CN102360670B - Composite material with ferrite magnetic layer and amorphous soft magnetic core as well as preparation method thereof - Google Patents
Composite material with ferrite magnetic layer and amorphous soft magnetic core as well as preparation method thereof Download PDFInfo
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- CN102360670B CN102360670B CN201110323862.4A CN201110323862A CN102360670B CN 102360670 B CN102360670 B CN 102360670B CN 201110323862 A CN201110323862 A CN 201110323862A CN 102360670 B CN102360670 B CN 102360670B
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Abstract
The invention provides a composite material with a ferrite magnetic layer and an amorphous soft magnetic core and a preparation method thereof. The composite wire has good functionality. The preparation method has a simple process as well as a low production cost and is suitable for industrial production. The nanometer granular composite material with the ferrite magnetic layer and the amorphous soft magnetic core has components in percentages by weight as follows: 3-6% of Si, 0.5-2% of Zr, 0.1-0.3% of Y, 0.1-0.2% of Ce, 0.6-0.9% of Ni, 2-5% of B, and Fe of the rest.
Description
technical field:
The invention belongs to the electron recombination Material Field, relate to information combined material of a kind of nano particle ferrite magnetosphere amorphous soft magnet core and preparation method thereof.
background technology:
No. CN200910096349.9 application discloses a kind of Fe-based amorphous alloy material and preparation method thereof.The chemical molecular formula of this alloy material is: (Fe
100-aco
a)
x-Dy
y-B
z-Si
w, the x in formula, y, z, w is atomic percentage: 60≤x≤75,5≤y≤25,20≤z≤25,0≤w≤10,0≤a≤10, and x+y+z+w=100.The preparation process of this alloy is as follows: technical pure raw metal and FeB alloy are pressed to the alloy formula batching, adopt vacuum induction melting to become foundry alloy, then with melt spinning, make amorphous thin ribbon.Copper roller linear velocity is 25～40m/s, and cavity air pressure is 0.05MPa, and expulsion pressure is poor is 0.05～0.10MPa.The material purity of component Fe, Co, Dy or the Si of described Fe-based amorphous alloy material is 99.5%～99.9%.Fe-based amorphous alloy material has the wide supercooling liquid phase region of 41K～60K.The base noncrystal alloy magnetic material has high saturation magnetization M
s=83.73emu/g～108.24emu/g, low coercive force H
ci=0.51Oe～0.30Oe.
Problem is that copper roller linear velocity is that 25～40m/s is higher, and institute's energy requirement is large, uneconomical.The amorphous formation ability that this alloy also is described in addition is little, and the physical property of alloy magnetic material is limited.
summary of the invention:
Purpose of the present invention is exactly for above-mentioned technological deficiency, and a kind of ferrite magnetosphere amorphous soft magnet core composite material is provided, and this composite filament has good functional.
Another object of the present invention is to provide a kind of ferrite magnetosphere amorphous soft magnet core composite material and preparation method thereof, and this preparation method's technique is simple, and production cost is low, is suitable for suitability for industrialized production.
The objective of the invention is to be achieved through the following technical solutions:
A kind of ferrite magnetosphere amorphous soft magnet core composite material, it is characterized in that: the weight percentage of its each composition is: 3～6%Si, 0.5-1%Zr, 0.1～0.3%Y, 0.1～0.2%Ce, 0.6-0.9%Ni, 2～5%B, all the other are Fe.
Above-mentioned ferrite magnetosphere amorphous soft magnet core wire composite material preparation method, it is characterized in that: preparation process is as follows:
the amorphous soft magnet core:according to above-mentioned amorphous soft magnet core alloying component, prepared burden, raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1610-1630 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1590-1600 ℃ of remelting tubular type crucible is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 20～24m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.4-0.6;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is the 3-5 micron; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
the present invention has following beneficial effect compared to existing technology:
Amorphous soft magnet core of the present invention adopts Si, Zr, Y, B, Fe to be used in conjunction with, and has guaranteed that ferrous alloy is easily decrystallized.But Y and Ce are used in conjunction with reinforced alloys, guarantee that alloy core material has enough intensity.Wherein element Ni, Y coordinate the crystallization that can suppress alloy.Wherein V can put forward heavy alloyed toughness.
Manganese-zinc ferrite powder in coating and the mutual coupling of amorphous soft magnet core, significantly improved the saturation magnetization of magnetically soft alloy material, obtained lower coercive force simultaneously.
Alloy property of the present invention is in Table 1.
The present invention is by adopting coating way, regulates Nanosized Mn-Zn Ferrite powder in coating and the coupling of inner amorphous soft magnet core, can significantly improve the saturation magnetization of magnetically soft alloy, can keep lower coercive force simultaneously.The present invention adopts iron to do matrix, does not use cobalt, at the cost that has guaranteed to greatly reduce under the high performance condition of material material.Material can be processed in batch, with short production cycle.This composite material preparation process is easy, and the composite material of production has certain superperformance, is convenient to very much suitability for industrialized production.
the accompanying drawing explanation:
The organization chart that Fig. 1 is inner amorphous core.
The dense structure of material is even as seen from Figure 1.
Embodiment
embodiment mono-:
Batching: the weight percentage of each composition is: 3%Si, and 0.5%Zr, 0.1%Y, 0. 1%Ce, 0.6%Ni, 2%B, all the other are Fe.Approximately 3 microns of coating layer thicknesses.Raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1610-1630 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1590-1600 ℃ of remelting tubular type crucible is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 20～24m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.4-0.6;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is 3 microns; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
embodiment bis-:
batching:the weight percentage of each composition is: 6%Si, and 1%Zr, 0.3%Y, 0.2%Ce, 0.9%Ni, 5%B, all the other are Fe.Approximately 5 microns of coating layer thicknesses.
Raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1610-1630 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1590-1600 ℃ of remelting tubular type crucible is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 22m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.5;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is 5 microns; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
embodiment tri-:
Batching: the weight percentage of each composition is: 4%Si, and 0.7%Zr, 0.2%Y, 0.2%Ce, 0.7%Ni, 3%B, all the other are Fe.Approximately 4 microns of coating layer thicknesses.
Raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1610 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1590 ℃ of remelting tubular type crucibles is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 20～24m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.5;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is 4 microns; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
embodiment tetra-: (proportioning components is example in this case scope of design not)
batching:the weight percentage of each composition is: 2%Si, and 0.3%Zr, 0.08%Y, 0.06%Ce, 0.5%Ni, 1%B, all the other are Fe.Coating layer thickness is 2 microns.
Raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1620 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1600 ℃ of remelting tubular type crucibles is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 24m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.6;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is 2 microns; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
embodiment five: (proportioning components is example in this case scope of design not)
Batching: the weight percentage of each composition is: 7%Si, and 2%Zr, 0.5%Y, 0. 3%Ce, 1%Ni, 6%B, all the other are Fe.Coating layer thickness is 6 microns.Raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1620 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1595 ℃ of remelting tubular type crucibles is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 22m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by commercially available granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.4;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is 6 microns; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
Performance parameter in conjunction with each product in following table:
The performance parameter of each product of table 1
| The alloy numbering | Composition | Saturation magnetization M s/ emu/g | Coercive force H ci / e |
| Contrast material | The material that No. CN200910096349.9 application makes | 83.73～108.24? | 0.51O ～0.30O |
| Product one | The product that embodiment mono-makes | 108 | 0．31 |
| Product two | The product that embodiment bis-makes | 110 | 0．28 |
| Product three | The product that embodiment tri-makes | 112 | 0．28 |
| Product four | The product that embodiment tetra-makes | 98 | 0．34 |
| Product five | The product that embodiment five makes | 102 | 0．30 |
By upper Biao Ke get, the product one made by the present invention, product two and three products have all improved saturation magnetization and have reduced coercive force.The performance specification of product five and product six, the constituent element composition of composite material is not in the composition range of design, and the material saturation magnetization can reduce, and coercive force can increase.Reason is constituent element composition deficiency, and the effect of alloying element is inadequate; The constituent element composition is too much, can form unnecessary compound, has reduced the magnetic property of material.
Claims (1)
1. a ferrite magnetosphere amorphous soft magnet core wire composite material preparation method, it is characterized in that: preparation process is as follows:
the amorphous soft magnet core:according to weight percentage, be: 3～6%Si, 0.5-1%Zr, 0.1～0.3%Y, 0.1～0.2%Ce, 0.6-0.9%Ni, 2～5%B, all the other are prepared burden for the alloying component of Fe, raw material Si, Zr, Y, Ce, Ni, B, the purity of Fe all is greater than 99.9%, raw material is put into to the vaccum sensitive stove melting, smelting temperature is 1610-1630 ℃, obtain foundry alloy, then the remelting tubular type crucible of putting into the vacuum induction quick quenching furnace carries out remelting, the top layout that remelting temperature is 1590-1600 ℃ of remelting tubular type crucible is the 2-4mm place under quick quenching furnace runner wheel rim, above-mentioned foundry alloy is placed in remelting tubular type crucible and melts, overflow the runner EDGE CONTACT with rotation after alloy molten from the crucible top under ar gas acting, the amorphous soft magnet core B alloy wire that the formation diameter is the 100-110 micron, the rotational line speed of runner wheel rim is 20～24m/s,
coating is prepared:add in proportion tetraethoxysilane, γ-methacryloxypropyl trimethoxy silane and ethanol in the there-necked flask of blender is housed, its mol ratio is 3:2:2; Under agitation splash into acetic acid, addition is 5g/100mL, after room temperature reaction 3h, adds methyl methacrylate and initator azodiisobutyronitrile, and addition is respectively 10g/100mL and 5g/100mL, and then under room temperature, stirring 20min, to obtain colloidal sol stand-by; Then the manganese-zinc ferrite powder and the colloidal sol that by granularity, are 50-100nm are mixed to get coating, and the weight ratio of manganese-zinc ferrite powder and colloidal sol is 6:0.4-0.6;
apply:then coating is applied on above-mentioned amorphous soft magnet core B alloy wire, coating layer thickness is the 3-5 micron; Through the 15min baking-curing, obtain soft-magnetic alloy powder coating amorphous soft magnet core magnetosensitive composite wire material, baking temperature is 130 ℃.
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| CN105632676A (en) * | 2016-04-04 | 2016-06-01 | 苏州思创源博电子科技有限公司 | Preparation method of iron-nickel-based soft magnetic alloy |
| CN105839005A (en) * | 2016-04-04 | 2016-08-10 | 苏州思创源博电子科技有限公司 | Preparation method for iron-aluminum-based magnetic material with coating |
| CN108950345A (en) * | 2018-08-16 | 2018-12-07 | 安徽信息工程学院 | inorganic functional composite material |
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| JPS58139408A (en) * | 1982-02-15 | 1983-08-18 | Hitachi Metals Ltd | Wound iron core |
| JP3623970B2 (en) * | 1992-06-17 | 2005-02-23 | 三井化学株式会社 | Fe-based soft magnetic alloy and manufacturing method |
| US6416879B1 (en) * | 2000-11-27 | 2002-07-09 | Nippon Steel Corporation | Fe-based amorphous alloy thin strip and core produced using the same |
| CN1173061C (en) * | 2002-08-16 | 2004-10-27 | 安泰科技股份有限公司 | Iron-base bulk amorphous soft-magnetic alloy material |
| CN1166800C (en) * | 2002-09-13 | 2004-09-15 | 安泰科技股份有限公司 | Iron based amorphous soft magnetization alloy |
| WO2008018179A1 (en) * | 2006-08-11 | 2008-02-14 | Mitsui Chemicals, Inc. | Antenna core and antenna |
| CN101572152B (en) * | 2009-03-11 | 2011-03-30 | 南京信息工程大学 | Soft magnetic amorphous alloy wire and preparation method thereof |
| CN102142309B (en) * | 2010-12-30 | 2013-04-10 | 长春工业大学 | Block amorphous/ferrite soft magnetic composite material and preparation method thereof |
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