tube furnace. Heating was at 500℃, with N2 + H2 for the first 2 hours.
The remaining 8 hours were held in N2 gas for a total of 10 hours. Grind the finished powder in a mortar, 325
It was sieved using a mesh sieve and the yield under the sieve was determined. -32
Analysis of M, Fe, Fe3O4, measurement of average particle size and saturation magnetization σS, and Example 1
The same weather resistance test (saturation magnetization σS ratio) and extrusion test were conducted. Table 1 shows the relationship between the amount of N2 at the initial stage of heating and the characteristics.
第１表より、Ｍ 、 Ｆ ｅが１重量％以上では、飽和
磁化σＳがｇＯｅｍｕ／ｇとなっていることがわかる。From Table 1, it can be seen that when M and Fe are 1% by weight or more, the saturation magnetization σS is gOemu/g.
第１表の値から、Ｍ 、 Ｆ ｅと歩留りおよび飽和磁
化σＳ比との関係を示すと、第１図のようになり１歩留
りと耐候性の観点から、Ｍ 、 Ｆ ｅを２５重優％以
内とすべきことが理解される。From the values in Table 1, the relationship between M, Fe, yield, and saturation magnetization σS ratio is shown in Figure 1.1 From the viewpoint of yield and weather resistance, M, Fe is 25% by weight. It is understood that it should be within the range.
なお、第１表の結果によれば、本発明の粉末のように、
Ｍ 、 Ｆ ｅとＦｅ３Ｏ４のいわば混合体であると、
鉄粉が単独で存在するときよりも、耐候性が改善されて
いるように見うけられる。これはＭ 、 Ｆ ｅの存在
形態にかかわることと考えられるが、詳しい機構は明ら
かでない。According to the results in Table 1, like the powder of the present invention,
M, Fe is a so-called mixture of e and Fe3O4,
Weather resistance appears to be improved compared to when iron powder is present alone. This is thought to be related to the existence form of M and Fe, but the detailed mechanism is not clear.
実施例３
次の実施例では、主に平均粒度の影響を調べた。原料と
しては、ヘマタイト微粉（平均粒度０．６ＪＬｍ）およ
びミルスケールを振動ミルで粉砕し、種々の平均粒度と
したものを用いた。これを実施例２と同様に熱処理した
が、加熱初期のＨ２量は１０％とした。熱処理後の粉末
を小型振動ミルで十分解砕したのち篩分けし、篩分は後
の測定を実施例２と同様に行い、第２表の結果を得た。Example 3 In the next example, the influence of average particle size was primarily investigated. As raw materials, fine hematite powder (average particle size: 0.6 JLm) and mill scale were pulverized with a vibration mill to give various average particle sizes. This was heat treated in the same manner as in Example 2, but the amount of H2 at the initial stage of heating was 10%. The heat-treated powder was thoroughly crushed in a small vibrating mill and then sieved, and the sieved fraction was measured in the same manner as in Example 2, and the results shown in Table 2 were obtained.
第２表より、平均粒度がｌｐｍを割ったものは耐候性（
σＳ比）が著しく劣化していること、および、平均粒度
が８０１Ｌｍを゛超えるものは、押出性が劣り、樹脂等
と混合して成形することが難しいことが理解される。From Table 2, the weather resistance (
It is understood that those with a significantly deteriorated σS ratio and an average particle size of more than 801 Lm have poor extrudability and are difficult to mix with a resin or the like and mold.
以上示したように、本発明による強磁性粉末は、電波吸
収材や電磁遮蔽材用として優れたものである。また飽和
磁化σＳが高く、耐候性があることから、その他の用途
、例えば乾式複写機のキャリアなどとしても、十分な使
用に耐えると思われる。As shown above, the ferromagnetic powder according to the present invention is excellent for use in radio wave absorbing materials and electromagnetic shielding materials. Furthermore, since it has a high saturation magnetization σS and is weather resistant, it is thought that it can be used satisfactorily for other uses, such as as a carrier for a dry type copying machine.
第１図は、強磁性粉末のＭ 、 Ｆ ｅ含有量と粉末の
歩留りおよび耐候性（飽和磁化σＳ比）との関係を示す
グラフである。FIG. 1 is a graph showing the relationship between the M and Fe contents of the ferromagnetic powder and the powder yield and weather resistance (saturation magnetization σS ratio).
Claims (1)
て、金属鉄含有量とマグネタイト含有量が、 １≦ｘ≦２５、かつ ｙ≧８７−２．２８ｘ ただしｘ：金属鉄含有量（重量％） ｙ：マグネタイト含有量（重量％） であることを特徴とする強磁性粉末。[Claims] 1. Iron oxide is used as a raw material, the average particle size is 1 to 80 μm, and the metallic iron content and magnetite content are 1≦x≦25, and y≧87-2.28x, where x : Metallic iron content (weight %) y : Magnetite content (weight %) A ferromagnetic powder characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60079752A JPS61238901A (en) | 1985-04-15 | 1985-04-15 | Ferromagnetic powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60079752A JPS61238901A (en) | 1985-04-15 | 1985-04-15 | Ferromagnetic powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61238901A true JPS61238901A (en) | 1986-10-24 |
| JPH0149762B2 JPH0149762B2 (en) | 1989-10-26 |
Family
ID=13698953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60079752A Granted JPS61238901A (en) | 1985-04-15 | 1985-04-15 | Ferromagnetic powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61238901A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316746A (en) * | 1991-02-05 | 1994-05-31 | Kawasaki Steel Corporation | High purity iron oxide and method for production hereof |
| KR20030015453A (en) * | 2001-08-14 | 2003-02-25 | 주식회사 티베이스 | An Electromagnetic Wave Attenuating Material Using The Scale Of Alloy Steel |
| US6827757B2 (en) | 2001-11-30 | 2004-12-07 | Jfe Steel Corporation | Magnetite-iron based composite powder, magnetite-iron based powder mixture, method for producing the same, method for remedying polluted soil, water or gases and electromagnetic wave absorber |
| KR100921261B1 (en) * | 2001-12-04 | 2009-10-09 | 토다 고교 가부시끼가이샤 | Iron Particles for Purifying Contaminated Soil or Ground Water, Process for Producing the Iron Particles, Purifying Agent Comprising the Iron Particles, Process for Producing the Purifying Agent and Method of Purifying Contaminated Soil or Ground Water |
| WO2016075213A1 (en) * | 2014-11-13 | 2016-05-19 | Ce-Sys Engineering Gmbh | Building material for shielding against electromagnetic waves, method for producing the same and use thereof |
| CN113145856A (en) * | 2021-03-15 | 2021-07-23 | 西安交通大学 | System and method for separation, reduction and storage and transportation of iron oxidation products |
-
1985
- 1985-04-15 JP JP60079752A patent/JPS61238901A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316746A (en) * | 1991-02-05 | 1994-05-31 | Kawasaki Steel Corporation | High purity iron oxide and method for production hereof |
| KR20030015453A (en) * | 2001-08-14 | 2003-02-25 | 주식회사 티베이스 | An Electromagnetic Wave Attenuating Material Using The Scale Of Alloy Steel |
| US6827757B2 (en) | 2001-11-30 | 2004-12-07 | Jfe Steel Corporation | Magnetite-iron based composite powder, magnetite-iron based powder mixture, method for producing the same, method for remedying polluted soil, water or gases and electromagnetic wave absorber |
| KR100921261B1 (en) * | 2001-12-04 | 2009-10-09 | 토다 고교 가부시끼가이샤 | Iron Particles for Purifying Contaminated Soil or Ground Water, Process for Producing the Iron Particles, Purifying Agent Comprising the Iron Particles, Process for Producing the Purifying Agent and Method of Purifying Contaminated Soil or Ground Water |
| WO2016075213A1 (en) * | 2014-11-13 | 2016-05-19 | Ce-Sys Engineering Gmbh | Building material for shielding against electromagnetic waves, method for producing the same and use thereof |
| CN113145856A (en) * | 2021-03-15 | 2021-07-23 | 西安交通大学 | System and method for separation, reduction and storage and transportation of iron oxidation products |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0149762B2 (en) | 1989-10-26 |
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