EP0585940B1 - Legierung mit ultrafeinen Kristallkörnern und hervorragender Korrosionsbeständigkeit - Google Patents

Legierung mit ultrafeinen Kristallkörnern und hervorragender Korrosionsbeständigkeit Download PDF

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Publication number
EP0585940B1
EP0585940B1 EP19930114142 EP93114142A EP0585940B1 EP 0585940 B1 EP0585940 B1 EP 0585940B1 EP 19930114142 EP19930114142 EP 19930114142 EP 93114142 A EP93114142 A EP 93114142A EP 0585940 B1 EP0585940 B1 EP 0585940B1
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Prior art keywords
alloy
group
alloys
element selected
corrosion resistance
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Expired - Lifetime
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EP19930114142
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English (en)
French (fr)
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EP0585940A1 (de
Inventor
Yoshihito Yoshizawa
Shunsuke Arakawa
Katsuhisa Sugimoto
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15383—Applying coatings thereon

Definitions

  • This invention relates to an ultrafine-crystalline alloy excellent in soft magnetic properties and corrosion resistance.
  • Silicon steel, Fe-Si alloys, amorphous alloys, etc. are well known as soft magnetic materials, and their important properties are high relative permeability ⁇ and saturation magnetic flux density Bs.
  • corrosion resistance is an important property since these magnetic materials would be used under various circumstances.
  • Fe-based amorphous alloys have, for example, high saturation magnetic flux density Bs, while they are inferior to Co-based amorphous alloys in soft magnetic properties.
  • the Co-based amorphous alloys are excellent in soft magnetic properties, while they do not have sufficient saturation magnetic flux density Bs.
  • U.S. Patent No. 4,881,989 discloses an Fe-based soft magnetic alloy with ultrafine crystal grains having both high saturation magnetic flux density Bs and high relative permeability ⁇ .
  • This Fe-based alloy having an average grain size of 50 nm (500 ⁇ ) or less is produced through a crystallization process after it is quenched rapidly into an amorphous state.
  • This Fe-based alloy with ultrafine crystal grains has good corrosion resistance to some extent because it contains Nb, etc. When this alloy is used for magnetic cores, it is preferably coated with an oxidation layer. The corrosion resistance of this Fe-based alloy, however, may not be sufficient depending on surroundings in which it is used.
  • JP-A-4-21746 discloses ultrafine-grain iron alloys having asymmetric magnetization curve, consisting of (Fe 1-a M a ) 100-x-y-z- ⁇ - ⁇ - ⁇ - A x Si y B z M 1 ⁇ M 2 ⁇ X ⁇ at.% and containing ⁇ 50 % fine crystals with an average diameter of ⁇ 1000 ⁇ m.
  • JP-A-4-9401 discloses powder manufactured from melt-quenched iron alloy having soft magnetic properties and being resistant to corrosion, which alloy contains, by at.%, 15-18 Si, 5-9 B, 1-4 Cr, 0.1-3 Cu, and 2-10 Nb, Mo, Ta and/or W. Said powder is provided with a dense oxide film.
  • EP-A-430 085 discloses a magnetic alloy with ultrafine crystal grains having an At.% composition of Fe 100-x-y- M x B y , wherein M is at least one of Ti, Zr, Hf, V, Nb, Mo, Ta, Cr, W and Mn, 4 ⁇ x ⁇ 15, 2 ⁇ y ⁇ 25 and 7 ⁇ x + y ⁇ 35, and optionally of (Si, Ge, P, Ga etc.) and/or (Au, Co, Ni etc.), at least 50 % of the alloy structure being occupied by crystal grains having an average grain size of 500 ⁇ or less.
  • EP-A-429 022 for a magnetic alloy having an At.% composition of Co 100-x-y-z-a-b Fe a M x B y X z T b , wherein M is at least one of Ti, Zr, Hf, V, Nb, Mo, Ta, Cr, W and Mn, X is at least one of Si, Ge, P, Ga, Al and N, T is at least one of Cu, Ag, Au, platinum group elements, Ni, Sn, Be, Mg, Ca, Sr and Ba, 0 ⁇ a ⁇ 30, 2 ⁇ x ⁇ 15, 10 ⁇ y ⁇ 25, 0 ⁇ z ⁇ 10, 0 ⁇ b ⁇ 10, and 12 ⁇ x + y + z + b ⁇ 35.
  • JP-A-2 159 315 discloses a heat treatment in grain refinement of a soft magnetic iron alloy containing Cu and Nb, W, Ta, Zr, Hf and/or Mo to obtain a microstructure containing ⁇ 50 % superfine grains and showing a magnetic permeability (at 1 kHz) of 92000 - 118 000.
  • JP-A-3-215 650 discloses iron alloys having perminvar characteristics which contain Fe; Cu, Ag and/or Au; Nb, W, Ta, Zr, Hf, Ti, V, Mn, Cr and/or Mo, wherein ⁇ 50 % of the texture consist of ultrafine crystal grains ⁇ 1000 ⁇ in average grain diameter.
  • an object of the present invention is to provide an alloy with ultrafine crystal grains having improved corrosion resistance.
  • the alloy having a specific surface layer shows extremely improved corrosion resistance.
  • the surface layers of the fine crystalline alloy according to the present invention can be identified by X-ray photoelectron spectroscopy ESCA.
  • ESCA is a chemical element analysis comprising the steps of applying X-ray to a sample and detecting photoelectrons emitted from the sample for identifying chemical bonds of elements by chemical shift values of bond energies.
  • the presence of hydroxides is confirmed by observing peaks attributed to hydroxides in an ESCA spectrum. Same is true of oxide components. More specific understanding can be attained by examples described below.
  • the fine crystalline alloys when they contain larger amounts of hydroxide components than those of oxide components in the surface layers, they show excellent corrosion resistance.
  • the surface layers are thin in the Fe-based alloys, Fe 0 under the surface layers (inside alloys) is strongly detected.
  • Fe 2+ and Fe 3+ are observed in the surface layers.
  • the fine crystalline alloys containing Si they show excellent corrosion resistance if the surface layers contain Si 4+ .
  • Si 4+ exists in the form of SiO 2
  • the fine crystalline alloys show excellent corrosion resistance in most cases.
  • the surface layers of the fine crystalline alloys contain oxides of at least one element selected from the group consisting of Ta, Nb and Cr, they have particularly excellent corrosion resistance. In that case, these elements are not necessarily in the state of complete oxides but usually are in an intermediate state between oxides and metals. When they contain at least one element selected from the group consisting of Zr, Hf and W, their corrosion resistance in an alkaline environment is improved.
  • average grain size is as small as 50 nm (500 ⁇ ) or less in the fine crystalline alloy, corrosion resistance is further improved, and magnetic and mechanical properties are also improved to a level preferable for practical applications.
  • Particularly desirable average grain size is from 2 nm (20 ⁇ ) to 20 nm (200 ⁇ ) since the structure of the fine crystalline alloy is fine and uniform in this average grain size range.
  • the fine crystalline alloys to which the present invention is applicable have a composition represented by the general formula: M 100-x-y-z- ⁇ - ⁇ - ⁇ A x Si y B z M' ⁇ M" ⁇ X ⁇ (atomic %) wherein M represents at least one element selected from the group consisting of Fe, Co and Ni; A represents at least one element selected from the group consisting of Cu, Ag and Au; M' represents at least one element selected from the group consisting of Nb, Mo, Ta, Ti, Zr, Hf, V, Cr and W; M" represents at least one element selected from the group consisting of Mn, Al, platinum group elements, Sc, Y, rare earth elements, Zn, Sn and Re; X represents at least one element selected from the group consisting of C, Ge, P, Ga, Sb, In, Be and As, 0 ⁇ x ⁇ 10, 0 ⁇ y ⁇ 30, 0 ⁇ z ⁇ 25, 0 ⁇ y+z ⁇ 30, 1 ⁇ 20, 0 ⁇ 20, and 0 ⁇ 20.
  • the element M is at least one ferromagnetic element selected from the group consisting of Fe, Co and Ni.
  • the element A representing at least one element selected from the group consisting of Cu, Ag and Au, which effectively makes the alloy structure finer in cooperation with the element M'.
  • the element M' representing at least one element selected from the group consisting of Nb, Mo, Ta, Ti, Zr, Hf, V, Cr and W makes the alloy structure considerably finer in cooperation with the element A.
  • at least one element selected from the group consisting of Nb, Ta and Cr makes it easier to provide the surface layer with improved corrosion resistance.
  • Si and B are effective elements for making the alloys amorphous, for improving magnetic properties, and for making the alloy structure finer.
  • Si functions to improve the corrosion resistance of the surface layers of the fine crystalline alloys, and if Si exists in the form of SiO 2 in the surface layers, their corrosion resistance is extremely improved.
  • the element M'' representing at least one element selected from the group consisting of Mn, Al, platinum group elements, Sc, Y, rare earth elements, Zn, Sn and Re is effective for improving corrosion resistance and for controlling magnetic properties.
  • the element X representing at least one element selected from the group consisting of C, Ge, P, Ga, Sb, In, N, Be and As is effective for making the alloy structure amorphous and for controlling magnetic properties.
  • the corrosion rate of the fine crystalline alloys in a 0.1-kmol ⁇ m -3 NaCl aqueous solution can be reduced to as small as 1 ⁇ 10 -8 kg ⁇ m -2 ⁇ s -1 or less.
  • the fine crystalline alloys of the present invention can be produced by the steps of preparing amorphous alloys by a liquid quenching method such as a single roll method, a double roll method, a rotating liquid spinning method, etc., or by a gas phase quenching method such as a sputtering method, a vapor deposition method, etc., and conducting a heat treatment on the amorphous alloys for turning at least 50% of the alloy structures into ultrafine crystal grains.
  • a liquid quenching method such as a single roll method, a double roll method, a rotating liquid spinning method, etc.
  • a gas phase quenching method such as a sputtering method, a vapor deposition method, etc.
  • the fine crystalline alloys of the present invention can also be produced by the steps of forming amorphous alloy layers in surface portions of alloys by applying laser rays thereto, and conducting a heat treatment thereon.
  • the powdery alloys of the present invention can be produced by conducting a heat treatment on atomized amorphous alloys.
  • the heat treatment is preferably conducted at 450°C-800°C.
  • the heat treatment temperature is lower than 450°C, fine crystallization is difficult even though the heat treatment is conducted for a long period of time.
  • the heat treatment time is generally 1 minute to 200 hours, preferably 5 minutes to 24 hours.
  • the heat treatment temperatures and time may be determined within the above ranges depending upon the compositions of the alloys.
  • the above heat treatment may be conducted in an inert atmosphere.
  • the heat treatment of the alloys of the present invention can be conducted in a magnetic field.
  • a magnetic field is applied in one direction, a magnetic anisotropy in one direction can be given to the resulting heat-treated alloys.
  • a rotating magnetic field by conducting the heat treatment in a rotating magnetic field, further improvement in soft magnetic properties can be achieved.
  • the heat treatment for fine crystallization can be followed by a heat treatment in a magnetic field.
  • the alloys of the present invention with ultrafine crystal grains can be directly produced without experiencing an amorphous phase by controlling quenching conditions.
  • the inert atmosphere should contain 0,1 - 3 volume % of oxygen and 10 - 100 ppm of steam.
  • the preferred oxygen content is about 0,5 volume %, and the preferred steam content is 20 - 50 ppm.
  • the heat treatment for forming the surface layers is preferably conducted at 250-700°C.
  • the heat treatment temperature is lower than 250°C, surface layers with good corrosion resistance cannot be obtained.
  • it exceeds 700°C crystal grains become too large in the resultant surface layers.
  • the heat treatment for forming the surface layers may be conducted at the same time as the heat treatment for fine crystallization.
  • the heat treatment may be conducted at 450-700°C for 10 minutes to 24 hours in an inert atmosphere containing oxygen and steam.
  • the present invention includes fine crystalline alloys having the above-mentioned surface layers formed by sputtering, vapor deposition, CVD etc.
  • the corrosion rates of the fine crystalline alloys were also measured in a 0.1-kmol ⁇ m -3 NaCl aqueous solution.
  • the measured corrosion rates of the fine crystalline alloys were as follows:
  • the 2p 3/2 spectra of Fe in the surface layers of these fine crystalline alloys are shown in Fig. 2.
  • the peaks attributed to Fe 2+ and Fe 3+ were observed, indicating that the surface layers contained Fe 2 O 3 , etc.
  • a peak corresponding to FeOOH was also observed in the surface layers.
  • the spectra of Fe 0 were observed in the surface layers of Samples 2 and 3 excellent in corrosion resistance. It was, therefore, confirmed that the surface layers were so thin that Fe under the surface layers could be detected.
  • the surface layers of the fine crystalline alloys were observed by X-ray photoelectron spectroscopy ESCA in the same way as described in Example 1.
  • the corrosion rates of the fine crystalline alloys were measured in a 0.1-kmol ⁇ m -3 NaCl aqueous solution.
  • the measured corrosion rates of the fine crystalline alloys were as follows:
  • the 2p 3/2 spectra of Fe in the surface layers of these fine crystalline alloys are shown in Fig. 5.
  • the spectra of Fe 0 were observed in the surface layers of Samples 5 and 6 excellent in corrosion resistance. It was, therefore, confirmed that the surface layers were so thin that Fe under the surface layers could be detected.
  • the peaks attributed to Fe 2+ and Fe 3+ were also observed, indicating that the surface layers contained Fe 2 O 3 , etc. Furthermore, a peak attributed to FeOOH was observed.
  • Alloy melts having compositions listed in Table 1 were rapidly quenched by a single roll method to produce thin amorphous alloy ribbons of 5 mm in width and about 18 ⁇ m in thickness. A heat treatment was then conducted on the alloy ribbons at 570°C in a nitrogen gas atmosphere containing 0.5% of oxygen and 30 ppm of steam for 1 hour. The heat-treated alloys had crystallized structures, 90% or more of which were occupied by ultrafine crystal grains of an average grain size of 10 nm (100 ⁇ ).
  • the surface layers of the fine crystalline alloys were then observed by ESCA in the same way as described in Example 1.
  • the ratio of hydroxide components to oxide components and the proportion of Si 4+ bonds in the surface layers were determined from the ratio in intensity of a peak attributed to each bond to the integrated spectrum intensity of the element.
  • the 1s spectrum of O was assumed to be attributed mainly to four components derived from (1) H 2 O adsorbed onto the surfaces of the fine crystalline alloys, derived from (2) hydroxides, derived from (3) SiO 2 formed by the oxidation of Si, one of alloy elements, and derived from (4) oxides of Fe, etc., one of alloy elements.
  • Each bond state of O was determined by comparing the observed 1s spectrum of O with a spectrum synthesized from spectra of each bond by approximation of the Gauss-Lorenz mixed distribution.
  • the ratio of the hydroxide components to the oxide components was defined as a ratio of (a) a proportion of peaks attributed to the hydroxide components in the integrated spectrum of O to (b) a proportion of peaks attributed to the oxide components in the integrated spectrum of O.
  • peaks in the 1s spectrum of O attributed to the hydroxides components and Si 4+ (SiO 2 ) are close to each other.
  • the intensity of a peak attributed to MOx in the 1s spectrum of O was presumed from the intensity of a peak attributed to Si 4+ (SiO 2 ) in the 2p spectrum of Si.
  • the corrosion rates of the fine crystalline alloys were also measured in 0.1-kmol ⁇ m -3 NaCl aqueous solution like Example 1.
  • the measured corrosion rates, the ratios of hydroxide components to oxide components, and the ratios of Si 4+ are listed in Tables 1 and 2.
  • the surface layers contained compounds of both Fe 2+ and Fe 3+ .
  • the present invention can provide fine crystalline alloys having excellent corrosion resistance.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Soft Magnetic Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Claims (6)

  1. Legierung mit ultrafeinen Kristallkörnern hervorragender Korrosionsbeständigkeit, wobei wenigstens 50 % des Legierungsgefüges von ultrafeinen Kristallkörnern einer Durchschnittskorngröße von 50 nm (500 Å) oder weniger eingenommen werden, welche Legierung eine durch die allgemeine Formel M100-x-y-z-α-β-γAxSiyBzM'αM"βXγ   (At.%), dargestellte Zusammensetzung hat, worin M wenigstens ein aus der aus Fe, Co und Ni bestehenden Gruppe gewähltes Element bedeutet; A wenigstens ein aus der aus Cu, Ag und Au bestehenden Gruppe gewähltes Element bedeutet; M' wenigstens ein aus der aus Nb, Mo, Ta, Ti, Zr, Hf, V, Cr und W bestehenden Gruppe gewähltes Element bedeutet; M" wenigstens ein aus der aus Mn, Al, Platingruppenelementen, Sc, Y, Seltenerdelementen, Zn, Sn und Re bestehenden Gruppe gewähltes Element bedeutet; X wenigstens ein aus der aus C, Ge, P, Ga, Sb, In, Be und As bestehenden Gruppe gewähltes Element bedeutet; 0 ≤ x ≤ 10, 0 ≤ y ≤ 30, 0 ≤ z ≤ 25, 0 ≤ y+z ≤ 30, 1 ≤ α ≤ 20, 0 ≤ β ≤ 20 und 0 ≤ γ ≤ 20,
    welche Legierung eine Hydroxidbestandteile enthaltende Oberflächenschicht aufweist, wobei die Hydroxidbestandteile im Gesamtanteil von 65 % oder mehr auf Basis von Oxidbestandteilen sind.
  2. Legierung nach Anspruch 1,
    wobei die Legierung eine Fe-Basislegierung ist und eine Fe2+- und Fe3+-Verbindungen enthaltende Oberflächenschicht hat und wobei ein Fe0-Spektrum in der Legierung durch Röntgenstrahlen-Photoelektronenspektroskopie beobachtet wird.
  3. Legierung nach Anspruch 1 oder 2,
    wobei die Legierung Si enthält und eine eine Si4+-Verbindung enthaltende Oberflächenschicht hat und wobei das Verhältnis von Si4+-Spitzen zu einem integrierten Wert des gesamten 2p-Spektrums von Si mehr als 55 % durch Röntgenstrahlen-Photoelektronenspektroskopie ist.
  4. Legierung nach irgendeinem der Ansprüche 1-3,
    wobei die Oberflächenschicht ein Oxid wenigstens eines aus der aus Ta, Nb und Cr bestehenden Gruppe gewählten Elements enthält.
  5. Legierung nach irgendeinem der Ansprüche 1-3,
    wobei die Oberflächenschicht ein Oxid wenigstens eines aus der aus Zr, Hf und W bestehenden Gruppe gewählten Elements enthält.
  6. Legierung nach irgendeinem der Ansprüche 1-5,
    wobei der Korrosionsgrad der Legierung in einer wässerigen 0,1 kmol·m-3 NaCl-Lösung 1 x 10-8 kg·m-2·s-1 oder weniger ist.
EP19930114142 1992-09-03 1993-09-03 Legierung mit ultrafeinen Kristallkörnern und hervorragender Korrosionsbeständigkeit Expired - Lifetime EP0585940B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP235467/92 1992-09-03
JP23546792A JPH0681086A (ja) 1992-09-03 1992-09-03 耐蝕性に優れた超微細結晶粒組織を有する合金

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EP0585940A1 EP0585940A1 (de) 1994-03-09
EP0585940B1 true EP0585940B1 (de) 1998-07-08

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Cited By (1)

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US8480864B2 (en) * 2005-11-14 2013-07-09 Joseph C. Farmer Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

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GB2234193B (en) * 1988-03-08 1991-11-13 Secr Defence Growing semiconductor crystalline materials
GB8805478D0 (en) * 1988-03-08 1988-04-07 Secr Defence Method & apparatus for growing semi-conductor crystalline materials
JPH0845723A (ja) * 1994-08-01 1996-02-16 Hitachi Metals Ltd 絶縁性に優れたナノ結晶合金薄帯およびナノ結晶合金磁心ならびにナノ結晶合金薄帯の絶縁皮膜形成方法
DE10349339A1 (de) 2003-10-23 2005-06-16 Crystal Growing Systems Gmbh Kristallzüchtungsanlage
DE102006024358B4 (de) * 2006-05-17 2013-01-03 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Hochfeste, bei Raumtemperatur plastisch verformbare Formkörper aus Eisenlegierungen
CN102610348B (zh) * 2012-04-11 2015-04-29 安泰科技股份有限公司 铁基纳米晶软磁合金材料及其制备方法
CN102867604A (zh) * 2012-09-10 2013-01-09 任静儿 一种软磁合金
CN103123841A (zh) * 2012-09-10 2013-05-29 顾建 一种磁性合金材料
CN102856031A (zh) * 2012-09-10 2013-01-02 任静儿 一种磁性粉末合金材料
CN102867605A (zh) * 2012-09-10 2013-01-09 任静儿 一种磁性合金
CN103123842A (zh) * 2012-10-22 2013-05-29 虞海香 一种磁性合金粉末材料
JP5875159B2 (ja) * 2012-12-19 2016-03-02 アルプス・グリーンデバイス株式会社 Ｆｅ基軟磁性粉末、前記Ｆｅ基軟磁性粉末を用いた複合磁性粉末及び前記複合磁性粉末を用いた圧粉磁心
DE102013224989A1 (de) * 2013-12-05 2015-06-11 Siemens Aktiengesellschaft Gamma/Gamma gehärtete Kobaltbasis-Superlegierung, Pulver und Bauteil
CN105244132A (zh) * 2015-11-03 2016-01-13 顾建 一种弱磁性合金材料
CN105401041A (zh) * 2015-11-13 2016-03-16 太仓旺美模具有限公司 一种高耐磨性金属材料
JP6294533B1 (ja) * 2017-04-03 2018-03-14 住友電気工業株式会社 ホウ化鉄材料の製造方法、及びホウ化鉄薄膜材料
CN107620015A (zh) * 2017-08-22 2018-01-23 宁波市鄞州亚大汽车管件有限公司 加油管及其制备工艺

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US5151137A (en) * 1989-11-17 1992-09-29 Hitachi Metals Ltd. Soft magnetic alloy with ultrafine crystal grains and method of producing same
CA2030446C (en) * 1989-11-22 2001-01-23 Yoshihito Yoshizawa Magnetic alloy with ultrafine crystal grains and method of producing same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8480864B2 (en) * 2005-11-14 2013-07-09 Joseph C. Farmer Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

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DE69319513D1 (de) 1998-08-13
CN1037534C (zh) 1998-02-25
JPH0681086A (ja) 1994-03-22
DE69319513T2 (de) 1999-01-14
EP0585940A1 (de) 1994-03-09
CN1092112A (zh) 1994-09-14

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