JP2009114505A - Magnetite-iron composite powder and its manufacturing method - Google Patents
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011164 primary particle Substances 0.000 claims abstract description 28
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 30
- 239000002245 particle Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000006247 magnetic powder Substances 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 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 2
- 239000011553 magnetic fluid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Abstract
Description
本発明は、電磁波吸収用磁性粉、高周波磁芯、磁性塗料や磁気インク等の磁気識別用顔料、磁性流体、触媒等の用途に用いられる金属磁性粉に関し、特に微細な一次粒径と高い飽和磁化σｓを併せ持つマグネタイト−鉄複合粉末と、その製造方法に関するものである。 The present invention relates to magnetic powder for electromagnetic wave absorption, high-frequency magnetic core, magnetic identification pigment such as magnetic paint and magnetic ink, magnetic fluid, catalyst, etc., and particularly fine primary particle size and high saturation. The present invention relates to a magnetite-iron composite powder having magnetization σs and a method for producing the same.
パソコンのＣＰＵ処理速度の高速化、無線ＬＡＮの普及などに伴い、圧粉磁心に使用される金属磁性粉に対しても、より高い周波数で優れた電磁気特性を有するものが求められている。従来、金属磁性粉は粒子の電気抵抗が低いために、高周波帯域で渦電流損失の影響を受けやすく、高周波での使用が困難とされていた。 With the increase in the CPU processing speed of personal computers and the widespread use of wireless LAN, metal magnetic powders used for dust cores are also required to have excellent electromagnetic characteristics at higher frequencies. Conventionally, metal magnetic powders are easily affected by eddy current loss in the high frequency band due to the low electrical resistance of the particles, making it difficult to use at high frequencies.
渦電流損失を抑え、高周波で優れた電磁気特性を実現するためには、金属磁性粉の粒子径を微細にすることが有利である。そこで、本発明者らは、微細な酸化鉄を還元した後に酸化処理を行う方法で、平均一次粒径が１μｍ程度の微細な金属磁性粉を製造する方法を提案した（特許文献１〜４参照）。 In order to suppress eddy current loss and realize excellent electromagnetic characteristics at high frequencies, it is advantageous to make the particle size of the metal magnetic powder fine. Therefore, the present inventors have proposed a method for producing fine metal magnetic powder having an average primary particle size of about 1 μm by a method of performing oxidation treatment after reducing fine iron oxide (see Patent Documents 1 to 4). ).
これらの方法を用いることで、平均一次粒径が０．７〜５μｍ程度の微細化を実現することができた。しかし、電子回路の高周波化に伴い、さらに高い周波数で使用可能とする要求が高まり、より微細な金属磁性粉が望まれている。 By using these methods, miniaturization with an average primary particle size of about 0.7 to 5 μm could be realized. However, with the increase in the frequency of electronic circuits, there is an increasing demand for use at higher frequencies, and finer metal magnetic powders are desired.
また、自動認識技術の進展に伴い、磁性塗料や磁気インクとして使用される金属磁性粉に対して、より微細かつ均一な粒度分布と高い飽和磁化σｓを併せ持つ金属磁性粉が望まれている。
しかしながら、本発明者らが提案した従来の方法（上記特許文献１〜４参照）では、平均一次粒径を０．７μｍ程度まで微細にすると、還元反応が不十分となり、高い飽和磁化を持つα−Ｆｅ相の生成率が低下して、σｓが低下するという問題があった。 However, in the conventional method proposed by the present inventors (see Patent Documents 1 to 4 above), if the average primary particle size is made fine to about 0.7 μm, the reduction reaction becomes insufficient and α having high saturation magnetization. There was a problem that the production rate of the -Fe phase was lowered and σs was lowered.
本発明はこのような事情のもとになされたものであり、飽和磁化σｓの高い鉄系の粉末を用いて、微細な一次粒径と高いσｓを併せ持つ、高性能なマグネタイト−鉄複合粉末およびその製造方法を提供することを目的とする。 The present invention has been made under such circumstances, and uses a high-performance magnetite-iron composite powder having both a fine primary particle size and a high σs using an iron-based powder having a high saturation magnetization σs, and It aims at providing the manufacturing method.
マグネタイト−鉄複合粉末の平均一次粒径を０．７μｍ以下に微細化する手段として、還元温度を低温にする方法がある。しかしながら、還元温度を５３０℃以下に下げると、還元反応の進行が不十分となり、σｓの低いマグネタイト相やウスタイト相の比率が多くなり、高いσｓを得ることができない。 As a means for reducing the average primary particle size of the magnetite-iron composite powder to 0.7 μm or less, there is a method of reducing the reduction temperature. However, when the reduction temperature is lowered to 530 ° C. or lower, the reduction reaction proceeds insufficiently, the ratio of the magnetite phase or the wustite phase having a low σs increases, and a high σs cannot be obtained.
そこで、本発明者らは、５３０℃以下の低い還元温度でも還元反応が進行する手段を鋭意検討した。その結果、原料のヘマタイト中に還元反応を促進する成分（Ｃｏ、Ｎｉ、Ｃｕ、Ｃｒ、Ｃａ）を添加することで、５３０℃以下の温度でも還元反応が進行し、高いσｓを実現できることを見出した。さらに、原料のヘマタイト中に粒成長を抑制する成分（ＳｉＯ２、Ｐ）を含有させることで、均一な粒度分布が得られることを見出した。 Therefore, the present inventors diligently studied a means for the reduction reaction to proceed even at a low reduction temperature of 530 ° C. or lower. As a result, it was found that by adding components (Co, Ni, Cu, Cr, Ca) that promote the reduction reaction to the raw material hematite, the reduction reaction proceeds even at a temperature of 530 ° C. or less, and high σs can be realized. It was. Furthermore, it has been found that a uniform particle size distribution can be obtained by containing components (SiO 2 , P) that suppress grain growth in the raw material hematite.
本発明は、上記の知見に基づきなされたもので、以下のような特徴を有する。
［１］平均一次粒径が０．３〜０．７μｍであり、Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上を合計で０．０１ｍａｓｓ％以上、１０ｍａｓｓ％未満、ＳｉＯ２を０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満、Ｐを０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満ならびにマグネタイトを含有することを特徴とするマグネタイト−鉄複合粉末。
［２］Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上、ＳｉＯ２およびＰを含有する酸化鉄を、還元性雰囲気下、４００℃超、５３０℃以下の温度で還元処理を行った後、さらに、酸化性雰囲気下で酸化処理を行いマグネタイトを生成させて、上記［１］に記載のマグネタイト−鉄複合粉末を製造することを特徴とするマグネタイト−鉄複合粉末の製造方法。
The present invention has been made based on the above findings and has the following characteristics.
[1] The average primary particle size is 0.3 to 0.7 μm, and one or two or more selected from Co, Ni, Cu, Cr and Ca are combined in a total of 0.01 mass% or more and less than 10 mass%. the SiO 2 0.005 mass% or more and less than 0.1mass%, P of 0.005 mass% or more, magnetite, characterized in that it contains 0.1mass% less and magnetite - iron composite powder.
[2] An iron oxide containing one or more selected from Co, Ni, Cu, Cr and Ca, SiO 2 and P, at a temperature above 400 ° C. and below 530 ° C. in a reducing atmosphere. After the reduction treatment, the magnetite-iron composite powder described in [1] above is produced by performing an oxidation treatment in an oxidizing atmosphere to generate magnetite. Production method.
本発明によれば、飽和磁化σｓが１９０ｅｕｍ／ｇ以上、平均一次粒径が０．３〜０．７μｍのマグネタイト−鉄複合粉末およびその製造方法が提供される。 According to the present invention, a magnetite-iron composite powder having a saturation magnetization σs of 190 eum / g or more and an average primary particle size of 0.3 to 0.7 μm and a method for producing the same are provided.
以下、本発明を実施するための最良の形態の一例を説明する。 Hereinafter, an example of the best mode for carrying out the present invention will be described.
まず、本発明のマグネタイト−鉄複合粉末は、平均一次粒径が０．３〜０．７μｍ、より好ましくは０．４〜０．６μｍの範囲内で良好な電磁気特性を示す。平均一次粒径が０．３μｍ未満では還元処理時における未反応成分の含有比率が高くなるため、高いσｓを得ることができない。また、粒子の保磁力Ｈｃが増大し、圧粉磁芯にした時の初透磁率やコアロスが劣化するため、好ましくない。一方、平均一次粒径が０．７μｍを超えると、電子部品として使用する場合は高周波の電磁気特性が劣化し、また、塗料として使用する場合は分散性が劣化するため、好ましくない。 First, the magnetite-iron composite powder of the present invention exhibits good electromagnetic properties when the average primary particle size is in the range of 0.3 to 0.7 μm, more preferably 0.4 to 0.6 μm. If the average primary particle size is less than 0.3 μm, the content ratio of unreacted components during the reduction treatment is high, and thus high σs cannot be obtained. Moreover, since the coercive force Hc of the particles increases and the initial magnetic permeability and core loss when the powder magnetic core is made deteriorate, it is not preferable. On the other hand, when the average primary particle size exceeds 0.7 μm, the electromagnetic characteristics of high frequency deteriorate when used as an electronic component, and the dispersibility deteriorates when used as a paint.
また、本発明のマグネタイト−鉄複合粉末は、５３０℃以下の低い温度で還元反応を促進させるために、Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上の合計の含有量を、０．０１ｍａｓｓ％以上、１０ｍａｓｓ％未満とすることが重要である。Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上の合計の含有量が０．０１ｍａｓｓ％未満では、還元温度５３０℃以下での還元反応を促進する効果が低く、σｓが低下するため好ましくない。また、Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上の合計の含有量が１０ｍａｓｓ％以上の場合、複合粉末の組成自体の磁気モーメントの低下や異相の析出によりσｓが低下するため、好ましくない。それぞれの含有量のより好ましい範囲は成分によって異なり、Ｃｏ、ＮｉおよびＣｕはそれぞれ０．１〜５ｍａｓｓ％、ＣｒおよびＣａはそれぞれ０．１〜３ｍａｓｓ％である。 In addition, the magnetite-iron composite powder of the present invention has a total of one or more selected from Co, Ni, Cu, Cr and Ca in order to promote the reduction reaction at a low temperature of 530 ° C. or lower. It is important that the content is 0.01 mass% or more and less than 10 mass%. When the total content of one or more selected from Co, Ni, Cu, Cr and Ca is less than 0.01 mass%, the effect of promoting the reduction reaction at a reduction temperature of 530 ° C. or lower is low, and σs Is unfavorable because of lowering. When the total content of one or more selected from Co, Ni, Cu, Cr, and Ca is 10 mass% or more, σs is caused by a decrease in the magnetic moment of the composition of the composite powder itself or precipitation of a different phase. Is unfavorable because it decreases. More preferable ranges of the respective contents differ depending on the components, and Co, Ni and Cu are 0.1 to 5 mass%, and Cr and Ca are 0.1 to 3 mass%, respectively.
さらに、本発明のマグネタイト−鉄複合粉末は、還元処理中の粒成長を抑制するために、シリカ（ＳｉＯ２）を０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満、および、リン（Ｐ）を０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満含有させることが重要である。ＳｉＯ２およびＰそれぞれのより好ましい含有量は、０．０１ｍａｓｓ％以上、０．０５ｍａｓｓ％未満である。ＳｉＯ２およびＰそれぞれの含有量が、０．００５ｍａｓｓ％未満では、還元処理中の粒成長の抑制効果が不十分で、０．７μｍ以下の平均一次粒径を得ることができない。また、ＳｉＯ２およびＰそれぞれの含有量が、０．１ｍａｓｓ％を超えると、還元反応が抑制され、還元処理時に未反応成分が多く残留してσｓが低下するため、好ましくない。 Further, the magnetite-iron composite powder of the present invention has a silica (SiO 2 ) content of 0.005 mass% or more, less than 0.1 mass%, and phosphorus (P) of 0 to suppress grain growth during the reduction treatment. It is important to contain 0.005 mass% or more and less than 0.1 mass%. The more preferable content of each of SiO 2 and P is 0.01 mass% or more and less than 0.05 mass%. If the content of each of SiO 2 and P is less than 0.005 mass%, the effect of suppressing grain growth during the reduction treatment is insufficient, and an average primary particle size of 0.7 μm or less cannot be obtained. Further, if the content of each of SiO 2 and P exceeds 0.1 mass%, the reduction reaction is suppressed, and a large amount of unreacted components remain during the reduction treatment, which lowers σs.
ここで、本発明に係るマグネタイト−鉄複合粉末は、以下のようにして製造される。まず、出発原料として、製造後のマグネタイト−鉄複合粉末中における、Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上の合計の含有量が０．０１ｍａｓｓ％以上、１０ｍａｓｓ％未満、さらに、ＳｉＯ２およびＰそれぞれの含有量が０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満となる酸化鉄を用いる。次に、これを水素或いは窒素などの還元性雰囲気下で、４００℃超、５３０℃以下の温度で還元処理を行う。その後、さらに、好ましい範囲として酸素濃度１〜１０ｖｏｌ．％の酸化性雰囲気下で、粒子表面を酸化処理してマグネタイトを生成させて安定化した後に、炉より取り出す。マグネタイトの好ましい含有量は０．０５〜３ｍａｓｓ％である。より好ましくは０．０８〜１．２ｍａｓｓ％である。 Here, the magnetite-iron composite powder according to the present invention is produced as follows. First, as a starting material, the total content of one or more selected from Co, Ni, Cu, Cr and Ca in the magnetite-iron composite powder after production is 0.01 mass% or more and 10 mass. The iron oxide is used in which the content of each of SiO 2 and P is 0.005 mass% or more and less than 0.1 mass%. Next, this is subjected to reduction treatment at a temperature higher than 400 ° C. and lower than 530 ° C. in a reducing atmosphere such as hydrogen or nitrogen. Thereafter, the oxygen concentration is preferably 1 to 10 vol. After the particle surface is oxidized and magnetite is generated and stabilized in an oxidizing atmosphere of 1%, it is taken out from the furnace. The preferable content of magnetite is 0.05 to 3 mass%. More preferably, it is 0.08-1.2 mass%.
前記出発原料である酸化鉄中にＣｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上を含有させることで５３０℃以下の還元温度での還元反応が促進する機構については明らかではないが、ＮｉＯ、ＣｕＯ、ＣｏＯなどはＦｅ２Ｏ３よりも低温で還元される成分であるため、これらの還元成分が核となってＦｅ２Ｏ３の還元を促進する機構が考えられる。従って、本発明では、酸化鉄の還元処理過程で原料中にＣｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる１種または２種以上の成分が存在することが重要であり、還元後の鉄粉に、後からこれらの成分を添加する方法では、本発明で得られるような粒子径（一次粒径）の微細化と高σｓを併せ持つマグネタイト−鉄複合粉末を製造することはできない。なお、処理温度が４００℃以下の場合には、酸化鉄の還元反応が進み難い。 Regarding the mechanism in which the reduction reaction at a reduction temperature of 530 ° C. or less is promoted by containing one or more selected from Co, Ni, Cu, Cr and Ca in the iron oxide as the starting material. is not clear, NiO, CuO, since such CoO is a component which is reduced at a lower temperature than Fe 2 O 3, mechanism by which these reducing components to promote the reduction of Fe 2 O 3 at the core are considered . Therefore, in the present invention, it is important that one or more components selected from Co, Ni, Cu, Cr, and Ca are present in the raw material during the iron oxide reduction treatment process. The method of adding these components to the iron powder later cannot produce a magnetite-iron composite powder having both a refined particle size (primary particle size) and high σs as obtained in the present invention. When the treatment temperature is 400 ° C. or lower, the reduction reaction of iron oxide is difficult to proceed.
また、前記出発原料である酸化鉄中にＳｉＯ２およびＰが存在することで、還元処理中における粒子の肥大化および粒子間のネック成長が抑制され、微細かつ均一な一次粒径の分布が得られることは、ＳＥＭ観察およびレーザー回折法による粒径分布測定で確認されている。従って、本発明では、酸化鉄の還元処理過程で原料中にＳｉＯ２およびＰが存在することが重要であり、還元後の鉄粉に、後からこれらの成分を添加する方法では、本発明で得られるような微細かつ均一な一次粒径のマグネタイト−鉄複合粉末を得ることはできない。 In addition, the presence of SiO 2 and P in the iron oxide that is the starting material suppresses the enlargement of the particles and the neck growth between the particles during the reduction treatment, thereby obtaining a fine and uniform distribution of the primary particle size. It has been confirmed by SEM observation and particle size distribution measurement by laser diffraction method. Therefore, in the present invention, it is important that SiO 2 and P are present in the raw material in the process of reducing iron oxide. In the method of adding these components to the iron powder after the reduction, the present invention A magnetite-iron composite powder having a fine and uniform primary particle size as obtained cannot be obtained.
以上、本発明により、平均一次粒径が０．３〜０．７μｍ、飽和磁化σｓが１９０ｅｍｕ／ｇ以上、より具体的には、飽和磁化σｓが１９０〜２００ｅｍｕ／ｇのマグネタイト−鉄複合粉末を得ることができる。 As described above, according to the present invention, a magnetite-iron composite powder having an average primary particle size of 0.3 to 0.7 μm and a saturation magnetization σs of 190 emu / g or more, more specifically, a saturation magnetization σs of 190 to 200 emu / g. Obtainable.
なお、本発明に係る微細かつ高σｓのマグネタイト−鉄複合粉末は、上述の方法により製造した状態のままで使用しても良いが、さらに機械処理や化成処理を施して、粒子表面の平滑性や絶縁性を改良して使用することもできる。 The fine and high σs magnetite-iron composite powder according to the present invention may be used in the state produced by the above-described method, but is further subjected to mechanical treatment or chemical conversion treatment to smooth the particle surface. It can also be used with improved insulation.
以下に本発明の具体的実施例を記載する。 Specific examples of the present invention will be described below.
［実施例１］
フェライト用酸化鉄（ＪＦＥケミカル社製ＪＣ−ＤＣ、空気透過法により測定した平均粒径０．８μｍ）に対し、表１に示した添加成分を酸化物の形態で添加し、純水とスチールボールを用いてボールミルで湿式混合した後、乾燥、整粒して各種添加成分を含有する酸化鉄を作製した。これを水素雰囲気中４６０〜５２０℃の温度で還元処理して、平均一次粒径の異なる種々の鉄粉を得た。炉内で常温まで冷却した後、炉を開放する前に５ｖｏｌ．％Ｏ２−Ｎ２雰囲気で１時間保持することにより、鉄粉の表層にマグネタイトを生成させてから、炉外に取り出した。
[Example 1]
To ferritic iron oxide (JC-DC manufactured by JFE Chemical Co., Ltd., average particle size 0.8 μm measured by air permeation method), the additive components shown in Table 1 were added in the form of oxides, and pure water and steel balls After being wet-mixed with a ball mill using an iron, it was dried and sized to produce iron oxide containing various additive components. This was reduced at a temperature of 460 to 520 ° C. in a hydrogen atmosphere to obtain various iron powders having different average primary particle sizes. After cooling to room temperature in the furnace, 5 vol. The magnetite was produced on the surface layer of the iron powder by holding in a% O 2 —N 2 atmosphere for 1 hour, and then taken out of the furnace.
得られた粉末の構成相をＸ線回折で測定し、Ｘ線回折のα−Ｆｅの主要ピーク（ｄ＝２．０２７）とマグネタイト（Ｆｅ３Ｏ４）の主要ピーク（ｄ＝２．５３３）の強度比からα−Ｆｅ相生成率（％）を算出し、マグネタイト含有率（％）は１００−[α−Ｆｅ相生成率]から算出した。平均一次粒径を空気通過法で測定し、σｓをＶＳＭ（振動試料型磁力計）で測定した。各試料のＳｉＯ２およびＰの含有量は、それぞれ０．０２〜０．０４ｍａｓｓ％の範囲であった。 The constituent phases of the obtained powder were measured by X-ray diffraction. The main peak of α-Fe (d = 2.027) and the main peak of magnetite (Fe 3 O 4 ) (d = 2.533) in X-ray diffraction. The α-Fe phase formation rate (%) was calculated from the strength ratio of the magnetite, and the magnetite content rate (%) was calculated from 100- [α-Fe phase formation rate]. The average primary particle size was measured by an air passage method, and σs was measured by a VSM (vibrating sample magnetometer). The content of SiO 2 and P in each sample was in the range of 0.02 to 0.04 mass%, respectively.
本発明例および比較例のα−Ｆｅ相生成率（％）、マグネタイト含有率（％）、平均一次粒径、σｓを表１に併せて示す。表１に示すように、本発明方法により、５３０℃以下の低い還元温度で、平均一次粒径０．３〜０．７μｍ、σｓ＝１９０〜２００ｅｍｕ／ｇのマグネタイト−鉄複合粉末を得ることができる。 Table 1 shows the α-Fe phase generation rate (%), magnetite content (%), average primary particle size, and σs of the inventive examples and comparative examples. As shown in Table 1, a magnetite-iron composite powder having an average primary particle size of 0.3 to 0.7 μm and σs of 190 to 200 emu / g can be obtained at a low reduction temperature of 530 ° C. or less by the method of the present invention. it can.
[実施例２]
フェライト用高純度酸化鉄（ＪＦＥケミカル社製ＪＣ−ＣＰＷ）に対して，還元後にＣｏ＝１ｍａｓｓ％となるような量のＣｏＯと、還元後の含有量が表２に示す量となるような量のＳｉＯ２およびＰを酸化物の形態で添加し、純水とスチールボールを用いてボールミルで湿式混合した後、乾燥、整粒して、所定量のＣｏ、ＳｉＯ２およびＰを含有する酸化鉄を作製した。これを水素雰囲気中５００℃の温度で還元処理して、ＳｉＯ２、Ｐの含有量の異なる種々の鉄粉を得た。炉内で常温まで冷却した後、炉を開放する前に５ｖｏｌ．％Ｏ２−Ｎ２雰囲気で２時間保持することにより、鉄粉の表層にマグネタイトを生成させてから炉外に取り出し、表２に示す種々のマグネタイト−鉄複合粉末を得た。
[Example 2]
For high-purity iron oxide for ferrite (JC-CPW manufactured by JFE Chemical Co., Ltd.), CoO in such an amount that Co = 1% by mass after reduction and an amount in which the content after reduction becomes the amount shown in Table 2 Of SiO 2 and P in the form of oxides, wet-mixed in a ball mill using pure water and steel balls, dried and sized, iron oxide containing a predetermined amount of Co, SiO 2 and P Was made. This was reduced at a temperature of 500 ° C. in a hydrogen atmosphere to obtain various iron powders having different contents of SiO 2 and P. After cooling to room temperature in the furnace, 5 vol. By holding in a% O 2 —N 2 atmosphere for 2 hours, magnetite was produced on the surface layer of the iron powder and then taken out of the furnace to obtain various magnetite-iron composite powders shown in Table 2.
得られた粉末に対して、上記実施例１と同様の方法で、α−Ｆｅ相生成率、マグネタイト含有率（％）平均一次粒径、σｓを測定した。 With respect to the obtained powder, the α-Fe phase generation rate, magnetite content rate (%) average primary particle size, and σs were measured in the same manner as in Example 1.
本発明例および比較例のα−Ｆｅ相生成率（％）、マグネタイト含有率（％）、平均一次粒径、σｓを表２に併せて示す。表２に示すように、本発明により、還元温度５００℃で、平均一次粒径０．３〜０．７μｍ、σｓ＝１９０〜２００ｅｍｕ／ｇのマグネタイト−鉄複合粉末を得ることができる。 Table 2 shows the α-Fe phase generation rate (%), magnetite content rate (%), average primary particle size, and σs of the inventive examples and comparative examples. As shown in Table 2, a magnetite-iron composite powder having an average primary particle size of 0.3 to 0.7 μm and σs of 190 to 200 emu / g at a reduction temperature of 500 ° C. can be obtained according to the present invention.
以上の実施例１，２で示した通り、本発明によれば、酸化鉄を５３０℃以下の還元温度で還元して、平均一次粒径平均一次粒径０．３〜０．７μｍ、σｓ＝１９０〜２００ｅｍｕ／ｇの微細かつ高σｓを併せ持つマグネタイト−鉄複合粉末を得ることができ、高周波インダクタ、電波吸収体、磁性インク、磁性流体、触媒等に用いて好適なマグネタイト−鉄複合粉末を提供することができる。 As shown in Examples 1 and 2 above, according to the present invention, iron oxide is reduced at a reduction temperature of 530 ° C. or lower to obtain an average primary particle size average primary particle size of 0.3 to 0.7 μm, σs = A magnetite-iron composite powder having a fineness of 190 to 200 emu / g and having a high σs can be obtained, and a magnetite-iron composite powder suitable for use in high-frequency inductors, radio wave absorbers, magnetic inks, magnetic fluids, catalysts, etc. is provided. can do.
Claims (2)
Ｃｏ、Ｎｉ、Ｃｕ、ＣｒおよびＣａの中から選ばれる1種または２種以上を合計で０．０１ｍａｓｓ％以上、１０ｍａｓｓ％未満、
ＳｉＯ２を０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満、
Ｐを０．００５ｍａｓｓ％以上、０．１ｍａｓｓ％未満ならびに
マグネタイトを含有することを特徴とするマグネタイト−鉄複合粉末。 The average primary particle size is 0.3 to 0.7 μm,
One or more selected from Co, Ni, Cu, Cr and Ca in total of 0.01 mass% or more and less than 10 mass%,
The SiO 2 0.005mass% or more and less than 0.1mass%,
A magnetite-iron composite powder characterized by containing P in an amount of 0.005 mass% or more and less than 0.1 mass% and magnetite.
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