CN101572153B - Amorphous soft magnetic alloy and inductance component using the same - Google Patents

Amorphous soft magnetic alloy and inductance component using the same Download PDF

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CN101572153B
CN101572153B CN2009101276380A CN200910127638A CN101572153B CN 101572153 B CN101572153 B CN 101572153B CN 2009101276380 A CN2009101276380 A CN 2009101276380A CN 200910127638 A CN200910127638 A CN 200910127638A CN 101572153 B CN101572153 B CN 101572153B
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浦田显理
藤原照彦
松元裕之
山田健伸
井上明久
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Northeastern University China
Tokin Corp
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NEC Tokin Corp
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Abstract

An amorphous soft magnetic alloy belt material prepared by the amorphous soft magnetic alloy is disclosed. The amorphous soft magnetic alloy has a composition expressed by a formula of (Fe[1-alpha]TM[alpha])[100-w-x-y-z]PwBxLySiz, wherein unavoidable impurities are contained, TM is at least one selected from Co and Ni, L is at least one selected from the group consisting of Al, V, Cr, Y, Zr, Mo, Nb, Ta, and W, 0<=alpha<=0.98, 2<=w<=16 at %, 2<=x<=16 at %, 0<y<=10 at %, and 0<=z<=8 at %). The depth of the amorphous soft magnetic alloy is 1 to 200[mu]m.

Description

Amorphous soft magnetic and the inductance component that uses this alloy
The application is dividing an application of patent application case (denomination of invention being " amorphous soft magnetic and the inductance component that uses this alloy " for February 2 2007 applying date, application number 200710006386.7).
Technical field
The present invention relates to a kind of amorphous soft magnetic, also relate to the web, band, powder, element and the parts that use this alloy in addition.
Background technology
Amorphous magnetic alloy rises prior to Fe-P-C, develops low-loss material Fe-Si-B, high saturation magnetic flux metric density (Bs) material Fe-B-C etc. afterwards.These materials are because loss is low is supposed to as transformer material, but because its cost is high and with to compare its Bs such as the conventional material of silicon steel sheet lower, so also be not used widely.In addition, because these amorphous alloys requirement cooling rates are 10 5K/sec or higher is so can only produce the band that thickness is merely about 200 μ m (laboratory highest level).Therefore, must with said band be wound in the magnetic core or with said tape lamination in magnetic core, this has greatly limited the application of amorphous alloy.
Since the latter half 1980s, begun to develop the alloy system of so-called metal glass, in this alloy system, with at that time before amorphous alloy opposite, observe glass transition and the supercooled liquid scope occurred at the low temperature side of crystallization temperature.The supercooled liquid scope is considered to be related to the stability of glass structure.Therefore, it is very good that the noncrystalline of this alloy system forms ability, and this never occurred before at that time.For example, have been found that Ln-Al-TM, Zr-Al-Ni, and have been found that Pd-Cu-Ni-P base alloy, therefrom can make the metal glass block element of about several millimeters thick respectively.Since middle 1990s, also found the Fe base metal glass, and reported and to have realized that thickness is the composition of 1mm or above metal glass block element.For example, found Fe-(Al, Ga)-(P, C, B, Si) (non-patent literature 1:Mater.Trans., JIM, 36 (1995), 1180), Fe-(Co, Ni)-(Zr, Hf, Nb)-B (non-patent literature 2:Mater.Trans., JIM, 38 (1997), 359; Patent documentation 1: japanese unexamined patent open (JP-A) No.2000-204452); Fe-(Cr; Mo)-and Ga-P-C-B (patent documentation 2: japanese unexamined patent open (JP-A) No.2001-316782), Fe-Co-RE-B (patent documentation 3: japanese unexamined patent open (JP-A) No.2002-105607) etc.Yet, with the alloy phase ratio of routine,, these alloys form ability although all having improved noncrystalline separately, and exist owing to containing a large amount of non magnetic one-tenth and grade and make the problem that saturation flux density is low.Be difficult to make that noncrystalline formation ability and magnetic property are all satisfactory.
Usually known amorphous alloy such as Fe-Si-B and Fe-P-C, is known high magnetic permeability and low-loss material, therefore is suitable for transformer core, magnetic head etc.Yet because that noncrystalline forms ability is low, thickness is the band of about 20 μ m and only becomes commercialized with the wire rod that thickness is about 100 μ m, and they also should be formed magnetic core lamination or winding in addition.Therefore, the degree of freedom of vpg connection is minimum.On the other hand, process dust core through the low-loss noncrystalline powder that will have good soft magnet performance and can realize three-dimensionally shapedly, therefore this be regarded as very hopeful.Yet, because it is not enough to form ability according to any said composition noncrystalline, so be difficult to adopt water atomization method or similar approach to make powder.In addition, if use the iron-nickel alloy material or the similar material of the cheapness that contains impurity, expection reduces noncrystalline and forms ability so, thereby reduces amorphous consistency, therefore causes weakening of soft magnet performance.With regard to the Fe base metal glass, all very strong although their noncrystalline separately forms ability equally, because they contain a large amount of nonmetal compositions, and the content of iron series element is very low, so be difficult to satisfy simultaneously the requirement of its magnetic property.In addition, because glass transition temperature is higher, the problem that heat treatment temperature etc. raises can appear equally also.
Summary of the invention
Therefore the objective of the invention is to, propose a kind of amorphous soft magnetic, through alloy composition being selected and being optimized, can make it have the supercooled liquid scope, and noncrystalline formation ability is very high, soft magnet performance is also fine.
Another object of the present invention is, proposes all to use band, powder, high frequency magnetic core, the block elements of this amorphous soft magnetic.
In order to realize aforementioned purpose; After process is carried out lucubrate to various alloy composites; Inventor of the present invention finds; Join in the Fe-P-B base alloy and through one or more elements that will from Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choose and to confirm, can realize improving noncrystalline and form ability and tangible supercooled liquid scope occurs, and accomplish the present invention those composition component.
In addition; Inventor of the present invention finds; Join in the Fe-P-B base alloy and in addition Ti, C, Mn and Cu element are joined in the Fe-P-B base alloy and to those composition component through one or more elements that will from Al, Cr, Mo and Nb, choose and confirm; Can realize improving noncrystalline and form ability and tangible supercooled liquid scope occurs, this has further improved alloy composite, and has accomplished the present invention.
According to an aspect of the present invention, a kind of amorphous soft magnetic band that is made by amorphous soft magnetic is provided, the expression formula of the composition of said amorphous soft magnetic is (Fe 1-αTM α) 100-w-x- Y-zP wB xL ySi z, wherein containing unavoidable impurities, TM is from Co and Ni, choose at least a; L is from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choose at least a; 0≤α≤0.98,2 atom %≤w≤16 atom %, 2 atom %≤x≤16 atom %; 0 atom %<y≤10 atom % and 0 atom %≤z≤8 atom %, the thickness of wherein said amorphous soft magnetic band are 1 to 200 μ m.
According to a further aspect in the invention, a kind of amorphous soft magnetic band of being processed by amorphous soft magnetic is provided, the expression formula of the composition of said amorphous soft magnetic is (Fe 1-αTM α) 100- W-x-y-zP wB xL ySi z(Ti pC qMn rCu s), wherein containing unavoidable impurities, TM is from Co and Ni, choose at least a, L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a; 0≤α≤0.3,2 atom %≤w≤18 atom %, 2 atom %≤x≤18 atom %, 15 atom %≤w+x≤23 atom %; 1 atom %≤y≤5 atom %, 0 atom %≤z≤4 atom %, wherein all to be illustrated in the gross mass of Fe, TM, P, B, L and Si be 100 o'clock interpolation ratio for each p, q, r and s; And confirm as 0≤p≤0.3,0≤q≤0.5,0≤r≤2; 0≤s≤1,0<r+s≤3, the thickness of wherein said amorphous soft magnetic band are 1 to 200 μ m.
According to another aspect of the invention, provide a kind of and twine the magnetic core that forms through above-mentioned amorphous soft magnetic band being carried out annular.
According to a further aspect in the invention, provide a kind of and said amorphous soft magnetic band is carried out the above-mentioned magnetic core that the annular winding forms through insulator.
In accordance with a further aspect of the present invention, provide a kind of and carry out the range upon range of magnetic core that forms through sheet spare or part to the basic identical shape of above-mentioned amorphous soft magnetic band.
Through Fe amorphous alloy composition of the present invention is selected, can obtain having supercooled liquid scope and noncrystalline and form very high, the good alloy of soft magnet performance of ability.
In addition, according to the present invention, can make the band, powder, high frequency magnetic core and the block elements that use noncrystalline to form the very high and good this amorphous soft magnetic of soft magnet performance of ability.
Description of drawings
Fig. 1 is the exterior perspective view according to an instance of the basic structure of high frequency magnetic core of the present invention;
Fig. 2 is for through being wrapped in coil the exterior perspective view of the inductance component that forms on the high frequency magnetic core shown in Figure 1;
Fig. 3 is the exterior perspective view according to another instance of the basic structure of high frequency magnetic core of the present invention;
Fig. 4 is for through being wrapped in coil the exterior perspective view of the inductance component that forms on the high frequency magnetic core shown in Figure 3;
Fig. 5 is the exterior perspective view according to the another instance of the basic structure of high frequency magnetic core of the present invention;
Fig. 6 is the Fe with different-thickness 78P 8B 10Mo 4The XRD result curve figure that band obtains according to X-ray diffraction (XRD) method; With
Fig. 7 is the Fe with varying particle size 78P 8B 10Mo 4The result curve figure that powder obtains according to X-ray diffraction (XRD) method.
Embodiment
Set forth in detail in the face of the present invention down.
At first, the first basic composition of amorphous soft magnetic of the present invention is set forth.
Inventor of the present invention is (Fe through many-sided discovering when passing through to select the composition expression formula to confirm alloy composite 1-αTM α) 100-w-x-y-zP wB xL ySi zThe time, can obtain the amorphous soft magnetic powder that excellent magnetic and noncrystalline form the high economy of ability, wherein contain unavoidable impurities; 0≤α≤0.98,2 atom %≤w≤16 atom % wherein, 2 atom %≤x≤16 atom %; 0 atom %<y≤10 atom %, 0 atom %≤z≤8 atom %, Fe; P; B and Si represent iron, phosphorus, boron and silicon respectively, and TM is from Co (cobalt) and Ni (nickel), choose at least a, and L is from the group that is made up of Al (aluminium), V (vanadium), Cr (chromium), Y (yttrium), Zr (zirconium), Mo (molybdenum), Nb (niobium), Ta (tantalum) and W (tungsten), choose at least a; And find to obtain high magnetic and good noncrystalline formation ability, can obtain by having block elements, ember, thin strip and the powder that the said said alloy of forming is processed through said amorphous alloy is suitably handled.
For example, the amorphous soft magnetic with said composition has good noncrystalline and forms ability, and available magnetic core thickness is 0.5mm or thicker, and cross-sectional area is 5mm 2Or littler, these sizes never occur traditionally, and its magnetic permeability in broadband or broadband high with have the high saturation magnetic flux metric density.
For example, with regard to noncrystalline magnetic band with said composition, through said band is twined can obtain having similar magnetic can magnetic core and through adopt insulator with said tape lamination or the range upon range of magnetic core that forms with its performance of further raising.
For example; With regard to noncrystalline Magnaglo with said composition; Through said powder suitably being mixed with adhesive and using rolled-up stock or molding die to carry out molded; And through powder surface being carried out oxidation processes or insulation coating, the dust core that can obtain having similar excellent performance.
That is to say, according to the present invention, be (Fe when passing through to select the composition expression formula to confirm selected alloy composite 1-αTM α) 100-w-x-y-zP wB xL ySi zThe time, can obtain the amorphous soft magnetic powder that excellent magnetic, noncrystalline form the fabulous economy of ability height and powder filling capacity, wherein contain the unavoidable impurities element; 0≤α≤0.98,2 atom %≤w≤16 atom % wherein, 2 atom %≤x≤16 atom %; 0 atom %<y≤10 atom %, 0 atom %≤z≤8 atom %, TM is from Co and Ni, choose at least a; L is from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choose at least a, in addition, owing to use rolled-up stock or molding die or analog; So that according to a kind of suitable manufacturing process; Through resulting powder being carried out oxidation processes or applying insulating barrier, resulting powder is formed molded product, produce dust core; So obtain the dust core of high magnetic permeability; This dust core is the magnetic permeability characteristic good on the broadband, and this never occurs under conventional situation, and the manufacturing cost of the high frequency magnetic core of therefore being processed by the soft magnetic material with high saturation magnetic flux metric density and high resistivity is lower.In addition, by twine a last circle or a multi-turn coil around said high frequency magnetic core, can make the inductance component of low-cost and high-performance, this never occurs under conventional situation, and therefore this inductance component is highly profitable industrial.
Wherein, first instance according to the of the present invention first basic composition provides a kind of amorphous magnetic alloy, and the expression formula of its composition is Fe 100-w-x-yP wB xL y(wherein Fe is a main component, can contain unavoidable impurities, and L is at least a element of from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choosing; 2 atom %≤w≤16 atom %; 2 atom %≤x≤16 atom %, 0 atom %<y≤10 atom %), it is good that the vitrifying of this alloy forms ability; Soft magnet performance is good, and has the supercooled liquid scope.
According to second instance of the present invention, a kind of amorphous magnetic alloy is provided, the expression formula of its composition is Fe 100-w-x-yP wB xL ySi z, wherein Fe is a main component, can contain unavoidable impurities; L is at least a element of from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choosing, 2 atom %≤w≤16 atom %, 2 atom %≤x≤16 atom %; 0 atom %<y≤10 atom %, 0 atom %<z≤8 atom %, it is good that the vitrifying of this alloy forms ability; Soft magnet performance is good, and has the supercooled liquid scope.
According to the 3rd instance of the present invention, a kind of amorphous magnetic alloy is provided, the expression formula of its composition is (Fe 1-αTM α) 100-w-x-yP wB xL y, wherein Fe is a main component, can contain unavoidable impurities; TM is at least a element of from Co and Ni, choosing, and L is at least a element of from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choosing, 0<α≤0.98; 2 atom %≤w≤16 atom %, 2 atom %≤x≤16 atom %, 0 atom %<y≤10 atom %; It is good that the vitrifying of this alloy forms ability, and soft magnet performance is good, and has the supercooled liquid scope.
According to the 4th instance of the present invention, a kind of amorphous magnetic alloy is provided, the expression formula of its composition is (Fe 1-αTM α) 100-w-x-yP wB xL ySi z, wherein Fe is a main component, can contain unavoidable impurities, TM is at least a element of from Co and Ni, choosing; L is at least a element of from the group that is made up of Al, Mo, Nb, Ta, W, V and Cr, choosing, 0<α≤0.98,2 atom %≤w≤16 atom %; 2 atom %≤x≤16 atom %, 0 atom %<y≤10 atom %, 0 atom %<z≤8 atom %; It is good that the vitrifying of this alloy forms ability, and soft magnet performance is good, and has the supercooled liquid scope.
As stated, in the present invention, soft magnet performance and noncrystalline form ability and are improved through said composition being limited and making it have the supercooled liquid scope.According to the present invention, when the supercooled liquid scope surpassed 20 ℃, soft magnet performance was better and noncrystalline formation ability is stronger.And supercooled liquid scope medium viscosity reduces rapidly.Therefore can utilize VISCOUS FLOW deformation to process.
According to the present invention, in aforementioned arbitrary instance, a kind of noncrystalline soft magnetic components is provided, when temperature raise, the noncrystalline soft magnetic components had 520 ℃ or begin temperature less than 520 ℃ glass transition.
According to the present invention, main component is Fe, P and B, and glass transition temperature is 450 ℃ to 500 ℃.The conventional compositions (Fe that such temperature is disclosed than non-patent literature 3 (Mat.Trans.43 (2002) pp.766-769) with supercooled liquid scope 0.75Si 0.10B 0.15) 96Nb 4Low about 100 ℃.Because the temperature required decline of heat treatment; Thereby be convenient to heat-treat; And through in addition heat-treat for a long time being lower than under the temperature of glass transition temperature; Can improve soft magnet performance widely, thereby can heat-treat simultaneously with copper cash, bobbin, resin etc. such as the noncrystalline magnetic element of band or dust core.
To set forth the second basic composition of amorphous soft magnetic of the present invention now, this amorphous soft magnetic also contains (Ti in addition in the aforementioned first basic composition pC qMn rCu s).
Inventor of the present invention finds, is (Fe through selecting the expression formula with the composition of confirming selected alloy 1-αTM α) 100-w-x-y-zP wB xL ySi z(Ti pC qMn rCu s), can obtain excellent magnetic and noncrystalline and form the high amorphous soft magnetic powder of ability, wherein contain unavoidable impurities; 0≤α≤0.3,2 atom %≤w≤18 atom %, 2 atom %≤x≤18 atom %; 15 atom %<w+x≤23 atom %, 1 atom %≤y≤5 atom %, 0 atom %≤z≤4 atom %; TM is from Co and Ni, choose at least a, and L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a, 0≤p≤0.3; 0≤q≤0.5; 0≤r≤2,0≤s≤1, wherein all to be illustrated in the gross mass of Fe, TM, P, B, L, Si be 100 o'clock interpolation ratio for each p, q, r and s; And find to obtain stronger magnetic and good noncrystalline formation ability, can obtain by having block elements, ember, thin strip and the powder that the said said alloy of forming is processed through said amorphous alloy is suitably processed.
For example, the amorphous soft magnetic with said composition has good performance and has showed that good noncrystalline forms ability, and available magnetic core thickness is 0.5mm or thicker, and cross-sectional area is 5mm 2Or littler, these sizes are never to occur under the conventional situation, and its wide band magnetic permeability high with have the high saturation magnetic flux metric density.
For example, with regard to noncrystalline magnetic band with said composition, through said band is twined can obtain having similar magnetic can magnetic core and through utilize insulator with said tape lamination or the range upon range of magnetic core that forms with its performance of further raising.
For example; With regard to noncrystalline Magnaglo with said composition; Through said powder suitably being mixed with adhesive and using rolled-up stock or molding die to carry out molded; And through the surface of powder being carried out oxidation processes or at the surface applied insulating barrier of powder, the dust core that can obtain having similar excellent performance.
That is to say, according to the present invention, be (Fe when passing through to select the composition expression formula to confirm selected alloy composite 1-αTM α) 100-w-x-y-zP wB xL ySi z(Ti pC qMn rCu s) time, can obtain excellent magnetic and noncrystalline and form the high amorphous soft magnetic powder of ability through improving, wherein contain the unavoidable impurities element, wherein TM is from Co and Ni, choose at least a; L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a, 0≤α≤0.3,2 atom %≤w≤18 atom %; 2 atom %≤x≤18 atom %, 15 atom %≤w+x≤23 atom %, 1 atom %≤y≤5 atom %; 0 atom %≤z≤4 atom %, 0≤p≤0.3,0≤q≤0.5; 0≤r≤2,0≤s≤1, wherein all to be illustrated in the gross mass of Fe, TM, P, B, L, Si be 100 o'clock interpolation ratio for each p, q, r and s; In addition, owing to use rolled-up stock or analog, so that according to suitable manufacturing process; To carry out oxidation processes or apply the powder that insulating barrier obtains forming molded product, produce dust core, so obtain the dust core of high magnetic permeability; This dust core is adapted at representing good magnetic permeability characteristic on the broadband magnetic, and this never occurs under conventional situation, and the manufacturing cost of the high frequency magnetic core of therefore being processed by the soft magnetic material with high saturation magnetic flux metric density and high resistivity is lower.
Wherein, be example with basic composition 2 of the present invention, a kind of amorphous magnetic alloy is provided, the expression formula of its composition is following, and it is very high that the noncrystalline of said alloy forms ability, and soft magnet performance is good, and has the supercooled liquid scope.
That is to say that according to the instance about basic composition 2 of the present invention, a kind of amorphous soft magnetic is provided, the expression formula of its composition is (Fe 1-αTM α) 100-w-x-yP wB xL ySi z(Ti pC qMn rCu s), wherein TM is from Co and Ni, choose at least a, L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a, 0≤α≤0.3; 2≤w≤18,2≤x≤18,15≤w+x≤23,1≤y≤5; 0≤z≤4,0≤p≤0.3 quality %, 0≤p≤0.3,0≤q≤0.5; 0≤r≤2,0≤s≤1, wherein all to be illustrated in the gross mass of Fe, TM, P, B, L, Si be 100 o'clock interpolation ratio for each p, q, r and s; And Tg (being glass transition temperature) is 520 ℃ or lower, and Tx (being crystallization start temperature) is 550 ℃ or lower, and the supercooled liquid scope of being represented by Δ Tx=Tx-Tg is 20 ℃ or bigger.
Amorphous soft magnetic is characterised in that it has aforementioned component, and Tg (being glass transition temperature) is 520 ℃ or lower, and Tx (being crystallization start temperature) is 550 ℃ or lower, and is 20 ℃ or bigger by the supercooled liquid scope that Δ Tx=Tx-Tg representes.Because Tg is 520 ℃ or lower, therefore being expected at the heat treatment temperature that is lower than conventional temperature annealing effect occurs, thereby can after magnet-wire is twined, heat-treat.When having served as cold liquid scope above 20 ℃, soft magnet performance is fabulous and noncrystalline formation ability is very high.And supercooled liquid scope medium viscosity reduces rapidly, therefore can utilize VISCOUS FLOW deformation to process.
According to the present invention, amorphous soft magnetic has the first or second basic composition, and its Curie temperature is 240 ℃ or higher.In this amorphous soft magnetic, if Curie temperature is low, magnetic property so at high temperature will worsen.Therefore, Curie temperature is limited in 240 ℃ or higher.
In addition; Inventor of the present invention finds; Through twine last circle or many turn coil around the high frequency magnetic core of processing by amorphous soft magnetic powder with aforementioned basic composition 1 or 2, can make the inductance component of low-cost and high-performance, this never occurs under conventional situation.
In addition, inventor of the present invention finds, limits through the granular size to noncrystalline soft magnetic metal powder (it forms expression formula as aforementioned basic composition 1 or 2), can obtain better dust core aspect the core loss under high frequency.
In addition, inventor of the present invention finds, through enclosing under the state in the magnetic at winding around, adopts press molding that magnet and winding around are formed integral body together, can obtain being suitable for the inductance component of big electric current under the high frequency.
Here; For the resistivity that increases moulded product it is carried out molded before; Alloy powder can be by thermal oxidation in air; Can under the temperature that is equal to or higher than as the softening point of the resin of adhesive, carry out moldedly,, perhaps can carry out molded in the supercooled liquid scope of alloy powder for the density that further increases moulded product so that obtain the high density molded product.
Particularly; Mixture through add the adhesive of said amorphous soft magnetic powder to amorphous soft magnetic powder with aforementioned basic composition 1 with the predetermined quality percentage carries out molded; Can obtain said moulded product, the composition expression formula of said basic composition 1 is (Fe 1- αTM α) 100-w-x-y-zP wB xL ySi z, wherein contain the unavoidable impurities element, 0≤α≤0.98; 2 atom %≤w≤16 atom %; 2 atom %≤x≤16 atom %, 0 atom %<y≤10 atom %, 0 atom %≤z≤8 atom %; TM is from Co and Ni, choose at least a, and L is from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choose at least a.
About having the amorphous soft magnetic powder of aforementioned basic composition 2, the expression formula of its composition is (Fe 1-αTM α) 100-w-x-y-zP wB xL ySi z(Ti pC qMn rCu s), wherein contain the unavoidable impurities element, 0≤α≤0.3,2 atom %≤w≤18 atom %; 2 atom %≤x≤18 atom %, 15 atom %≤W+x≤23 atom %, 1 atom %≤y≤5 atom %, 0 atom %≤z≤4 atom %; 0≤p≤0.3 quality %, 0≤q≤0.5 quality %, 0≤r≤2 quality %; 0≤s≤1 quality %, TM is from Co and Ni, choose at least a, L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a.
To set forth in detail respectively the forming of alloy composite alloy composite of noncrystalline soft magnetic metal powder of the present invention here.
Main component Fe element is used to produce magnetic and is that to obtain the high saturation magnetic flux metric density necessary.Part Fe can be replaced by Co that representes with TM or Ni.With regard to Co, if require that the high saturation magnetic flux metric density is arranged, so the content of Co be preferably 0.05 or above and 0.2 or below.On the other hand, with regard to Ni, adding Ni can increase the supercooled liquid scope and reduce Bs, so the content of Ni is preferably 0.1 or still less.Just reduce material cost, preferably do not add expensive Co or Ni.
According to the present invention, P is necessary element, and its content is 2 atom % or above and 18 atom % or following, but its content is 16 atom % or following when being added with Ti, C, Mn and Cu.The content of P is confirmed as 2 atom % or above and 18 atom % or following or 16 atom % or following reason to be; When the content of P is lower than 2 atom %; The supercooled liquid scope will reduce and noncrystalline formation ability can reduce; And when its content surpassed 18 atom % or 16 atom %, Curie temperature all can reduce with noncrystalline formation ability and the supercooled liquid scope also can reduce.Preferably the content with P is set in 2 atom % or above and 12 atom % or following.
According to the present invention, B is essential element, and its content is 2 atom % or above and 18 atom % or following, but its content is 16 atom % or following when being added with Ti, C, Mn and Cu.The content of B is confirmed as 2 atom % or above and 18 atom % or following or 16 atom % or following reason to be; When the content of B is lower than 2 atom %; Curie temperature and noncrystalline form that ability all can reduce and the supercooled liquid scope also can reduce; And when its content surpassed 18 atom % or 16 atom %, the supercooled liquid scope will reduce and noncrystalline formation ability can reduce.Preferably the content with B is set in 6 atom % or above and 16 atom % or following.
When being added with Ti, C, Mn and Cu, the total content of P and B is 15 atom % or above and 23 atom % or following.The total content of P and B is confirmed as 15 atom % or above and 23 atom % or following reason be, when said total content was lower than 15 atom % or surpasses 23 atom %, the supercooled liquid scope will reduce and noncrystalline forms ability and can reduce.The total content of P and B is preferably 16 atom % or above and 22 atom % or following.
L is the element that the noncrystalline that obviously improves the Fe-P-B alloy forms ability, and its content is 10 atom % or following, but its content is 5 atom % or following when being added with Ti, C, Mn and Cu.According to the present invention, the content of L is confirmed as 10 atom % or following or 5 atom % or following reason be, when the content of L surpassed 10 atom % or 5 atom %, saturation flux density can significantly reduce and Curie temperature also can significantly reduce.The reason that the content of L is confirmed as above 1% or 0% is, when the content of L is less than 1% or 0%, can't form amorphous phase.
Si can be used for replacing the P of Fe-P-B alloy and the element of B, and can improve noncrystalline and form ability, and its content is 8 atom % or following, but its content is 4 atom % or following when being added with Ti, C, Mn and Cu.The content of Si is confirmed as 8 atom % or following or 4 atom % or following reason to be; When the content of Si surpasses 8 atom % or 4 atom %; Glass transition temperature and crystallization temperature all can rise, and the supercooled liquid scope then can reduce and noncrystalline formation ability can reduce.
Ti, Mn and Cu are the elements that effectively improves the corrosion resistance of alloy.The content of Ti is confirmed as 0.3 quality % or following reason is, when the content of Ti surpassed 0.3 quality %, noncrystalline formed ability and will significantly reduce.The content of Mn is confirmed as 2 quality % or following reason is, when the content of Mn surpassed 2 quality %, saturation flux density will significantly reduce and Curie temperature also can significantly reduce.The content of Cu is confirmed as 1 quality % or following reason is, when the content of Cu surpassed 1 quality %, noncrystalline formed ability and will significantly reduce.C is the element that effectively improves the Curie temperature of alloy.The content of C is confirmed as 0.5 quality % or following reason is, when the content of C surpassed 0.5 quality %, noncrystalline forms ability and will significantly reduce, and was the same as the situation of Ti.
The amorphous soft magnetic powder adopts water atomization method (water atomizing method) or aerosolization method (gas atomizing method) to produce, and preferably its granularity at least 50% or more than be 10 μ m or bigger.The water atomization method is produced the method for a large amount of alloy powders in particular at low cost, and in industry, to adopt this method to produce said powder be very useful.Yet, with regard to traditional noncrystalline composition, its granular size be 10 μ m or bigger alloy powder by crystallization, so its magnetic property significantly worsens, the result, product yield significantly reduces, thereby this point has hindered its industrialization.On the other hand and since when granular size be 150 μ m or more hour, the alloy composite of noncrystalline soft magnetic metal powder of the present invention is easy to amorphous materialization, so product yield is higher, thereby be highly profitable with regard to this point of cost.In addition because the alloy powder that adopts the water atomization method to produce has been formed with suitable oxide-film on powder surface, so through with mixed with resin in alloy powder and form the magnetic core that moulded product can easily obtain having high resistivity.With regard in the employing water atomization method of this place explanation alloy powder of producing and the alloy powder that adopts the aerosolization method to produce any; If it is being equal to or less than under the temperature conditions of crystallization temperature in air by heat treatment; Will form better oxidation film so, therefore improve the resistivity of the magnetic core of processing by this alloy powder.This point can reduce core loss.On the other hand, with regard to the high-frequency inductor parts, known metal dust through use fine particle size can reduce eddy current loss.Yet; With regard to usually known alloy composite, have shortcoming, promptly when the center granular size be that mean particle size is 30 μ m or more hour; Powder at production period by significantly oxidation, the performance that therefore is difficult to utilize the powder of common water atomization device fabrication to obtain being scheduled to.On the other hand, because the alloy corrosion resistance of noncrystalline soft magnetic metal powder is very high, so even the particles of powder size still can relatively easily make the good powder of the performance with a spot of oxygen in thinner hour, this is more useful.
Basically, through will being mixed in the noncrystalline soft magnetic metal powder with 10 quality % or lower amount, and using rolled-up stock or adopt the molded moulded product that obtains, make high frequency magnetic core thus such as the adhesive of silicone resin.
Through in rolled-up stock or moulded parts, carrying out compression forming, can obtain moulded product thus to the noncrystalline soft magnetic metal powder with the mixture that 5 quality % or amount still less are added to adhesive wherein.In this case, the powder filling rate of moulded product is 70% or more, when applying 1.6 * 10 4Magnetic density is 0.4T or bigger during the magnetic field of A/m, and resistivity is 1 Ω cm or bigger.When magnetic density is that 0.4T or more and resistivity are 1 Ω cm or when bigger, the performance of moulded product is better than FERRITE CORE, so its validity obtains increasing.
In addition; Through under the temperature conditions of the softening point that is equal to or higher than adhesive; In rolled-up stock, carry out compression forming to the noncrystalline soft magnetic metal powder with the mixture that 3 quality % or amount still less are added to adhesive wherein, can obtain moulded product thus.In this case, the powder filling rate of moulded product is 80% or more, when applying 1.6 * 10 4Magnetic density is 0.6T or bigger during the magnetic field of A/m, and resistivity is 0.1 Ω cm or bigger.When magnetic density is that 0.6T or more and resistivity are 0.1 Ω cm or when bigger, the performance of moulded product is better than current commercial dust core, so its serviceability obtains increasing.In addition,, carry out compression forming, can obtain moulded product thus to the noncrystalline soft magnetic metal powder with the mixture that 1 quality % or amount still less are added to adhesive wherein through in the temperature range of the supercooled liquid scope of noncrystalline soft magnetic metal powder.In this case, the powder filling rate of moulded product is 90% or more, when applying 1.6 * 10 4Magnetic density is 0.9T or bigger during the magnetic field of A/m, and resistivity is 0.01 Ω cm or bigger.When magnetic density is that 0.9T or more and resistivity are 0.01 Ω cm or when bigger, the magnetic density of moulded product equals the magnetic density of the laminate steel core of amorphous and high silicon content in the practical ranges basically.Yet the magnetic hysteresis loss of the moulded product here is little, and its core loss characteristic corresponding to its high resistivity is very good, has therefore further improved its validity as magnetic core.
And; If after molded, all heat-treat being equal to or higher than under the temperature conditions of its Curie temperature aforementioned each moulded product of giving as high frequency magnetic core; As the heat treatment of removing strain, can further reduce core loss so and can further improve its validity as magnetic core.
In the powder that makes by amorphous soft magnetic with basic composition 1 of the present invention or 2; Tg (being glass transition temperature) is 520 ℃ or lower; Tx (being crystallization start temperature) is 550 ℃ or lower, and the supercooled liquid scope of being represented by Δ Tx=Tx-Tg is 20 ℃ or bigger.Because Tg is 520 ℃ or lower, so annealing effect is expected at the heat treatment temperature that is lower than conventional temperature, thereby can after magnet-wire is twined, heat-treat.When having served as cold liquid scope above 20 ℃, soft magnet performance is fabulous and noncrystalline formation ability is very high.And supercooled liquid scope medium viscosity reduces rapidly, therefore can utilize VISCOUS FLOW deformation to process.
In addition, the present invention can be frequency when being 1kHz initial permeability be 5000 or higher noncrystalline soft magnetism band.And the present invention can form the block magnetic element of noncrystalline, and its thickness is 0.5mm or thicker, and cross-sectional area is 0.15mm 2Or it is bigger.
Here; According to the present invention; Through forming like above-mentioned selection and optimization; Can adopt metal mould cast method to make the block magnetic element of noncrystalline, its diameter is that 1.5mm and its noncrystalline form ability apparently higher than traditional noncrystalline band, therefore can be different from lamination or the compression forming of powder or the formation of the block elements that curing molding is realized magnetic core of band.
When on the part magnetic circuit, forming breach as required and twining a circle or many turn coil, can make the inductance component as product of its good characteristic that shows high magnetic permeability in high-intensity magnetic field around this high frequency magnetic core.
To set forth in further detail the present invention with reference to accompanying drawing now.
With reference to Fig. 1, it illustrates an instance according to the basic structure of high frequency magnetic core 1 of the present invention, and its state makes high frequency magnetic core 1 form the shape of annular slab for using aforementioned amorphous soft magnetic powder.
With reference to Fig. 2, show the inductance component 10 that forms around the high frequency magnetic core 1 through coil 3 is wrapped in, wherein, coil 3 twines predetermined times around the high frequency magnetic core 1 of annular slab shape, form the inductance component 10 with lead-out wire part 3a and 3b thus.
With reference to Fig. 3; It illustrates another instance according to the basic structure of high frequency magnetic core 1 of the present invention; Wherein, use aforementioned amorphous soft magnetic powder to make high frequency magnetic core 1 form the shape (annular plate shape) of annular slab, on its part magnetic circuit, form breach 2 then.
With reference to Fig. 4; It illustrates the inductance component 20 that forms around the high frequency magnetic core 1 with breach 2 through coil 3 is wrapped in; Wherein, coil 3 twines predetermined times around the high frequency magnetic core with breach 21 of annular slab shape, forms the inductance component 20 with lead-out wire part 3a and 3b thus.
Through (it has aforementioned noncrystalline metal and forms to the noncrystalline soft magnetic metal powder; And maximum particle size is screen size 45 μ m or littler; Medium particle diameter is 30 μ m or littler) and carry out molded with the mixture that 10 quality % or amount still less are added to adhesive wherein; Can obtain having the dust core of extraordinary low loss characteristic under high frequency, this never occurs under conventional situation.Through coil being applied on this dust core, can obtain the good inductance component of Q quality factor.In addition,, adopt compression forming that magnet and winding around are formed integral body together, can obtain being suitable for the inductance component of big electric current under the high frequency through enclosing under the state in the magnet at winding around.
The concrete reason that the particles of powder size is limited is; If the screen size of maximum particle size surpasses 45 μ m; The Q quality factor of high-frequency region will worsen so; In addition, only if the centrophyten size is 30 μ m or littler, the Q quality factor under 500kHz or higher frequency can not surpass 40.In addition, only if the centrophyten size is 20 μ m or littler, the Q value under 1MHz or higher frequency (1/tan δ) can not become 50 or bigger.Because the resistivity of the alloy of amorphous soft magnetic powder itself exceeds about 2 to 10 times of traditional material, the Q quality factor preferably become big under the identical situation of granular size.If whether the Q quality factor are identical unimportant, can reduce the powder manufacturing cost through the scope that increases available granular size so.
With reference to Fig. 5; It illustrates the another instance according to the basic structure of high-frequency inductor parts 103 of the present invention; Wherein, Under the state of enclosing in the magnet 8 at winding around 6, adopt compression forming to integrate with winding around element 7 by the magnet 8 that aforementioned amorphous soft magnetic powder is processed, can form inductance component 103.The coil extension that numeral " 5 " expression is extended from winding around 6.
According to the present invention, the such state of " noncrystalline " expression wherein adopts common X-ray diffraction method that the surface of band or powder is measured, and the X-ray diffraction that obtains thus (XRD) resolution chart only is a broad peak.On the contrary, when spike occurring, can be judged to be " crystalline phase " owing to crystalline phase.
According to the present invention, when in the inert gas atmosphere such as Ar atmosphere, when the temperature of amorphous band or powder raises, during temperature raises, after the glass transition phenomenon occurring crystalline polamer appears.The beginning temperature of this glass transition phenomenon is represented with glass transition temperature (Tg), and the temperature range between glass transition temperature (Tg) and crystallization temperature (Tx) is represented with supercooled liquid scope (Tx-Tg).Be set in the rate of heat addition under the condition of 40K/min glass transition temperature, crystallization temperature and supercooled liquid scope are carried out assessment.
[instance]
To set forth in detail the present invention with instance below.
(instance 1 to 15)
Alloy composite according to predetermined carries out weighing to simple metal material Fe, P, B, Al, V, Cr, Y, Zr, Nb, Mo, Ta and W respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is respectively 20 μ m and 200 μ m through regulating rotary speed.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt single-roller method to form the band of 20 μ m and 200 μ m then.
With regard to the band of each 200 μ m; Use X-ray diffraction method that the slowest free coagulation surface of cooling rate that does not contact with the copper roll is measured; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.In addition, use the band of 20 μ m, hot property is judged through differential scanning calorimetry or calorimetry (DSC).In view of the above glass transition temperature and crystallization temperature are measured, and therefrom calculated the supercooled liquid scope.With regard to magnetic property, the band of 20 μ m is formed the magnetic core of winding, through the impedance analysis device initial permeability is measured then, and through DC B-H tracing instrument coercive force is measured.In this case, under glass transition temperature, in Ar atmosphere, each sample carried out 5 minutes heat treatment.Those samples that do not have glass transition temperature carry out 5 minutes heat treatment respectively under the temperature that is lower than 30 ℃ of crystallization temperatures.
As shown in table 1, because the alloy composite of instance 1 to 15 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and vitrifying formation ability is good, and soft magnet performance is also fine.Fig. 6 is the Fe with different-thickness 78P 8B 10Mo 4The XRD result curve figure of band.Visible by Fig. 6, the X-ray diffraction resolution chart up to the broad peak of 200 μ m, is " amorphous phase " therefore only.This point equally also is suitable for other instance.In fact, being difficult to produce thickness is 1 μ m or thinner band.On the other hand, comparative example 2,4 and 5 does not have the supercooled liquid scope, and vitrifying formation ability is lower, and soft magnet performance is relatively poor.In the comparative example 1 and 3 each all has the supercooled liquid scope, although it is smaller, it is lower that vitrifying forms ability, and can not to make thickness be 200 μ m or thicker band.
(instance 16 to 24)
Alloy composite according to predetermined carries out weighing to simple metal material Fe, P, B, Al, V, Cr, Nb, Mo, Ta, W and Si respectively, carrying out high-frequency heating with its fusing through in the decompression Ar atmosphere of finding time indoor, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is respectively 20 μ m and 200 μ m through regulating rotary speed.
With regard to the band of each 200 μ m; Use X-ray diffraction method that the slowest free coagulation surface of cooling rate that does not contact with the copper roll is measured; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.In addition, use the band of 20 μ m, hot property is judged through DSC.In view of the above glass transition temperature and crystallization temperature are measured, and therefrom calculated the supercooled liquid scope.With regard to magnetic property, the band of 20 μ m is formed the magnetic core of winding, through the impedance analysis device initial permeability is measured then, and through DC B-H tracing instrument coercive force is measured.In this case, under glass transition temperature, in Ar atmosphere, each sample carried out 5 minutes heat treatment.Those samples that do not have glass transition temperature carry out 5 minutes heat treatment respectively under the temperature that is lower than 30 ℃ of crystallization temperatures.
As shown in table 2, because the alloy composite of instance 16 to 24 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and vitrifying formation ability is good, and soft magnet performance is also fine.On the other hand, comparative example 6 does not have the supercooled liquid scope, and vitrifying formation ability is lower, and therefore can not make thickness is 200 μ m or thicker band, and the soft magnet performance of comparative example 6 is relatively poor.
(instance 25 to 29)
Alloy composite according to predetermined carries out weighing to simple metal material Fe, Co, Ni, P, B and Mo respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is respectively 20 μ m and 200 μ m through regulating rotary speed.
With regard to the band of each 200 μ m; Use X-ray diffraction method that the slowest free coagulation surface of cooling rate that does not contact with the copper roll is measured; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.In addition, use the band of 20 μ m, hot property is judged through DSC.In view of the above glass transition temperature and crystallization temperature are measured, and therefrom calculated the supercooled liquid scope.With regard to magnetic property, the band of 20 μ m is formed the magnetic core of winding, through the impedance analysis device initial permeability is measured then, and through DC B-H tracing instrument coercive force is measured.In this case, under glass transition temperature, in Ar atmosphere, each sample carried out 5 minutes heat treatment.Those samples that do not have glass transition temperature carry out 5 minutes heat treatment respectively under the temperature that is lower than 30 ℃ of crystallization temperatures.
As shown in table 3, because the alloy composite of instance 25 to 29 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and vitrifying formation ability is good, and soft magnet performance is also fine.On the other hand, although comparative example 7 has the supercooled liquid scope, and have excellent vitrifying formation ability, it does not at room temperature have magnetic.
(instance 30 to 33)
Alloy composite according to predetermined carries out weighing to simple metal material Fe, Co, Ni, P, B, Mo and Si respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is respectively 20 μ m and 200 μ m through regulating rotary speed.
With regard to the band of each 200 μ m; Use X-ray diffraction method that the slowest free coagulation surface of cooling rate that does not contact with the copper roll is measured; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.In addition, use the band of 20 μ m, hot property is judged through DSC.In view of the above glass transition temperature and crystallization temperature are measured, and therefrom calculated the supercooled liquid scope.With regard to magnetic property, the band of 20 μ m is formed the magnetic core of winding, through the impedance analysis device initial permeability is measured then, and through DC B-H tracing instrument coercive force is measured.In this case, under glass transition temperature, in Ar atmosphere, each sample carried out 5 minutes heat treatment.Those samples that do not have glass transition temperature carry out 5 minutes heat treatment respectively under the temperature that is lower than 30 ℃ of crystallization temperatures.
As shown in table 4, because the alloy composite of instance 30 to 33 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and vitrifying formation ability is good, and soft magnet performance is also fine.On the other hand, although comparative example 8 has the supercooled liquid scope, and have excellent vitrifying formation ability, it does not at room temperature have magnetic.
(instance 34 to 36)
Alloy composite according to predetermined carries out weighing to simple metal material Fe, P, B, Al, Nb and Mo respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, adopt the water atomization method to make the noncrystalline soft magnetic powder.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt the water atomization method to form the noncrystalline soft magnetic powder then.
Resulting noncrystalline soft magnetic powder all is classified into 200 μ m or littler particle size; Use X-ray diffraction method that it is measured then; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.
As shown in table 5, because the alloy composite of instance 34 to 36 drops in the compositing range of the present invention, so can adopt the water atomization method to make the noncrystalline soft magnetic powder.Fig. 7 is for having the Fe of variable grain size through classification 78P 8B 10Mo 4The XRD result curve figure of powder.Visible by Fig. 7, the X-ray diffraction resolution chart up to the broad peak of 200 μ m, is " amorphous phase " therefore only.This point equally also is suitable for other instance.On the other hand, comparative example 9 does not have vitrifying to form ability, and therefore resulting powder is in crystalline phase.Can not obtain the noncrystalline soft magnetic powder.
(instance 37 to 60)
Alloy composite according to predetermined carries out weighing to material Fe, Co, Ni, Fe-P, Fe-B, Fe-Si, Al, Fe-V, Fe-Cr, Y, Zr, Fe-Nb, Fe-Mo, Ta, W, Ti, C, Mn and Cu respectively; Carrying out high-frequency heating with its fusing, make foundry alloy thus then through in the Ar atmosphere pressure-reducing chamber of finding time.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is respectively 20 μ m and 200 μ m through regulating rotary speed.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt single-roller method to form the band of 20 μ m and 200 μ m then.
With regard to the band of each 200 μ m; Use X-ray diffraction method that the slowest free coagulation surface of cooling rate that does not contact with the copper roll is measured; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.In addition, use the band of 20 μ m, hot property is judged through DSC.In view of the above glass transition temperature and crystallization temperature are measured, and therefrom calculated the supercooled liquid scope.With regard to magnetic property, use the band of 20 μ m, and use vibrating sample magnetometer (VSM) that its saturation flux density is measured.
As show 6-1 with shown in the table 6-2, and because the alloy composite of instance 37 to 60 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and noncrystalline forms very capablely, soft magnet performance is also fine.On the other hand, comparative example 10,11,12,13,14,15,17 and 20 has only little or does not have the supercooled liquid scope, and noncrystalline to form ability lower.It is higher that comparative example 16,18 and 19 noncrystalline form ability, but Tc and Bs are then lower.In comparative example 15, the supercooled liquid scope is less, and it is lower that noncrystalline forms ability, and glass transition temperature is higher.
(instance 61 to 70)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make each band that thickness is 50 μ m.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt single-roller method to form the band of 50 μ m then.
Each band is carried out the rate of corrosion inspection.The band of 50 μ m is placed in the 1 standard NaCl solution, and weight change is checked, and goes out rate of corrosion from surface area and Time Calculation.Its result is as shown in table 7.
As shown in table 7, because the alloy composite of instance 61 to 70 drops in the compositing range of the present invention, so their corrosion resistance is very strong, promptly their rate of corrosion is lower.On the contrary, the corrosion resistance of comparative example 21 is very low, and promptly its rate of corrosion is bigger.
(instance 71 to 73)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is 20 μ m.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt single-roller method to form the band of 20 μ m then.
The band of each 20 μ m all is formed the magnetic core of winding, and the stacked part of magnetic core is measured initial permeability through the impedance analysis device through inserting the bonded and insulation of silicone resin therebetween then.In this case, 350 ℃ of heat treatments of in Ar atmosphere, each sample being carried out 60 minutes.On the other hand, to the sample processed by METGLAS 2605-S2 425 ℃ of heat treatments of carrying out 60 minutes.
As shown in table 8, because the alloy composite of instance 71 to 73 drops in the compositing range of the present invention, so their soft magnet performance is fine.On the contrary, the soft magnet performance of comparative example 22 is very poor.
(instance 74 to 78)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is 20 μ m to 170 μ m through regulating rotary speed.
For relatively, make foundry alloy through high-frequency heating with composition identical with commercial METGLAS 2605-S2, adopt single-roller method to form the band of 20 μ m then.
To each band sheet all carry out range upon range ofly, to form range upon range of magnetic core, magnetic core width is 1mm, length is 16mm, thickness is 1mm.The band sheet is bonded to together through silicone resin is inserted therebetween, and mutually insulated, on each range upon range of magnetic core, after the coil of application 1 200 circles, through the impedance analysis device Ls and Q is measured.In this case, 350 ℃ of heat treatments of in Ar atmosphere, each sample being carried out 60 minutes.On the other hand, under 425 ℃, the sample that is made up of METGLAS 2605-S2 carried out 60 minutes heat treatment.The measurement result of sample is as shown in table 9.
As shown in table 9, because the alloy composite of instance 74 to 78 drops in the compositing range of the present invention, so their high-frequency soft magnetic performance is fine.On the contrary, because the thickness of comparative example 23 surpasses 150 μ m, so its high frequency characteristics is because eddy current loss and very poor.In addition, the composition of comparative example 24 drops on outside the compositing range of the present invention, its high-frequency soft magnetic poor performance.
(instance 79 to 82)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use the water atomization method to make powder.
For relatively, through high-frequency heating, make foundry alloy thus with composition identical with commercial METGLAS2605-S2, adopt the water atomization method to form powder then.
Resulting powder all is classified into 200 μ m or littler particle size; Use X-ray diffraction method that it is measured then; Obtain the X-ray diffraction resolution chart thus; Decidable is " amorphous phase " when resulting X-ray diffraction resolution chart has only broad peak, and then decidable is " crystalline phase " in other cases.
As shown in table 10, because the alloy composite of instance 79 to 82 drops in the compositing range of the present invention, so can adopt the water atomization method to make the noncrystalline soft magnetic powder.On the other hand, comparative example 25 and 26 does not have vitrifying to form ability, and therefore resulting powder is in crystalline phase.Can not obtain the noncrystalline soft magnetic powder.
(instance 83 to 86)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use the water atomization method to make the noncrystalline soft magnetic powder.Said powder is mixed, so that become graininess, then (10 tons/cm of 980MPa respectively with the silicone resin that is dissolved in the solvent of 5 quality % 2) pressure under said powder is pressed into overall diameter is 18mm, interior diameter is 12mm, thickness is the dust core of 3mm.
In order to compare, the silicone resin in the solvent that is dissolved in of also being mixed with 5 quality % respectively for the Fe powder, Fe-Si-Cr powder and the ferro-silicon-aluminium powder that adopt the water atomization method to make is so that become graininess, then (10 tons/cm of 980MPa 2) pressure under said powder is pressed into overall diameter respectively is 18mm, interior diameter is 12mm, thickness is the dust core of 3mm.
With regard to resulting dust core, through the impedance analysis device initial permeability is measured, and Fe loss and density are measured through alternating-current B-H tracing instrument.In this case, in the heat treatment of in Ar atmosphere, each sample being carried out 60 minutes under 350 ℃.On the other hand, under 500 ℃, the sample that is made up of Fe powder and Fe-Si-Cr powder is carried out 60 minutes heat treatment, and under 700 ℃, the sample that is made up of the ferro-silicon-aluminium powder carried out 60 minutes heat treatment.Measured initial permeability, loss and density are as shown in table 11.
As shown in table 11, be appreciated that the dust core that constitutes owing to the noncrystalline soft magnetic powder by instance 83 to 86 falls within the scope of the invention, so its loss is very low.On the other hand, comparative example 27 is the dust cores that are made up of iron powder, and density is bigger, the non-constant of initial permeability and high-frequency loss.Equally in comparative example 28 and 29, the non-constant of loss.
(instance 87 to 110)
At first,, respectively simple metal element material Fe, Co, Ni, P, B, Si, Mo, Al, V, Cr, Y, Zr, Nb, Ta and W are carried out weighing, make foundry alloy thus according to predetermined alloy composite as the powder production process.Afterwards, utilize prepared foundry alloy, use the water atomization method to make various soft-magnetic alloy powders.
Then; As the moulded product production process, resulting alloy powder all is classified into 45 μ m or littler particle size, then will be as the silicone resin of adhesive amount and the said powder with 4 quality %; Afterwards; Use to have overall diameter and be 27mm, interior diameter is the rolled-up stock molding die of the groove of 14mm, at room temperature respectively said powder is applied (the about 12t/cm with 1.18GPa 2) pressure so that have the height 5mm, obtain the respective molded product thus.
In addition; After resulting moulded product is carried out resin solidification; Weight and size to moulded product are measured, and are to twine the coil that respectively has the suitable number of turns on the magnetic core respectively at moulded product then, make corresponding inductance component (each is all as shown in Figure 2) thus.
Then, with regard to each resulting sample is inductance component, uses LCR to measure meter and under 100kHz, try to achieve magnetic permeability by inductance value, in addition, when applying with 1.6 * 10 4During the magnetic field of A/m, use dc magnetic energy measurement equipment that saturation flux density is measured.In addition, the upper surface and the lower surface of each magnetic core polished, carry out XRD (X-ray diffraction) then and measure to observe phase.The result is shown in table 12-1 and table 12-2.
The proportion of composing of corresponding sample has been shown in table 12; And when in the XRD figure case that obtains through the XRD measurement, only detecting the broad peak that is specific to amorphous phase, can be judged to be " amorphous phase "; And when observing the spike that causes owing to crystalline phase with broad peak; Perhaps when only observing spike under the situation that is not having broad peak, can be judged to be " crystalline phase ".With regard to those samples with the composition that demonstrates amorphous phase, carry out heat through DSC and analyze, so that glass transition temperature (Tg) and crystallization temperature (Tx) are measured, and definite for those all samples Δ Tx be 20 ℃ or bigger.Adopt direct current two-terminal method that the resistivity of respective molded product (magnetic core) is measured, and confirm that all samples all have 1 Ω cm or bigger value preferably.
The rate of heat addition in DSC is set to 40K/min.Be appreciated that by instance 87 to 89 and comparative example 30 to 33; When the content of P or B is lower than 2% or when being higher than 16%; Can not form the amorphous phase that can obtain high magnetic permeability, and when the content of the content of P and B all 2% or above and 16% or following scope in the time, can form amorphous phase.Be appreciated that by instance 90 to 92 and comparative example 34 and 35,, can not form amorphous phase, and be higher than 0% and be 10% or when following when the content of Mo, can form amorphous phase when the content of Mo is 0% or when being higher than 10%.Be appreciated that with comparative example 36 by instance 93 and 94, even when the Si of adding 8% or less amount scope, also can form amorphous phase.Be appreciated that by instance 95 to 102, even when Mo is replaced by Al, V, Cr, Y, Zr, Nb, Ta or W, also can form amorphous phase.Be appreciated that by instance 103 to 110 Fe can partly be replaced by Co and/or Ni, but is appreciated that by comparative example 37 and 38; If Fe is replaced fully; Although obtained amorphous phase so, the magnetic density vanishing, so this is not suitable for the field of the invention.
(instance 111 to 132)
At first,, respectively simple metal element material Fe, Co, Ni, P, B, Si, Mo, Al, V, Cr, Y, Zr, Nb, Ta, W, Ti, C, Mn and Cu are carried out weighing, make foundry alloy thus according to predetermined alloy composite as the powder production process.Afterwards, utilize prepared foundry alloy, use the water atomization method to make various soft-magnetic alloy powders.
Then; As the moulded product production process, resulting alloy powder all is classified into 45 μ m or littler particle size, then will be as the silicone resin of adhesive amount and the said powder with 4 quality %; Afterwards; Use to have overall diameter and be 27mm, interior diameter is the rolled-up stock of the groove of 14mm, at room temperature respectively said powder is applied (the about 12t/cm with 1.18GPa 2) pressure therefore so that have the height of 5mm, obtain the respective molded product.
In addition; After resulting moulded product is carried out resin solidification; Weight and size to moulded product are measured, and are to use the coil that respectively has the suitable number of turns on the magnetic core respectively at moulded product then, make corresponding inductance component (each is all as shown in Figure 2) thus.
Then, with regard to each resulting sample is inductance component, uses LCR to measure meter and under 100kHz, try to achieve magnetic permeability by inductance value, in addition, when applying with 1.6 * 10 4During the magnetic field of A/m, use dc magnetic energy measurement equipment that saturation flux density is measured.In addition, the upper surface and the lower surface of each magnetic core polished, carry out XRD (X-ray diffraction) then and measure to observe phase.The result is shown in table 13-1 and table 13-2.
At table 13-1 and the proportion of composing of showing to have illustrated among the 13-2 corresponding sample; And when in the XRD figure case that obtains through the XRD measurement, only detecting the broad peak that is specific to amorphous phase, can be judged to be " amorphous phase "; And when observing the spike that causes owing to crystalline phase with broad peak; Perhaps when only observing spike under the situation that is not having broad peak, can be judged to be " crystalline phase ".With regard to those samples with the composition that demonstrates amorphous phase, carry out heat through DSC and analyze, so that glass transition temperature (Tg) and crystallization temperature (Tx) are measured, and definite for those all samples Δ Tx be 20 ℃ or bigger.Adopt direct current two-terminal method that the resistivity of respective molded product (magnetic core) is measured, and confirm that all samples all have 1 Ω cm or bigger value preferably.
As show 13-1 with shown in the table 13-2, and because the alloy composite of instance 111 to 132 drops in the compositing range of the present invention, so they have the supercooled liquid scope respectively, and noncrystalline formation ability is good, soft magnet performance is also fine.On the other hand, be appreciated that it is lower that the noncrystalline of comparative example 39 to 53 forms ability, therefore can only obtain crystalline phase, and can not obtain good magnetic property.
(instance 133)
In instance 133, adopt the water atomization method to make and consist of Fe 77P 10B 10Nb 2Cr 1Ti 0.1C 0.1Mn 0.1Cu 0.1Alloy powder, resulting then alloy powder is classified into 45 μ m or littler particle size, then it is carried out XRD and measures, and confirms to be specific to the broad peak of amorphous phase afterwards.In addition, carry out heat analysis,, confirm that thus Δ Tx (Tg-Tx) is 36 ℃ to measure glass transition temperature (Tg) and crystallization temperature (Tx) through DSC.Then, powder is remained below 400 ℃ of the temperature of glass transition temperature,, on powder surface, form oxide thus so that in atmosphere, carry out 0.5 hour heat treatment.
In addition, will join as the silicone resin of adhesive in the said powder that is formed with oxide, with 5%, 2.5%, 1% and 0.5% amount respectively to obtain powder separately.Use and have overall diameter and be 27mm; Interior diameter is the rolled-up stock of the groove of 14mm; At room temperature, be higher than 150 ℃ of the resin softening temperature or respectively resulting powder is applied (about 12 tons/cm with 1.18GPa 480 ℃ of the supercooled liquid scope of noncrystalline soft magnetic metal powder 2) pressure therefore so that have the height of 5mm, obtain the respective molded product.
After resulting moulded product is carried out resin solidification; Weight and size to moulded product are measured; Be to use the coil that respectively has the suitable number of turns on the magnetic core respectively at moulded product then, make corresponding inductance component (each is all as shown in Figure 2) thus.
Then, with regard to each resulting inductance component of the 1st to the 12nd sample, the magnetic density that can cause powder filling rate (%), dc magnetic is (1.6 * 10 4During A/m) and dc resistivity (Ω cm) measure.The result is as shown in table 14.
Be appreciated that by table 14, when the addition (amount of resin) of adhesive surpasses 5%, can obtain comparing with iron oxygen magnetic core>=10E4 (=10 5) high resistivity, even and can not observe this effect through improving molding temperature yet, and just enough such as the molded condition of room temperature.Be appreciated that, when amount of resin is 5%, also can obtain 1 Ω cm or above high resistivity, but equally at room temperature carry out molded just enough.In addition, be appreciated that with regard to 2.5% amount of resin, when under 150 ℃, carrying out when molded, the powder filling rate is significantly improved, increasing magnetic density, and obtained 0.1 Ω cm or above resistivity in addition.In addition, be appreciated that with regard to 1% or 0.5% amount of resin, when carrying out when molded at 480 ℃, the powder filling rate is significantly improved, increasing saturation flux density, and obtained 0.01 Ω cm or above resistivity in addition.
(instance 134)
In instance 134; Inductance component corresponding to the 10th sample in instance 133 is made, and uses through same alloy powder and same manufacture process and at 450 ℃ of high frequency magnetic cores that in nitrogen atmosphere, make through 0.5 hour heat treatment and makes inductance component.In addition, for relatively, use and make inductance component as the sendust of core material, 6.5% the base amorphous material of silicon steel, Fe.Each inductance component is all as shown in Figure 2, but also can be the inductance component that on the part magnetic circuit, has breach as shown in Figure 4.With regard in these inductance components each, to the magnetic density that can cause by dc magnetic (1.6 * 10 4During A/m), dc resistivity (Ω cm), be used for the standardized magnetic permeability of inductance value and core loss (20kHz 0.1T) is measured.The result is as shown in Tble 15.
Be appreciated that by table 15 magnetic density of inductance component of the present invention equals to use the magnetic density of the inductance component of the base amorphous magnetic core of Fe basically, its core loss then is lower than the core loss of the inductance component that uses sendust core, and its performance is very good.In addition, be appreciated that the magnetic permeability and the core loss that have through the inductance component of heat treated magnetic core are improved, so its more excellent performance.
(instance 135)
In instance 135; Respectively with the ratio shown in the table 16; The particle size that will have alloy composite shown in the table 16 and screened through the standard filter screen separately is that 20 μ m or littler water atomized powder are added in the powder identical with the powder that makes according to instance 133, obtains corresponding powder thus.
In addition; Amount with 1.5 quality % will join in resulting each powder as the silicone resin of adhesive; Use then to have overall diameter and be 27mm, interior diameter is the rolled-up stock of the groove of 14mm, at room temperature resulting powder is applied (about 12 tons/cm with 1.18GPa 2) pressure therefore so that have the height of 5mm, obtain the respective molded product.After molded, in 450 ℃ Ar atmosphere, moulded product is heat-treated.
Then; After resulting moulded product is carried out resin solidification; Weight and size to moulded product are measured, and are to use the coil that respectively has the suitable number of turns on the magnetic core respectively at moulded product then, make corresponding inductance component (each is all as shown in Figure 2) thus.
Then, with regard to each resulting sample was inductance component, (20kHz 0.1T) measured to powder filling rate (%), magnetic permeability and core loss.The result is shown in table 16.
Be appreciated that to have the soft magnetic powder than granule through adding to the noncrystalline metal dust by table 16, the powder filling rate of inductance component of the present invention is improved, so magnetic permeability also is improved.On the other hand, be appreciated that and since when addition above 50% the time, the effect of improvement is weakened, the core loss characteristic can extremely worsen, so addition is preferably 50% or still less.
(instance 136)
In instance 136, make and consist of Fe 77P 10B 10Nb 2Cr 1Ti 0.1C 0.1Mn 0.1Cu 0.1Alloy powder; Make through changing creating conditions of water atomization method; Make it have ratio of height to diameter shown in table 17 (aspect ratio); Resulting then powder is classified into 45 μ m or littler particle size, then it is carried out XRD and measures, and confirms to be specific to the broad peak of amorphous phase thus.In addition, all powder is carried out heat analysis,, confirm that thus supercooling temperature range delta Tx is 20 ℃ to measure glass transition temperature and crystallization temperature through DSC.
In addition, the amount with 3.0 quality % will join in the resulting powder, afterwards as the silicone resin of adhesive; Use and have overall diameter and be 27mm; Interior diameter is the rolled-up stock of the groove of 14mm, at room temperature, resulting powder is applied (15 tons/cm of 1.47GPa 2) pressure so that have the height 5mm, obtain the respective molded product thus.After molded, in Ar atmosphere, moulded product is heat-treated at 450 ℃.
Then; After resulting moulded product is carried out resin solidification; Weight and size to moulded product are measured, and are to use the coil that respectively has the suitable number of turns on the magnetic core respectively at moulded product then, make corresponding inductance component (each is all as shown in Figure 2) thus.
Then, be inductance component to each resulting sample, powder filling rate (%) and magnetic permeability are measured.The result is shown in table 17.
Be appreciated that by table 17 through increasing the ratio of height to diameter of noncrystalline metal dust, the magnetic permeability of inductance component of the present invention is improved.On the other hand, be appreciated that and since when ratio of height to diameter above 2.0 the time, initial permeability is higher, but the magnetic permeability when DC stacked worsens, so the ratio of height to diameter of powder is preferably 2.0 or littler.
(instance 137)
At first,, material is carried out weighing, to obtain composition F e as the powder production process 77P 10B 10Nb 2Cr 1Ti 0.1C 0.1Mn 0.1Cu 0.1, and, utilize said composition, use hydraulic atomized method to make to have the soft magnetic alloy powder of different medium particle diameters.
Then, as the moulded product production process, resulting alloy powder is screened through utilizing various standard filter screens; Make powder shown in table 18 thus; Then will be as the silicone resin of adhesive amount and said powder with 3 quality %, the overall diameter with 3.5 circles is 8mm then, interior diameter is 4mm; Highly be 2mm coil together; Said powder is placed the rolled-up stock of 10mm * 10mm, and said coil is provided so that the center that after molded, is positioned at moulded product, at room temperature respectively said powder applied with (5 tons/cm of 490MPa then 2) pressure therefore so that have the height of 4mm, obtain the respective molded product.Under 150 ℃, resulting moulded product is carried out resin solidification then.With regard to the condition of the 5th sample, equally also, make sample thus 450 ℃ of heat treatments of in nitrogen atmosphere, moulded product being carried out 0.5 hour.
Then, with regard to each resulting sample was inductance component, the peak value of the inductance value of 1MHz, crest frequency and Q can be tried to achieve the measurement that inductance and impedance are carried out under correspondent frequency by using LCR to measure meter.The result is shown in table 18.
Then, with regard to each sample inductance component, use common DC-DC converter evaluation kit (dc-dc converter evaluation kit) that power conversion efficient is measured.Measuring condition is input 12V, output 5V, driving frequency 300kHz, output current 1A.The result is also shown in table 18.
Shown in table 18; Through filter screen particle diameter (sieve particle size) is made as 45 μ m or littler; And medium particle diameter is made as 30 μ m or littler, can make the Q crest frequency of inductance component of the present invention be 5000kHz or more than, the Q peak value be 40 or more than; Make simultaneously power conversion efficient be 80% or more than, this is extraordinary.In addition, through the filter screen particle diameter being made as 45 μ m or littler, and medium particle diameter is made as 20 μ m or littler, can make the Q crest frequency be 1MHz or more than, the Q peak value be 50 or more than, in this case, power conversion efficient be 85% or more than, this is extraordinary.In addition, be appreciated that,, can further improve conversion efficiency through inductance component is heat-treated.
(instance 138)
At first,, material is carried out weighing, to obtain composition F e as the powder production process 77P 10B 10Nb 2Cr 1Ti 0.1Mn 0.1Cu 0.1, and, utilize said composition, use hydraulic atomized method to make soft magnetic alloy powder.
Then; As the moulded product production process; Through utilizing various standard filter screens that resulting alloy powder is screened; Make powder shown in table 19 thus, will apply (5t/cm to said powder then as the silicone resin of adhesive amount and said powder then with 3 quality % with 490Mpa 2) pressure be 32mm so that form overall diameter, interior diameter is 20mm, highly is the annular of 5mm, makes the respective molded product thus.Under 150 ℃, resulting moulded product is carried out resin solidification.For relatively, adopt the sample of the powder that can make the Si that uses Fe-6.5 quality % in the same way.
Then, twining ten loop diameters around each sample that makes is 0.1mm, is covered with the copper cash of amide-imide (amide-imide) coating, makes inductance component thus.
Then, with regard to each resulting inductance component, can try to achieve the measurement that inductance and impedance are carried out at the correspondent frequency place by using LCR to measure meter at the peak value of inductance value, crest frequency and the Q at 10kHz place.The result is shown in table 19.
Then, with regard in these inductance components each, use common DC-DC converter evaluation kit that power conversion efficient is measured.Measuring condition is input 12V, output 5V, driving frequency 10kHz, output current 1A.The result is also shown in table 19.
(instance 139 and 140)
Alloy composite according to predetermined carries out weighing to material Fe, Fe-P, Fe-B, Fe-Cr, Fe-Nb, Ti, C, Mn and Cu respectively, carrying out high-frequency heating with its fusing through in the Ar atmosphere pressure-reducing chamber of finding time, makes foundry alloy thus then.Afterwards, utilize prepared foundry alloy, use single-roller method to make the band that thickness is 20 μ m.
The band of each 20 μ m all is formed the magnetic core of winding, and the stacked part of magnetic core is through inserting the bonded and insulation of therebetween silicone resin, then through the impedance analysis device to measuring at the initial permeability at 1kHz place.In this case, under room temperature, 250 ℃, 300 ℃, 400 ℃, 450 ℃ and 550 ℃, in Ar atmosphere, each sample carried out 5 minutes heat treatment respectively.
Shown in table 20, when in Curie temperature or above and crystallization temperature or following temperature range, heat-treating, instance 139 of the present invention and 140 alloy composite can demonstrate extraordinary soft magnet performance.Especially when in crystallization temperature or when above, soft magnet performance worsens rapidly.
Commercial Application
As stated, use noncrystalline soft magnetic metallic material low cost to obtain high frequency magnetic core of the present invention with high saturation magnetic flux metric density and high resistivity.In addition, very good through the high frequency band magnetic property that coil is applied to the inductance component that forms on the said high frequency magnetic core, this never occurs under conventional situation.Therefore can low-cost make the dust core of high-performance high magnetic permeability, this never occurs under conventional situation.High frequency magnetic core of the present invention be suitable for various electronic equipments such as choke coil and power of transformer parts.
In addition, the high frequency magnetic core of the present invention that is made up of the powder of fine particle size can realize making the high-performance inductance component that is used for high frequency.High frequency magnetic core by the fine particle size powder constitutes can also be realized in addition; Carry out compression forming through enclosing under the state in the magnet at winding around; Thereby magnet and winding around are integrated, make small size thus but be suitable for the inductance component of big electric current.Therefore high frequency magnetic core of the present invention is suitable for the inductance component of choke coil, transformer etc.
Table 1
Alloy composite atom % Band 200 μ m Tc ℃ T ℃ Tx ℃ Tx-Tg ℃ Bs T Initial permeability 1kHz
Comparative example 1 Fe 78P 0B 18Mo 4 Crystalline phase 262 490 514 24 1.27 4000
Instance 1 Fe 78P 2B 16Mo 4 Amorphous phase 261 485 514 29 1.29 8000
Instance 2 Fe 78P 8B 10Mo 4 Amorphous phase 256 466 506 40 1.28 15000
Instance 3 Fe 78P 16B 2Mo 4 Amorphous phase 250 456 496 40 1.27 12000
Comparative example 2 Fe 78P 18B 0Mo 4 Crystalline phase 250 - 490 - 1.25 3500
Comparative example 3 Fe 82P 8B 10Mo 0 Crystalline phase 342 440 458 18 1.61 4000
Instance 4 Fe 81P 8B 10Mo Amorphous phase 318 446 477 31 1.53 5500
Instance 5 Fe 78P 8B 10Mo 4 Amorphous phase 256 466 506 40 1.28 15000
Instance 6 Fe 78P 8B 10Mo 5 Amorphous phase 242 480 520 40 1.20 14000
Instance 7 Fe 72P 8B 10Mo 10 Amorphous phase 178 513 538 25 0.76 6000
Comparative example 4 Fe 70P 8B 10Mo 12 Crystalline phase 162 - 552 - 0.44 4500
Instance 8 Fe 78P 8B 10Al 4 Amorphous phase 365 456 487 31 1.53 7000
Instance 9 Fe 78P 8B 10V 4 Amorphous phase 260 463 495 32 1.36 8000
Instance 10 Fe 78P 8B 10Cr 4 Amorphous phase 259 454 480 26 1.31 7000
Instance 11 Fe 78P 8B 10Y 4 Amorphous phase 292 482 507 25 1.29 6000
Instance 12 Fe 78P 8B 10Zr 4 Amorphous phase 259 470 502 32 1.28 9000
Instance 13 Fe 78P 8B 10Nb 4 Amorphous phase 258 476 516 40 1.27 17000
Instance 14 Fe 78P 8B 10Ta 4 Amorphous phase 252 504 546 42 1.25 15000
Instance 15 Fe 78P 8B 10W 4 Amorphous phase 246 486 529 43 1.23 13000
Comparative example 5 METGLAS Crystalline phase 400 - 525 - 1.58 4000
Table 2
Alloy composite atom % Band 200 μ m Tc ℃ Tg ℃ Tx ℃ Tx-Tg ℃ Bs T Initial permeability 1kHz
Instance 16 Fe 78P 8B 10Si0Mo 4 Amorphous phase 255 466 506 40 1.28 15000
Instance 17 Fe 78P 7B 9Si 2Mo 4 Amorphous phase 257 472 508 36 1.27 13000
Instance 18 Fe 78P 3B 9Si 8Mo 4 Amorphous phase 262 489 509 20 1.27 9000
Comparative example 6 Fe 78P 2B 8Si 10Mo 4 Amorphous phase 262 - 522 - 1.26 4500
Instance 19 Fe 78P 7B 9Si 2Al 4 Amorphous phase 367 464 497 33 1.55 8000
Instance 20 Fe 78P 7B 9Si 2V 4 Amorphous phase 265 467 505 38 1.39 7500
Instance 21 Fe 78P 7B 9Si 2Cr 4 Amorphous phase 262 466 501 35 1.30 6500
Instance 22 Fe 78P 7B 9Si 2Nb 4 Amorphous phase 262 480 518 38 1.24 14000
Instance 23 Fe 78P 7B 9Si 2Ta 4 Amorphous phase 253 485 522 37 1.22 12000
Instance 24 Fe 78P 7B 9Si 2W 4 Amorphous phase 249 497 541 44 1.20 11000
Table 3
Alloy composite atom % Band 200 μ m Tc ℃ Tg ℃ Tx ℃ Tx-Tg ℃ Bs T Initial permeability 1kHz
Instance 25 (Fe 1.0Co 0.0) 78P 8B 10Mo 4 Amorphous phase 255 466 506 40 1.28 15000
Instance 26 (Fe 0.8Co 0.2) 78P 8B 10Mo 4 Amorphous phase 278 468 510 42 1.28 14000
Instance 27 (Fe 0.8Ni 0.2) 78P 8B 10Mo 4 Amorphous phase 251 462 511 49 1.20 16000
Instance 28 (Fe 0.1Co 0.9) 78P 8B 10Mo 4 Amorphous phase 243 470 512 42 0.45 40000
Instance 29 (Fe 0.05Ni 0.05Co 0.9) 78P 8B 10Mo 4 Amorphous phase 245 469 508 39 0.41 68000
Comparative example 7 (Fe 0.9Ni 1.0) 78P 8B 10Mo 4 Amorphous phase - 460 508 48 0 -
Table 4
Alloy composite atom % Band 200um ?Tc?℃ Tg ℃ Tx ℃ Tx-Tg ℃ Bs T Initial permeability 1kHz
Instance 30 (Fe 1.0Co 0.0) 78P 7B 9Si 2Mo 4 Amorphous phase ?257 472 508 36 1.27 13000
Instance 31 (Fe 0.8Co 0.2) 78P 7B 9Si 2Mo 4 Amorphous phase ?281 474 510 36 1.28 6500
Instance 32 (Fe 0.8Ni 0.2) 78P 7B 9Si 2Mo 4 Amorphous phase ?250 466 513 47 1.17 10000
Instance 33 (Fe 0.05Ni 0.05Co 0.9) 78P 7B 9Si 2Mo 4 Amorphous phase ?245 478 517 39 0.41 70000
Comparative example 8 (Fe 0.0Ni 1.0) 78P 7B 9Si 2Mo 4 Amorphous phase ?246 455 493 38 0 -
Table 5
Alloy composite atom % Powder-200 μ m
Instance 34 Fe 78P 6B 12Mo 4 Amorphous phase
Instance
35 Fe 78P 6B 12Al 4 Amorphous phase
Instance 36 Fe 78P 6B 12Nb 4 Amorphous phase
Comparative example 9 METGLAS Crystalline phase
Figure G2009101276380D00371
Figure G2009101276380D00381
Table 7
Alloy composite atom % Additive weight % Rate of corrosion 1 standard NaClmm/
Instance 61 Fe 77P 10B 10Nb 2Cr 1 Ti 0C 0Mn 0Cu 0 0.28
Instance 62 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 0.22
Instance 63 Fe 77P 10B 10Nb 2Cr 1 Ti 0.3C 0.1Mn 0.1Cu 0.1 0.18
Instance 64 Fe 77P 10B 10Nb 2Cr 1 Ti 0.5C 0.1Mn 0.1Cu 0.1 0.12
Instance 65 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 1.0Cu 0.1 0.20
Instance 66 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 2.0Cu 0.1 0.16
Instance 67 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 3.0Cu 0.1 0.15
Instance 68 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.5 0.11
Instance 69 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 1.0 0.06
Instance 70 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 1.5 0.04
Comparative example 21 METGLAS 2.7
Table 8
Alloy composite atom % Additive weight % Thickness μ m The magnetic permeability 50kHz of toroidal core
Instance 71 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 20 9800
Instance 72 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.5 20 10000
Instance 73 Fe 77P 7B 13Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 20 11300
Comparative example 22 METGLAS 20 4000
Table 9
Alloy composite atom % Additive weight % Thickness μ m The L μ H 50kHz of lamination magnetic core The Q 50kHz of lamination magnetic core
Instance 74 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 20 42 52
Instance 75 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 105 29 32
Instance 76 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 150 28 28
Comparative example 23 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 170 19 25
Instance 77 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.3Mn 0.1Cu 0.1 20 41 49
Instance 78 Fe 77P 7B 13Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 25 38 58
Comparative example 24 METGLAS 20 20 26
Table 10
Alloy composite atom % Additive weight % Powder-200 μ m
Instance 79 F6 77P 7B 13Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 Amorphous phase
Instance 80 Fe 77P 9B 11Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 Amorphous phase
Instance 81 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 Amorphous phase
Instance 82 Fe 77P 11B 9Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 Amorphous phase
Comparative example 25 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.7Mn 0.1Cu 0.1 Crystalline phase
Comparative example 26 Glass metal Crystalline phase
Table 11
Alloy composite atom % Additive weight % Initial permeability 50kHz Loss mW/cc 50kHz-300mT Density %
Instance 83 Fe 77P 7B 13Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 26 760 74
Instance 84 Fe 77P 9B 11Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 25 820 73
Instance 85 Fe 77P 10B 10Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 26 860 73
Instance 86 Fe 77P 11B 9Nb 2Cr 1 Ti 0.1C 0.1Mn 0.1Cu 0.1 27 920 74
Comparative example 27 Fe 18 6320 85
Comparative example 28 Fe-Si-Cr 26 2850 82
Comparative example 29 Sendust 24 2200 78
Table 12-1
Alloy composite atom % Magnetic density/T is 1.6 * 10 4The A/m place Initial permeability is at the 100kHz place The XRD measurement result
Comparative example 30 Fe 79P 1B 16Mo 4 0.64 25 Crystalline phase
Instance 87 Fe 78P 2B 16Mo 4 0.63 30 Amorphous phase
Instance 88 Fe 75P 16B 5Mo 4 0.60 30 Amorphous phase
Comparative example 31 Fe 74P 17B 5Mo 4 0.59 24 Crystalline phase
Comparative example 32 Fe 79P 16B 1Mo 4 0.63 20 Crystalline phase
Instance 89 Fe 78P 16B 2Mo 4 0.62 32 Amorphous phase
Instance 90 Fe 75P 5B 16Mo 4 0.59 30 Amorphous phase
Comparative example 33 Fe 74P 5B 17Mo 4 0.58 25 Crystalline phase
Comparative example 34 Fe 82P 8B 10Mo 0 0.79 24 Crystalline phase
Instance 91 Fe 81P 8B 10Mo 1 0.75 30 Amorphous phase
Instance 92 Fe 78P 8B 10Mo 4 0.62 32 Amorphous phase
Instance 93 Fe 72P 8B 10Mo 10 0.37 30 Amorphous phase
Comparative example 35 Fe 71P 8B 10Mo 11 0.30 25 Crystalline phase
Instance 94 Fe 78P 7B 9Mo 4Si 2 0.62 32 Amorphous phase
Instance 95 Fe 72P 7B 9Mo 4Si 8 0.55 30 Amorphous phase
Comparative example 36 Fe 71P 7B 9Mo 4Si 9 0.53 24 Crystalline phase
Instance 96 Fe 72P 8B 10Al 4 0.75 30 Amorphous phase
Instance 97 Fe 78P 8B 10V 4 0.67 31 Amorphous phase
Instance 98 Fe 78P 8B 10Cr 4 0.64 30 Amorphous phase
Instance 99 Fe 78P 8B 10Y 4 0.63 30 Amorphous phase
Instance 100 Fe 78P 8B 10Zr 4 0.63 31 Amorphous phase
Instance 101 Fe 78P 8B 10Nb 4 0.62 32 Amorphous phase
Instance 102 Fe 78P 8B 10Ta 4 0.61 32 Amorphous phase
Instance 103 Fe 78P 8B 10W 4 0.60 31 Amorphous phase
Table 12-2
Alloy composite atom % Magnetic density/T is 1.6 * 10 4The A/m place Initial permeability is at the 100kHa place The XRD measurement result
Instance 104 (Fe 0.8Co 0.2) 78P 8B 10Mo 4 0.63 31 Amorphous state
Instance 105 (Fe 0.8Ni 0.2) 78P 8B 10Mo 4 0.59 32 Amorphous state
Instance 106 (Fe 0.1Co 0.9) 78P 8B 10Mo 4 0.22 34 Amorphous state
Instance 107 (Fe 0.05Ni 0.05Co 0.9) 78P 8B 10Mo 4 0.20 37 Amorphous state
Comparative example 37 (Fe 0.0Ni 1.0) 78P 8B 10Mo 4 0 - Amorphous state
Instance 108 (Fe 0.8Co 0.2) 78P 7B 9Si 2Mo 4 0.63 30 Amorphous state
Instance 109 (Fe 0.8Ni 0.2) 78P 7B 9Si 2Mo 4 0.57 32 Amorphous state
Instance 110 (Fe 0.05Ni 0.05Co 0.9) 78P 7B 9Si 2Mo 4 0.20 37 Amorphous state
Comparative example 38 (Fe 0.0Ni 1.0) 78P 7B 9Si 2Mo 4 0 Amorphous state
Figure G2009101276380D00461
Figure G2009101276380D00471
Table 14
Sample number into spectrum Amount of resin Molding temperature Powder filling rate % Magnetic density/T is 1.6 * 10 4The A/m place Resistivity Ω cm
1 0.5% Room temperature 68.1 0.44 ≥100
2 1.0% Room temperature 69.9 0.45 ≥100
3 2.5% Room temperature 72.7 0.47 ≥100
4 5.0% Room temperature 71.5 0.46 ≥100
5 0.5% 150℃ 80.3 0.73 5
6 1.0% 150℃ 81.9 0.75 10
7 2.5% 150℃ 82.6 0.75 15
8 5.0% 150℃ 72.7 0.47 ≥100
9 0.5% 480℃ 95.2 1.13 0.1
10 1.0% 480℃ 92.4 1.09 0.5
11 2.5% 480℃ 83.0 0.76 10
12 5.0% 480℃ 73.4 0.48 ≥100
Table 15
The sample title Magnetic density/T is 1.6 * 10 4The A/m place Resistivity Ω cm Magnetic permeability Core loss 20kHz 0.1T
The present invention 10,900 0.5 150 60mW/cc
The present invention's (heat treatment) 11,100 0.5 200 20
The MnZn ferrite 5,500 ≥10E4 100 8
Sendust 6,500 100 80 90
6.5% silicon steel 10,000 100μ 100 250
The base amorphous phase material of Fe 13,000 150μ 100 400
*Owing on the part magnetic circuit, form the power specification of breach
Table 16
Sample number into spectrum Alloy composite The powder ratio % that adds Powder filling rate % Magnetic permeability is at the 100kHz place Core loss 20kHz 0.1T
Comparative example 54 - - 74.5 34 20kW/m 3
1 3%SiFe 5 75.1 37 25
2 3%SiFe 10 75.7 39 35
3 3%SiFe 20 76.3 40 55
4 3%SiFe 30 76.9 41 65
5 3%SiFe 40 77.5 42 75
6 3%SiFe 50 78.0 44 85
7 3%SiFe 60 78.2 44 190
8 Sendust 30 75.7 38 75
9 The Mo permalloy 30 78.0 43 80
10 Pure iron powder 30 79.5 48 90
Table 17
Figure G2009101276380D00511
Table 18
Sample number into spectrum Filter screen particle diameter μ m Medium particle diameter (D50) μ m L (μ H) is at the 1MHz place The crest frequency of Q The peak value of Q Power conversion efficient
Comparative example 55 45 34 0.60 ?300kHz ?31 79.8%
1 45 29 0.63 ?600kHz ?43 83.3
2 45 24 0.66 ?800kHz ?46 83.9
3 45 19 0.69 ?1.5MHz ?61 85.5
4 45 16 0.67 ?2.5MHz ?66 85.6
5 45 12 0.65 ?3.5MHz ?75 85.9
5 (heat treatments) 45 12 0.75 ?3.0MHz ?81 87.6
Comparative example 56 63 28 0.69 ?400kHz ?33 79.5
Figure G2009101276380D00531

Claims (12)

1. amorphous soft magnetic band that is made by amorphous soft magnetic, the expression formula of the composition of said amorphous soft magnetic is (Fe 1-αTM α) 100-w-x-y-zP wB xL ySi z, wherein containing unavoidable impurities, TM is from Co and Ni, choose at least a; L is from the group that is made up of Al, V, Cr, Y, Zr, Mo, Nb, Ta and W, choose at least a; 0≤α≤0.98,2 atom %≤w≤16 atom %, 2 atom %≤x≤16 atom %; 0 atom %<y≤10 atom % and 0 atom %≤z≤8 atom %
Wherein crystallization start temperature Tx is 550 ℃ or lower, and glass transition temperature Tg is 520 ℃ or lower, and is 20 ℃ or bigger by the supercooled liquid scope that Δ Tx=Tx-Tg representes, the thickness of wherein said amorphous soft magnetic band is 1 to 200 μ m.
2. amorphous soft magnetic band as claimed in claim 1, wherein said amorphous soft magnetic band frequency be the magnetic permeability of 1kHz be 5000 or more than.
3. one kind twines the magnetic core form through amorphous soft magnetic band as claimed in claim 1 being carried out annular.
4. magnetic core as claimed in claim 3 carries out the annular winding through insulator to said amorphous soft magnetic band and forms.
5. one kind through carrying out the range upon range of magnetic core that forms with the multi-disc of basic identical shape amorphous soft magnetic band as claimed in claim 1.
6. magnetic core as claimed in claim 5, it is through the said amorphous soft magnetic band of the multi-disc of said basic identical shape is carried out range upon range of formation via intervenient insulator.
7. amorphous soft magnetic band of being processed by amorphous soft magnetic, the expression formula of the composition of said amorphous soft magnetic is (Fe 1-αTM α) 100-w-x-y-zP wB xL ySi z(Ti pC qMn rCu s), wherein containing unavoidable impurities, TM is from Co and Ni, choose at least a, L is from the group that is made up of Al, Cr, Mo and Nb, choose at least a; 0≤α≤0.3,2 atom %≤w≤18 atom %, 2 atom %≤x≤18 atom %, 15 atom %≤w+x≤23 atom %; 1 atom %≤y≤5 atom %, 0 atom %≤z≤4 atom %, wherein all to be illustrated in the gross mass of Fe, TM, P, B, L and Si be 100 o'clock interpolation ratio for each p, q, r and s; And confirm as 0≤p≤0.3,0≤q≤0.5,0≤r≤2; 0≤s≤1,0<r+s≤3, the thickness of wherein said amorphous soft magnetic band are 1 to 200 μ m.
8. amorphous soft magnetic band as claimed in claim 7, wherein said amorphous soft magnetic band are that the magnetic permeability of 1kHz is 5000 or higher in frequency.
9. one kind twines the magnetic core form through amorphous soft magnetic band as claimed in claim 7 being carried out annular.
10. magnetic core as claimed in claim 9, it carries out the annular winding through insulator to said amorphous soft magnetic band and forms.
11. one kind through carrying out the range upon range of magnetic core that forms with the multi-disc of basic identical shape amorphous soft magnetic band as claimed in claim 7.
12. magnetic core as claimed in claim 11, it is through carrying out range upon range of formation with the said amorphous soft magnetic band of the multi-disc of said basic identical shape via intervenient insulator.
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