CN101104907A - Nano-crystal soft-magnetic Fe44Co(43-x)Zr7B5Al(1+x) with high curie temperature - Google Patents

Nano-crystal soft-magnetic Fe44Co(43-x)Zr7B5Al(1+x) with high curie temperature Download PDF

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CN101104907A
CN101104907A CNA2007101181216A CN200710118121A CN101104907A CN 101104907 A CN101104907 A CN 101104907A CN A2007101181216 A CNA2007101181216 A CN A2007101181216A CN 200710118121 A CN200710118121 A CN 200710118121A CN 101104907 A CN101104907 A CN 101104907A
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CN100494454C (en
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毕晓昉
孙瑶
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Beihang University
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Beihang University
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Abstract

The invention discloses a nano-sized soft magnetism Fe44Co43-XZr7B5Al1 plus X alloy with high Curie temperature. The Atomic percentage of X in the nano-sized soft magnetism Fe44Co43-XZr7B5Al1 plus X alloy is 0-6 the nano-sized soft magnetism Fe44Co43-XZr7B5Al1 plus X alloy is prepared by single-roller rapid quenching method, and has a coercivity of 2-100 A/m, Curie temperature of 1004-1015 DEG C, and magnetic intensity of 159-178emu/g.

Description

Nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy
Technical field
The present invention relates to a kind of nanocrystalline magnetically soft alloy material, more particularly say, be meant a kind of nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy.
Background technology
It has high-curie temperature the generator general requirement of using under hot environment (＞600 ℃), and also should have soft magnetic performance at the high-curie temperature environment, could guarantee the works better of generator under hot environment like this.
Soft magnetic materials is meant remanent magnetism (Mr) and all very little (ferromagnetic material of Hc＜800A/m=of coercive force (Hc).The characteristics of this material are that easy magnetization, easy degaussing and magnetic hysteresis loop are narrower.Soft magnetic materials is commonly used to make the iron core of electrical equipment such as generator, transformer, electro-magnet.So-called nano-crystal soft magnetic alloy is a kind of novel soft magnetic materials, and its grain-size is distributed in the remaining noncrystal substrate about 1～100nm.
" HITPERM " nano-crystal soft magnetic alloy that U.S.'s success in 1998 is researched and developed, its basal component is Fe 44Co 44Zr 7B 4Cu 1This nano-crystal soft-magnetic Fe 44Co 44Zr 7B 4Cu 1The Curie temperature of alloy (Tc) is 980 ℃, at coercive force (Hc) 2Oe (being 159A/m) that exchanges under the 4KHz condition.
The Curie temperature of Co element (Tc) is generally 1123 ℃.In FeCo base soft magnetic materials technical field,
It is generally acknowledged that the increase of Co constituent content helps improving the Curie temperature (Tc) of FeCo base soft magnetic materials on the one hand, coercive force can increase with the increase of Co element on the other hand.
Summary of the invention
The objective of the invention is to propose a kind of nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy, this non-retentive alloy replaces the Cu element by interpolation Al element and partly replacing the Co element has improved Fe 44Co 43-XZr 7B 5Al 1+XThe Curie temperature of alloy makes nano-crystal soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XThe environmental adaptation temperature of alloy on the high temperature generator is higher, solves the restriction that high temperature generator use temperature is subjected to the material Curie temperature effectively.
The present invention is a kind of nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy, nano-crystal soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XThe atomic percent of X is 0～6 in the alloy.
Nano-crystal soft-magnetic Fe of the present invention 44Co 43-XZr 7B 5Al 1+XThe advantage of alloy: (1) is by the organizational controls of amorphous nano-crystalline two phase structure, Fe 44Co 43-XZr 7B 5Al 1+XThe coercive force of alloy reaches 2～100A/m, the soft magnetic performance excellence; (2) behind the noncrystal substrate nano-crystallization, the saturation magnetization Ms of unit reaches 159～178emu/g; (3) to Fe 44Co 43-XZr 7B 5Al 1+XWhen alloy carries out the temperature-stable property testing, Fe of the present invention 44Co 43-XZr 7B 5Al 1+XAlloy is with the rising of temperature, and the saturation magnetization Ms of its unit descends slowly, and fall is little, and temperature stability is good; (4) nano-crystal soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XThe Curie temperature of alloy is 1004～1015 ℃, the brilliant soft-magnetic Fe of ratio nano 44Co 44Zr 7B 4Cu 1The Curie temperature of alloy (980 ℃) has improved more than 20 ℃, has higher use temperature; (5) nano-crystal soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XAlloy adopts single-roller rapid quenching with quenching to prepare amorphous and gets rid of band, and its technology is simple, and amorphous formation ability is strong, can realize industrial production.
Description of drawings
Fig. 1 is a nano-crystal soft-magnetic Fe of the present invention 44Co 42Zr 7B 5Al 2The thermogram of the quenching attitude of alloy.
Fig. 2 is a nano-crystal soft-magnetic Fe 44Co 42Zr 7B 5Al 2Alloy is at the magnetic hysteresis loop of 500 ℃ of annealed state.
Fig. 3 is a nano-crystal soft-magnetic Fe 44Co 42Zr 7B 5Al 2The X-ray diffractogram of alloy.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy, its preparation process has:
The first step: press Fe 44Co 43-XZr 7B 5Al 1+XAtomic percent takes by weighing the iron Fe of purity 99.99%, cobalt Co, the zirconium Zr of purity 99.5%, the aluminium Al of purity 99.99% and the ferro-boron bulk of boracic 20% of purity 99.8%;
Second step: alloy melting
The Fe-Co-Zr-B-Al bulk that the first step prepares is made ingot casting with electric arc furnace (the photoelectricity WS-6 of Beijing thing section) melting, and melting condition is heating current 200 ± 20A;
Line cutting clamp dog then, and after block put into 95% acetone soln and carry out ultrasonic cleaning 5～20min, in 99% spirituous solution, carry out ultrasonic surface again and clean 10～25min, take out oven dry and make dry block, stand-by;
30～50 ℃ of bake out temperatures, drying time 15～45min;
The 3rd step: get rid of band
The dry block that second step made is put into the silica tube that single roller gets rid of band machine (HVDS-II), regulate the rotation rotating speed 50～70m/s of single roller, make amorphous ribbon;
The 4th step: crystallization
Amorphous ribbon is put into vacuum heat treatment furnace, be evacuated to 4 * 10 -3Pa, and with ar purging 2～4 times; And then be evacuated to 4 * 10 -3Pa is warming up to 450～680 ℃, insulation 20～120min, and furnace cooling promptly makes the amorphous nano-crystalline soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XAlloy.
Embodiment 1
70um is thick in preparation, the amorphous nano-crystalline soft-magnetic Fe that 3mm is wide 44Co 42Zr 7B 5Al 2Alloy
The first step: press Fe 44Co 42Zr 7B 5Al 2Atomic percent takes by weighing the iron Fe of purity 99.99%, cobalt Co, the zirconium Zr of purity 99.5%, the aluminium Al of purity 99.99% and the ferro-boron bulk of boracic 20% of purity 99.8%; Use electronic balance weighing;
Second step: alloy melting
The Fe-Co-Zr-B-Al bulk that the first step prepares is made ingot casting, melting condition heating current 200A with electric arc furnace (the photoelectricity WS-6 of Beijing thing section) melting;
Line cuts into 5 * 5 * 10mm then 3Fritter, and after block put into 95% acetone soln and carry out ultrasonic cleaning 10min, in 99% spirituous solution, carry out ultrasonic surface again and clean 10min, take out oven dry and make dry block, stand-by;
30 ℃ of bake out temperatures, drying time 30min;
The 3rd step: get rid of band
The dry block that second step made is put into the silica tube that single roller gets rid of band machine (HVDS-II), and the rotation rotating speed of regulating single roller is 68m/s, makes amorphous ribbon;
The 4th step: crystallization
Amorphous ribbon is put into vacuum heat treatment furnace, be evacuated to 4 * 10 -3Pa, and with ar purging 2 times; And then be evacuated to 4 * 10 -3Pa is warming up to 500 ℃, insulation 20min, and furnace cooling promptly makes the amorphous nano-crystalline soft-magnetic Fe 44Co 42Zr 7B 5Al 2Alloy.Referring to shown in Figure 3, " B number " curve is quenching attitude X-ray diffraction analysis figure among the figure, and Fe is described 44Co 42Zr 7B 5Al 2Alloy is non-crystalline state at this moment, and " A number " curve is the X-ray diffraction analysis figure of 500 ℃ of annealed state, and Fe is described 44Co 42Zr 7B 5Al 2It is mutually nanocrystalline to separate out FeCo after the alloy annealing, and grain-size is the nanometer crystalline phase of 12.6nm.Analytical instrument adopts Japanese Rigaku D-MAX2200TC of science, the Cu target, and 40KV, 40mA, scanning speed 6 degree/minute.
Adopt instrument differential scanning calorimeter (Netzsch Sta449C) to survey the amorphous nano-crystalline soft-magnetic Fe 44Co 42Zr 7B 5Al 2The various transition temperatures of alloy, referring to shown in Figure 1, " I number " curve representation differential scanning calorimetric heating curve among the figure, the heating curve of " II number " curve representation thermogravimetric analysis.Wherein, the first initial crystallization temperature is 512.2 ℃, and the second initial crystallization temperature is 701.0 ℃, and α-γ structural transformation peak temperature is 1004.3 ℃, reflect on thermogravimetric (TG) analytic curve that Curie temperature is 1004.6 ℃ when heating up, this test temperature rate is 20 ℃/min.The nano-crystal soft-magnetic Fe that the present invention makes 44Co 42Zr 7B 5Al 2The Curie temperature of alloy is 1004 ℃, the brilliant soft-magnetic Fe of ratio nano 44Co 44Zr 7B 4Cu 1The Curie temperature of alloy (980 ℃) has improved 24 ℃.Adopt nano-crystal soft-magnetic Fe of the present invention 44Co 42Zr 7B 5Al 2Alloy is made the iron core of generator, makes generator have higher use temperature.
In order to obtain Fe 44Co 42Zr 7B 5Al 2The soft magnetic performance of alloy adopts vibrating sample magnetometer (VSM) (Lakeshore 7307 models) that it is carried out the soft magnetic performance test, referring to shown in Figure 2, shows Fe 44Co 42Zr 7B 5Al 2The alloy coercive force is 44A/m, and the unit mass saturation magnetization is 159.37emu/g.
Embodiment 2
70um is thick in preparation, the amorphous nano-crystalline soft-magnetic Fe that 3mm is wide 44Co 39Zr 7B 5Al 5Alloy
The first step: press Fe 44Co 39Zr 7B 5Al 5Atomic percent takes by weighing the iron Fe of purity 99.99%, cobalt Co, the zirconium Zr of purity 99.5%, the aluminium Al of purity 99.99% and the ferro-boron bulk of boracic 20% of purity 99.8%; Use electronic balance weighing;
Second step: alloy melting
The Fe-Co-Zr-B-Al bulk that the first step prepares is made ingot casting, melting condition heating current 220A with electric arc furnace (the photoelectricity WS-6 of Beijing thing section) melting;
Line cuts into 5 * 5 * 10mm then 3Fritter, and after block put into 95% acetone soln and carry out ultrasonic cleaning 20min, in 99% spirituous solution, carry out ultrasonic surface again and clean 25min, take out oven dry and make dry block, stand-by;
45 ℃ of bake out temperatures, drying time 15min;
The 3rd step: get rid of band
The dry block that second step made is put into the silica tube that single roller gets rid of band machine (HVDS-II), and the rotation rotating speed of regulating single roller is 50m/s, makes amorphous ribbon;
The 4th step: crystallization
Amorphous ribbon is put into vacuum heat treatment furnace, be evacuated to 4 * 10 -3Pa, and with ar purging 4 times; And then be evacuated to 4 * 10 -3Pa is warming up to 680 ℃, insulation 100min, and furnace cooling promptly makes the amorphous nano-crystalline soft-magnetic Fe 44Co 39Zr 7B 5Al 5Alloy.
Adopt instrument differential scanning calorimeter (Netzsch Sta449C) to survey the amorphous nano-crystalline soft-magnetic Fe 44Co 39Zr 7B 5Al 5The transition temperature of alloy is 1014.7 ℃ at α-γ structural transformation peak temperature, reflects on thermogravimetric (TG) analytic curve that Curie temperature is 1014.6 ℃ when heating up, and this test temperature rate is 20 ℃/min.Fe 44Co 39Zr 7B 5Al 5The alloy coercive force is 100A/m, and the unit mass saturation magnetization is 177.57emu/g.
Following table is classified the magnetic property of different components after crystallization under the different crystallization conditions is handled as:
Component (at%) Crystallization condition Curie temperature (℃) Coercive force (A/m) Saturation magnetization (emu/g)
Vacuum tightness (Pa) Temperature (℃) Insulation (min)
Fe 44Co 43Zr 7B 5Al 1 4×10 -3 550 60 1009 10 160
Fe 44Co 41Zr 7B 5Al 3 450 120 1007 2 163
Fe 44Co 40Zr 7B 5Al 4 500 80 1007 80 170
Fe 44Co 38Zr 7B 5Al 6 480 100 1011 60 171
Fe 44Co 37Zr 7B 5 Al 7 600 30 1006 70 175
The present invention adopts the nano-crystal soft-magnetic Fe of single-roller rapid quenching with quenching preparation 44Co 43-XZr 7B 5Al 1+XAlloy and nano-crystal soft-magnetic Fe 44Co 44Zr 7B 4Cu 1The alloy phase ratio though reduced the use of Co element, does not reduce its Curie temperature (Tc), on the contrary, because the Al element, makes nano-crystal soft-magnetic Fe of the present invention to the substituting of Cu element and Part of Co element 44Co 43-XZr 7B 5Al 1+XAlloy when having kept original excellent soft magnetic performance, the brilliant soft-magnetic Fe of its Curie temperature (Tc) ratio nano 44Co 44Zr 7B 4Cu 1The Curie temperature of alloy (980 ℃) has improved more than 20 ℃.

Claims (4)

1. nano-crystal soft-magnetic Fe with high-curie temperature 44Co 43-XZr 7B 5Al 1+XAlloy is characterized in that: nano-crystal soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XThe atomic percent of X is 0～6 in the alloy.
2. nano-crystal soft-magnetic Fe according to claim 1 44Co 43-XZr 7B 5Al 1+XAlloy is characterized in that: the nano-crystal soft magnetic alloy component is Fe 44Co 42Zr 7B 5Al 2Or Fe 44Co 43Zr 7B 5Al 1Or Fe 44Co 39Zr 7B 5Al 5
3. nano-crystal soft-magnetic Fe according to claim 1 44Co 43-XZr 7B 5Al 1+XAlloy is characterized in that: coercive force is 2～100A/m, and Curie temperature is 1004～1015 ℃, and the specific magnetising moment is 159～178emu/g.
4. one kind prepares nano-crystal soft-magnetic Fe according to claim 1 44Co 43-XZr 7B 5Al 1+XThe method of alloy is characterized in that having the following steps:
The first step: press Fe 44Co 43-XZr 7B 5Al 1+XAtomic percent take by weighing the iron Fe of purity 99.99%, cobalt Co, the zirconium Zr of purity 99.5%, the aluminium Al of purity 99.99% and the ferro-boron bulk of boracic 20% of purity 99.8%;
Second step: alloy melting
The Fe-Co-Zr-B-Al bulk that the first step prepares is made ingot casting with arc melting, and melting condition is heating current 200 ± 20A;
Line cutting clamp dog then, and after block put into 95% acetone soln and carry out ultrasonic cleaning 5～20min, in 99% spirituous solution, carry out ultrasonic surface again and clean 10～25min, take out oven dry and make dry block, stand-by;
30～50 ℃ of bake out temperatures, drying time 15～45min;
The 3rd step: get rid of band
The dry block that second step made is put into the silica tube that single roller gets rid of the band machine, regulate the rotation rotating speed 50～70m/s of single roller, make amorphous ribbon;
The 4th step: crystallization
Amorphous ribbon is put into vacuum heat treatment furnace, be evacuated to 4 * 10 -3Pa, and with ar purging 2～4 times; And then be evacuated to 4 * 10 -3Pa is warming up to 450～680 ℃, insulation 20～120min, and furnace cooling promptly makes the amorphous nano-crystalline soft-magnetic Fe 44Co 43-XZr 7B 5Al 1+XAlloy.
CNB2007101181216A 2007-06-29 2007-06-29 Nano-crystal soft-magnetic Fe44Co(43-x)Zr7B5Al(1+x) with high curie temperature Expired - Fee Related CN100494454C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102254665A (en) * 2010-05-17 2011-11-23 中国科学院宁波材料技术与工程研究所 Iron-cobalt-based nano-crystalline soft magnetic alloy and preparation method thereof
CN105200298A (en) * 2015-09-08 2015-12-30 杨雯雯 Nanocrystalline soft magnetic alloy material and preparation method thereof
CN108624852A (en) * 2017-03-15 2018-10-09 南京理工大学 A kind of ferrozirconium amorphous multilayer film of high-curie temperature and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102254665A (en) * 2010-05-17 2011-11-23 中国科学院宁波材料技术与工程研究所 Iron-cobalt-based nano-crystalline soft magnetic alloy and preparation method thereof
CN102254665B (en) * 2010-05-17 2014-04-09 苏州宝越新材料科技有限公司 Preparation method of iron-cobalt-based nano-crystalline soft magnetic alloy
CN105200298A (en) * 2015-09-08 2015-12-30 杨雯雯 Nanocrystalline soft magnetic alloy material and preparation method thereof
CN108624852A (en) * 2017-03-15 2018-10-09 南京理工大学 A kind of ferrozirconium amorphous multilayer film of high-curie temperature and preparation method thereof
CN108624852B (en) * 2017-03-15 2020-04-10 南京理工大学 high-Curie-temperature Fe-Zr amorphous multilayer film and preparation method thereof

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