CN101840764B - Low-cost high-saturation magnetic induction intensity iron-based amorphous soft magnetism alloy - Google Patents
Low-cost high-saturation magnetic induction intensity iron-based amorphous soft magnetism alloy Download PDFInfo
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Abstract
The invention provides a low-cost high-saturation magnetic induction intensity iron-based amorphous soft magnetism alloy. The alloy comprises the following ingredients in percentage by atoms: 0 to 15 of Si, 3 to 20 of B, 0.001 to 12 of P, 0.001 to 5 of C, 0.0001 to 0.1 of Al, 0.001 to 0.5 of Mn, 0.0001 to 0.5 of Sb, 0.0001 to 0.1 of Ti, 0.0001 to 0.5 of S, 0.0001 to 0.5 of Sn, 0.0003 to 0.2 of W and the balance of Fe and unavoidable impurities. The soft magnetism alloy of the invention has the characteristics of strong amorphous forming capability, high saturation magnetic induction intensity, low cost and the like. After the alloy is annealed, the saturation magnetic induction intensity is higher than 1.6 T, and the coercive force is lower than 5A/m.
Description
Technical field
The present invention relates to the magnetic functional material field, particularly a kind of iron base amorphous magnetically-soft alloy of low-cost high-saturation magnetic induction intensity.
Background technology
After amorphous soft magnetic material comes out; Especially iron-based non-crystalline alloy exists that resistivity is high, magnetic permeability is high, and the characteristics of loss very low (only be equivalent to orientation silicon steel 1/3～1/5); Compare with silicon steel in addition; Technology is simple, need not specially process, and therefore is considered to make the desirable core material of power transformer.And adopt non-crystaline amorphous metal to replace the thin silicon steel almost to start to walk simultaneously with the making of Fe-based amorphous band as the research work of power transformer iron core.
But compare with silicon steel, still there is its weak point in Fe-based amorphous alloy, and promptly activity coefficient and saturation induction density are relatively low.The B of crystalline state orientation silicon steel for example
sValue is about 2T, and typical Fe-based amorphous alloy Fe
78Si
9B
13B
sValue is 1.56T.When the preparation magnetic element,, often hope that the saturation induction density of these devices is higher in addition, because this means the perhaps reduction of exciting power that reduces of plant bulk like transformer core, motor rotor and magnetic switch etc.For activity coefficient, method in common is to improve strip surface quality, the for example uniformity of surface smoothness and thickness of strip.But because amorphous band itself is thinner, be merely tens microns, the potentiality that make activity coefficient promote are limited.And for the latter, numerous researcher's past attempts attempt to obtain the iron-based non-crystalline alloy that saturation induction density is higher than 1.6T.Wherein most typical example is that saturation induction density is the Metglas2605Co alloy of 1.8T, but comprises 18% Co atom in this alloy, costs an arm and a leg, and can not be used for industrial magnetic product.In addition, disclose a kind of amorphous state Fe-B-C alloy in the U.S. Pat 4226619, its saturation induction density is more than 1.7T, but the coercive force of alloy is bigger, and too crisp, can't in reality, use.Hitachi Metals discloses the Fe-Si-B-C alloy of a kind of HB1 by name in publication number is the one Chinese patent application of CN1721563A; Its saturation induction density is more than 1.6T; But it adopts the method for carburizing in preparing process; This has improved production cost undoubtedly, has reduced the controllability of product quality.
Japan Patent JP59016947 discloses the alloy that a kind of expression formula is FeSiBC, and wherein the content to P, Al and three kinds of impurity of S limits, by percentage to the quality, and P＜0.015, S＜0.02, Al＜0.03.Patent EP0058269A1 discloses the alloy that a kind of expression formula is FeSiB, and wherein the high-load to various microalloy elements limits, and for example P is limited to below the 0.008at%, and Sn content is limited to below the 0.001at%, and C is limited to below the 0.02at%.But experiment shows when elements such as an amount of interpolation P, C and Al are higher than the upper content limit of these patents announcements in amorphous soft magnetic alloy, its favourable one side is arranged.For example P be added with the amorphous formation ability that helps improve alloy system, and an amount of interpolation of C can improve soft magnet performance, improves the saturation induction density of alloy.
Japan Patent JP57185957A discloses the alloy that a kind of expression formula is FeSiBPC, and its saturation induction density is more than 1.5T, but B content wherein is too low, and atom % is below 5.And research shows, the B element is the important element that forms amorphous alloy, and when its content was lower than 5at%, the amorphous formation ability of alloy was relatively poor, and the thermal stability of alloy is relatively poor.
The expression formula that Japan Patent JP9202946 discloses a kind of Mn of containing is the alloy of FeSiBC, but its iron content is lower, and atom % is only below 82.Because the saturation induction density and the iron content of alloy have confidential relation, therefore, the saturation induction density of alloy can not obtain bigger raising.
Japan Patent JP85051887 discloses the alloy that a kind of composition is FeSiBC, and wherein the content of C is limited to 3.25～4at%.Research shows, when C content is higher than 3at%,, catches fire easily to the preparation condition requirement harshness of alloy, and the easy embrittlement of the band of preparation, and thermal stability descends.
Chinese patent CN101194039A has announced a kind of Fe-Si-B-C-P-N multicomponent alloy of the N of containing element; But experiment shows; Because N ultralow solid solubility in molten steel according to prior art, is difficult to realize the stable control of N content in the amorphous alloy ribbon; And the poor heat stability that contains the N alloy can't at high temperature be used.
U.S. Pat 5958153A has announced that a kind of P content is lower than 0.1%, thickness is (FeSiBC) in the expression formula of 40-90 μ m
100-xP
xAlloy strip steel rolled stock, but the P in the alloy mixes with the unavoidable impurities form, Fe content is relatively low, saturation induction density is also low, this is difficult to satisfy the requirement of power device to high saturated magnetic induction.Similarly, patent JP9-95760, patent JP 2001-279387 also mix as the unavoidable impurities element with P.
U.S. Pat 5626690 has been announced a kind of FeSiBP (C) alloy that initiatively adds the P element, but all alloy Fe content of giving an example are all at 80 atom % and following, and Si content is higher than 10 atom %, and P content is lower than 2 atom %.But research shows, during the Si too high levels, will make the viscosity of molten steel increase, and preparation brings technologic difficulty to band, and when Si content was high, the saturation induction density of alloy did not increase with Fe content and improves simultaneously.This all makes the saturation induction density of this alloy be limited to about 1.5T.
Japan Patent JP 2008248380 discloses the FeSiBP alloy of a kind of Al of containing, and its core loss value is below 0.1W/kg, but Al is prone to the oxidation element, when content is high, under air, is difficult to preparation.And the P too high levels of giving an example is 8～20 atom %.Research shows that P is that (Si, B, P, C, Ge) contributes maximum one to the saturation induction density that reduces alloy in the metalloid element commonly used, so the P too high levels, can reduce the saturation induction density of alloy.
In sum; Still lack in the market and have iron base amorphous magnetically-soft alloy and the goods thereof that high saturated magnetic induction has low-cost characteristic simultaneously concurrently, so this area still exists having the needs of high saturated magnetic induction, iron base amorphous magnetically-soft alloy simultaneously with low cost.
Summary of the invention
The invention provides a kind of with low cost, amorphous formation ability is strong, saturation induction density is high iron base amorphous magnetically-soft alloy.The admitted facts in this area are, for preparation raw materials such as pure iron, ferrophosphorus and ferro-borons, its cost does not raise with the linear relationship ground that is lowered into of impurity content, but raise with the exponential form that is lowered into of impurity content.For example the Armco iron price of 99wt% is about 10 yuan/kilogram, and the price of the pure iron of 99.5wt% is about 100 yuan/kilogram, and the pure iron price of 99.9wt% is then about 1500 yuan/kilogram.This is because the purification of preparation raw material often needs higher cost.And for raw materials such as ferro-boron, ferrophosphorus, because itself element complexity and variation, the cost that causes purifying is higher.Therefore, for the production and the preparation of amorphous alloy, directly adopt the low cost raw material preparation that contains S, Al and Ti element, be research and development engineer's target always.
The inventor is according to weak point of the prior art; A kind of Fe-based amorphous alloy has been proposed; Its composition mentality of designing be with than the FeB binary system of large-amorphous forming capacity as foundry alloy; Add the Si element that can improve the non-crystaline amorphous metal Curie temperature in right amount according to designing requirement, and add elements such as proper C, Mn, W, Sn and Sb, prepare the iron base amorphous magnetically-soft alloy and the goods thereof of excellent performance through production technologies such as melting, fast quenching, atomizings.
The invention provides a kind of iron base amorphous magnetically-soft alloy of low-cost high-saturation magnetic induction intensity.The atom % of the component of this alloy satisfies: Si content: 0～15, and B content: 3～20, P content: 0.001～12; C content: 0.001～5, Al content: 0.0001～0.1, Mn content: 0.001～0.5; Sb content: 0.0001～0.5, Ti content: 0.0001～0.1, S content: 0.0001～0.5; Sn content: 0.0001～0.5, W content: 0.0003～0.2, all the other are Fe and unavoidable impurities.
Iron base amorphous magnetically-soft alloy of the present invention is particularly suitable for the iron core of motor.Adopt the prepared product of Fe-based amorphous alloy of the present invention to compare, have characteristics such as amorphous formation ability is strong, saturation induction density is high, with low cost with prior art products.
Description of drawings
Fig. 1 is the loss of embodiment 4-1 and Comparative Examples and (Ti+Al+S) relation of content.
Fig. 2 is the coercive force of embodiment 4-1 and Comparative Examples and (Ti+Al+S) relation of content.
Fig. 3 is the saturation induction density of embodiment 4-1 and Comparative Examples and (Ti+Al+S) relation of content.
Fig. 4 is the loss of embodiment 4-2,4-3,4-4 and Comparative Examples and (Ti+Al+S) relation of content.
Embodiment
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, at first, the Mn element can suppress the crystallization that impurity element causes on the non-crystaline amorphous metal surface, and improves soft magnet performance; Secondly, the interpolation of Mn can suppress the band embrittlement that the impurity element S in the alloy causes effectively, and this is because Mn and S are prone in molten steel, form the MnS compound.The inventor finds; This high-melting-point field trash is under the condition of cooling fast; And under the condition that Sn and Sb element exist in the present invention; MnS exists with bulk or line inclusion form, but is distributed in alloy inside with small uniform particles, and has therefore farthest reduced embrittlement and soft magnet performance deterioration that the S element causes; At last,, not only can improve the surface quality of non-crystaline amorphous metal, can also appropriateness improve the saturation induction density of alloy when Mn content is controlled at 0.5at% when following.And S almost is the impurity element that must contain in ferro-boron, silicon and the source of iron, so the interpolation of Mn increased the tolerance of S element, and the source that this has widened the preparation raw material has reduced the cost of raw material.When if Mn content is lower than 0.001at%, can't embody the effect that the Mn element suppresses crystallization.So the Mn constituent content is 0.001～0.5at%, more preferably content is 0.005～0.5at%, and most preferred scope is 0.01～0.3at%.
Simultaneously, an amount of existence of S element can suppress the performance embrittlement that the Sn element in the raw material causes.This mainly is because the S element can combine to generate lower boiling SnS with Sn, in high-temperature molten steel, vapors away and reaches the purpose of reduction S and Sn simultaneously.But the content of S element can not be too high, when the S constituent content surpasses 0.5at%, will cause the non-crystaline amorphous metal embrittlement serious, and soft magnet performance worsens, and improves even add Sn, and effect is also limited.So the atom % of S constituent content is 0.0001～0.5, is preferably 0.0005～0.3, is more preferably 0.001～0.3.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the interpolation of element sb has special effect.Element al and Ti are generally considered to be the impurity element in the amorphous alloy, because the existence of these two kinds of elements can cause soft magnet performance to worsen, so often hope that the content of these two kinds of elements in the raw material is low more good more.The experiment proof; Combination forms aluminium oxide and titanium oxide to these two kinds of elements with O owing to being easy to, and accumulates in the generation segregation of non-crystaline amorphous metal surface easily, has hindered the surface segregation of neccessary composition; Make amorphous form elements Si and obviously reduce, cause the crystallization on non-crystaline amorphous metal surface easily at surface enrichment.In addition, the superficial layer of crystallization also can produce compression to amorphous inside, and this double action makes soft magnet performance worsen, and loss is multiplied.To this difficult problem, the inventor is unexpected to be found, through in alloying component, adding a spot of Sb element, the soft magnet performance that can obviously suppress to cause when Ti and Al element exist worsens, and promptly improves the tolerance of Ti and Al impurity element relatively.Think that through further research an amount of Sb at the surface enrichment of non-crystaline amorphous metal, has suppressed Ti and the Al segregation on the surface after adding alloy, avoided of the segregation of the Si element of Ti and Al element inhibition on the surface.The inventor also finds, when having the Mn element simultaneously in the alloy, and an amount of adding of Sb, the MnS that can cause generating and/or the average-size of AlN particle are thinner, more, and mostly the particle size is below the 10nm even is thinner.The particle of these refinements still remains after annealing at non-crystaline amorphous metal, is disperse and evenly distributes, and the fragility of promptly not obvious increase non-crystaline amorphous metal does not cause the crystallization of alloy yet, but and under high frequency condition the refinement magnetic domain, reduce the alloy loss.In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the addition of Sb element is below 0.5at%.If content surpasses 0.5at%, not only reduce the saturation magnetization of alloy, and form a large amount of segregations easily; Cause alloy embrittlement; And Sb content is lower than at 0.0001 o'clock, and the effect of Sb element is difficult to bring into play, so Sb atoms of elements % of the present invention satisfies: 0.0001≤Sb≤0.5; The scope that is more preferably is: 0.0005≤Sb≤0.4, most preferred scope are 0.001≤Sb≤0.3.China abounds with the Sb element, and price is not high, and therefore, a spot of interpolation does not cause the rising of alloy total cost.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the content of Al and Ti element can not be too high, otherwise can cause the loss of alloy sharply to increase, even have inhibiting Sb element to exist to Al and Ti, also is difficult to improve soft magnet performance.Therefore, in the present invention, Al and Ti atoms of elements % need satisfy: 0.0001≤Al≤0.1; 0.0001≤Ti≤0.1, the scope that is more preferably are 0.0001≤Al≤0.05,0.0001≤Ti≤0.05; Most preferred scope is 0.0001≤Al≤0.01,0.0001≤Ti≤0.01.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the interpolation of element S n has special effect.At first, the existence of Sn can reduce the S content in the alloy.Because general low-purity prepares and contains more S element in the raw material; And an amount of existence ability and the S of Sn generate lower boiling SnS compound under hot conditions; And this compound is in the amorphous alloy component that contains a large amount of Si elements and C element of the present invention; Highly volatile falls, thereby reaches the purpose that in the foundry alloy molten steel, reduces S and Sn content simultaneously.Secondly; The inventor herein finds; Because the chemical property of Sn is stable, be difficult for S outside other elements form compounds, the existence of therefore an amount of Sn has increased the complexity between the non-crystaline amorphous metal constituent element; And reduced the fusing point of alloy, this for optimal preparation technology, clear meaning has reduced the wastage.Once more, the inventor also finds, the existence of Sn can also effectively suppress the soft magnet performance that Al and Ti element caused and worsen.Because the existence of these two kinds of elements can cause soft magnet performance to worsen, so often hope that the content of these two kinds of elements in the raw material is low more good more.The experiment proof; Combination forms aluminium oxide and titanium oxide to these two kinds of elements with O owing to being easy to, and accumulates in the generation segregation of non-crystaline amorphous metal surface easily, has hindered the surface segregation of neccessary composition; Make amorphous form the enrichment of element S i and obviously reduce, cause the crystallization on non-crystaline amorphous metal surface easily on the surface.Simultaneously crystallization superficial layer also can produce compression to amorphous, this double action makes soft magnet performance worsen, loss is multiplied.To this difficult problem, the inventor finds, in alloy system, adds a spot of Sn element, can significantly suppress because the decline and the loss increase at double of the saturation induction density that Ti and Al element cause.Discover, this be since Sn on non-crystaline amorphous metal surface priority enrichment, and stop Ti and of the segregation of Al element, thereby make elements Si ability normal segregation on the surface.Simultaneously, because the particular design of this alloying component, excessive Sn element can vapor away with the formation of SnS again, reaches the purpose that reduces Sn and S simultaneously.At last, the inventor finds that also inner at non-crystaline amorphous metal, when not containing Sn, a spot of MnS and/or AlN field trash become chain and wire to exist.And after adding a spot of Sn, a spot of MnS and/or AlN field trash particle average-size attenuate, and be more, and the particle size is many below 10nm.Further research is thought, add a spot of Sn after because Sn is insoluble to Fe, at the AlN surface enrichment, the enrichment of Sn has reduced interface energy, thereby has suppressed growing up of AlN.This effect makes the AlN field trash be reduced to minimum to the deterioration of non-crystaline amorphous metal soft magnet performance.Although the Sn element has important function in the present invention, the content of Sn element can not surpass 0.5at%, because too high levels will cause the non-crystaline amorphous metal embrittlement, is difficult for preparation, and when content was too low, the above-mentioned effect of Sn element was difficult to bring into play.So the content range of Sn element is 0.0001～0.5at%, preferred scope is 0.001～0.4at%, and most preferred scope is 0.002～0.3at%.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the existence of element W also has important effect.Because the atomic radius of W is bigger, joins in the alloy system, can improve the self-diffuse activation energy of elements such as Fe, B, Si, thereby in melt, increase the viscosity of alloy, has improved the amorphous formation ability of alloy system.The existence of W also increased elements such as aforementioned Ti, Al in alloy melt through diffuseing to form the resistance of field trash, further reduced of the infringement of elements such as Ti, Al to soft magnet performance.In addition, W joins in the magnetically soft alloy, is approximately zero magnetostriction coefficient owing to have, and can improve the magnetic permeability of alloy, because W has high melt point, can improve the thermal stability of alloy simultaneously, and improves the Curie temperature of alloy.But W reduce the fastest magnesium-yttrium-transition metal of saturation induction density of alloy, and price is more expensive, so content can not be too high owing to be except that ferromagnetic element.In the Fe-based amorphous alloy of high saturated magnetic induction cheaply of the present invention, the content of W element is 0.0003～0.2at%, and preferred range is 0.001～0.1at%, and most preferred scope is 0.001～0.05at%.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention; B atoms of elements % content will satisfy: 5≤B≤18; Preferred scope is 7≤B≤16, and most preferred scope is 8≤B≤15, when B atom % greater than 18 the time; Ferromagnetic element content reduces relatively, causes the saturation induction density of alloy to reduce.And at B atom % less than 5 o'clock, the thermal stability of alloy is too poor, is difficult to prepare amorphous alloy.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, Si atoms of elements % content will satisfy: 5≤Si≤15, the scope that is more preferably are 5≤Si＜13, and most preferred scope is 6≤Si＜12.When Si atom % greater than 15 the time, the content of P and B is suppressed, the amorphous formation ability variation of alloy, and the viscosity of alloy melt increases, and is difficult for preparing non-crystaline amorphous metal, when Si atom % less than 5 the time, the Curie temperature of alloy is low, thermal stability is too poor.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, P atoms of elements % content will satisfy: 0.002≤P≤5, the scope that is more preferably are 0.01≤P≤5, and most preferred scope is 0.01≤P≤3.When P atom % greater than 5 the time, cause the saturation induction density of alloy to reduce.When P atom % less than 0.002 the time, the raising amorphous formation ability of P element, the effect that suppresses crystallization can't be brought into play.
In the Fe-based amorphous alloy of low-cost high-saturation magnetic induction intensity of the present invention, the C element has little atomic size, and its an amount of interpolation can improve the saturation induction density of alloy.Aspect preparation technology, the adding of C can reduce the viscosity of molten steel, improves the flowability of molten steel.In the present invention, when C atom % greater than 5 the time, the amorphous formation ability variation of alloy, coercive force rises, loss increases, soft magnet performance worsens.Therefore C atom % content will satisfy: 0.002≤C≤3.25, the scope that is more preferably are 0.02≤C≤2, and most preferred scope is 0.01≤C≤1.5.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, Fe can partly be replaced by at least a element among the V below the 2.5 atom %, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, Pb, Y, Au, Cu, Tl, Nb, Zr, Hf, Be, the Bi.These elements are non-ferromagnetic elements, and when its content was higher than 2.5 atom %, the saturation induction density of alloy reduced.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, Fe can partly be replaced by Ni and/or the Co below the 15 atom %.
In the Fe-based amorphous alloy of high saturation induction intensity of the present invention, except that above-mentioned alloying element, surplus is made up of Fe, wherein possibly contain a spot of impurity element, and like S, O etc., but the total weight percent of all impurity elements is less than 0.5%.
The preparation method of the Fe-based amorphous alloy of high saturation induction intensity of the present invention is identical with prior art; Be at nitrogen or/and under the argon gas protection; Adopt induction furnace to carry out the foundry alloy melting, adopt single-roller method or double roller therapy to be prepared into amorphous band and sheet material then, perhaps adopt atomization to be prepared into powder; Perhaps adopt copper mold casting method to be prepared into bar, perhaps adopt fiber elongation method to be prepared into a material.Choose and be lower than 100 ℃ of crystallization temperatures to the temperature range that is lower than 10 ℃ of crystallization temperatures as heat treatment temperature, best heat treatment temperature is to be lower than 75 ℃ of crystallization temperatures to the temperature range that is lower than 15 ℃ of crystallization temperatures as heat treatment temperature T
a, can be expressed as T with formula
a=(T
x-75 ℃)～(T
x-15 ℃), annealed 5～60 minutes, can obtain the Fe-based amorphous alloy of high saturation induction intensity.
The saturation induction density B of alloy
sAdopt vibrating specimen magnetometer (VSM) to measure, the magnetic flux density when being 10000A/m with magnetic field is as the saturation induction density of alloy.SY 8232B-H tester is adopted in the loss measurement of non-crystaline amorphous metal, and test condition is magnetic strength 1.4T, and frequency is 60Hz, is designated as P
14/60The coercive force H of alloy
cWith maximum permeability μ
MaxAdopt soft magnetism DC B-H hysteresisograph to record.
First group of embodiment
According to the composition range of Fe-based amorphous alloy of the present invention, we carry out this serial experiments.Table 1 is for preparing burden according to composition of the present invention, with master alloy ingot melting to 1250 ℃, and adopts single-roller method to prepare wide 20 ± 0.2mm, the thickness amorphous thin ribbon at 27～29 μ m with the roller speed of 32m/s.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, with iron core through 430/440 ℃ of isothermal annealing 30 minutes, cool to the furnace alloy below 200 ℃ after, air cooling is to room temperature, the soft magnet performance index that measures is seen shown in the table 1.
Can find out that by the composition of giving an example in the table 1 the saturation induction density Bs of amorphous alloy of the present invention is higher, more than 1.6T reaches.It can also be seen that by table 1, outside the influencing factor of getting rid of test and impurity, B
sThe size of value and Fe content have direct corresponding relationship, and when promptly iron content was high, the saturation induction density of alloy was higher.But when the P constituent content is too much, then can reduce the saturation induction density of alloy.And C element, Sn element and Sb constituent content then can improve preparation technology's difficulty when higher, increase the coercive force of alloy simultaneously.Even but like this, still can coercive force be remained on below the 5A/m.And it can also be seen that the maximum permeability μ of the present invention's example by table 1
MaxMainly concentrate between 20～500,000, and loss P
14/60Then at 0.5W/kg and following.
In order to contrast conveniently, our also given an example simultaneously composition alloy of multiple prior art, its performance parameter index is listed in the table 2.Contrast table 2 can find out that with table 1 contrast the saturation induction density of the alloy of existing composition is lower, for example 1～No. 11 in the table 2 and 16～No. 22 alloys.Though 12～No. 14 alloys in the table 2 have higher saturation induction density (more than 1.70T), significantly weak point is arranged, i.e. the coercive force of silicon steel and loss is all bigger, and magnetic permeability is low.And the coercive force of 13～No. 14 alloys is bigger equally, and thermal stability is relatively poor simultaneously, and is difficult to preparation because of C content is high.15～No. 16 alloys in the table 2 have higher saturation induction density because of adding Co, but its expensive cost has suppressed its application potential as industrial magnetic product.Equally, 17～No. 22 alloys in the table 2 make also that because of containing a large amount of Ni elements alloy costs an arm and a leg, and are unfavorable for industrialized extensive use.
Embodiment and the Comparative Examples among the table 2 in the comparison sheet 1 can be found out; FeSiBPC alloy of the present invention; Higher saturation induction density and magnetic permeability are not only arranged; And lower coercive force and loss are arranged, and add the characteristics that cost of alloy is lower, be easy to prepare, can be referred to as the iron base amorphous magnetically-soft alloy of the high saturated magnetic induction of excellent combination property.
Table 1 first group of embodiment of the present invention
Annotate: subscript bal. represents surplus
First group of Comparative Examples of table 2
Second group of embodiment
According to the composition range of Fe-based amorphous alloy of the present invention, we carry out this serial experiments.Table 3 is for preparing burden according to composition of the present invention, with master alloy ingot melting to 1250 ℃, and adopts single-roller method to prepare wide 20 ± 0.2mm, the thickness amorphous thin ribbon at 28～30 μ m with the roller speed of 35m/s.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, with iron core through 420/430 ℃ of isothermal annealing 30 minutes, cool to the furnace alloy below 200 ℃ after, air cooling is to room temperature, the soft magnet performance index that measures is seen shown in the table 3.
Second group of embodiment of table 3 the present invention
Annotate: subscript bal. represents surplus
The 3rd group of embodiment
According to the composition range of Fe-based amorphous alloy of the present invention, we carry out this serial experiments.Table 4 is for preparing burden according to composition of the present invention, with master alloy ingot melting to 1250 ℃, and adopts single-roller method to prepare wide 20 ± 0.2mm, the thickness amorphous thin ribbon at 28～30 μ m with the roller speed of 35m/s.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, with iron core through 420/430 ℃ of isothermal annealing 30 minutes, cool to the furnace alloy below 200 ℃ after, air cooling is to room temperature, the soft magnet performance index that measures is seen shown in the table 4.
Table 4 the 3rd group of embodiment of the present invention
Annotate: subscript bal. represents surplus
The 4th group of embodiment
According to the composition range of Fe-based amorphous alloy of the present invention, we carry out this serial experiments.Prepare burden according to composition of the present invention,, and adopt single-roller method to prepare wide 20 ± 0.2mm, thickness amorphous thin ribbon at 28～30 μ m with the roller speed of 28m/s with master alloy ingot melting to 1250 ℃.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, with iron core through 430 ℃ of isothermal annealings 30 minutes, cool to the furnace alloy below 200 ℃ after, air cooling is to room temperature.
Be an amount of interpolation of the Sb among the present invention that systematically gives an example, Sn, Mn, the W inhibitory action to (Ti, Al, S) element, this experiment is specially to Fe
Bal.Si
11B
6P
0.5C
0.5Add (Ti+Al+S) element of different content in the alloy, and add according to 1: 1: 2 ratio.The detection of constituent content adopts direct-reading spectrometer and CS analyzer to test.Adding proportion is 2: 1: 2 in alloy simultaneously: 0.5, total amount is (Sb+Sn+Mn+W) element of 0.2at%, measures loss, saturation induction density and coercive force under different (Ti+Al+S) constituent contents.Be convenient contrast, we have prepared the Fe that does not add (Sb+Sn+Mn+W) element, interpolation (Ti+Al+S) element simultaneously
Bal.Si
11B
6P
0.5C
0.5Alloy is as comparing alloy (being the Comparative Examples among Fig. 1～Fig. 4).The performance index that measure are seen Fig. 1～Fig. 3, and wherein embodiment 4-1 is for adding the alloy of (Sb+Sn+Mn+W) element, and Comparative Examples is not for adding the alloy of element sb, Sn, Mn and W.Fig. 4 is the loss of the alloy that adds different element combinations among Sb, Sn, Mn and the W and comparative example alloy and (Ti+Al+S) relation with contents curve.Wherein embodiment 4-2 is that 0.2at% and ratio are the alloy of 1: 2: 0.5 (Sn+Mn+W) for being added with total amount; Embodiment 4-3 is that 0.2at% and ratio are the alloy of 2: 2: 0.5 (Sb+Mn+W) for being added with total amount; Embodiment 4-4 is that 0.2at% and ratio are the alloy of 2: 0.5 (Mn+W) for being added with total amount; The same Fig. 1 of Comparative Examples is the alloy that does not add Sb, Sn, Mn and W.
Can find out by Fig. 1～Fig. 2, only contain the Fe of (Ti+Al+S) element
Bal.Si
11B
6P
0.5C
0.5Alloy, loss and coercive force all increase and increase fast with (Ti+Al+S) constituent content, and after adding (Sb+Sn+Mn+W) element of 0.2at%, the loss of alloy and coercive force increase all become slowly, only when (Ti+Al+S) content is big, begin to increase.Can find out by Fig. 3, reduce B a little although add the saturation induction density of (Sb+Sn+Mn+W) alloy of 0.2at%
sDescend slowly, the increase with (Ti+Al+S) content does not have the bigger range of decrease.Can find out that by Fig. 4 add (Mn+W) element separately, loss decreases, but is not very remarkable.And add (Sn+Mn+W) or (Sb+Mn+W) after, the loss of alloy then has comparatively significantly and to reduce.Contrast by Fig. 1～Fig. 4 can be found out, in the alloy that contains Ti, Al, S impurity, adds an amount of a certain proportion of Sb, Sn, Mn, W alloy, has played the effect that suppresses coercive force and loss increase, improves soft magnet performance.
Claims (29)
1. an iron base amorphous magnetically-soft alloy is characterized in that, the atom % of this alloy compositions satisfies:
Si content: 0～15;
B content: 3～20;
P content: 0.001～12;
C content: 0.001～5;
Al content: 0.0001～0.1;
Mn content: 0.001～0.5;
Sb content: 0.0001～0.5;
Ti content: 0.0001～0.1;
S content: 0.0001～0.5;
Sn content: 0.0001～0.5;
W content: 0.0003～0.2;
All the other are Fe and unavoidable impurities.
2. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % content of Mn constituent content is 0.005～0.5.
3. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Mn atoms of elements % content is 0.01～0.3.
4. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % of S constituent content is 0.0005～0.3.
5. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % content of S constituent content is 0.001～0.3.
6. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % of Sb constituent content is 0.0005～0.4.
7. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Sb atoms of elements % content is 0.001～0.3.
8. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % of Al constituent content is 0.0001～0.05.
9. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the atom % content of Al constituent content is 0.0001～0.01.
10. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, the scope of Ti atoms of elements % is 0.0001～0.05.
11. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Ti atoms of elements % content is 0.0001～0.01.
12. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Sn atoms of elements % is 0.001～0.4.
13. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Sn atoms of elements % content is 0.002～0.3.
14. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, W atoms of elements % is 0.001～0.1.
15. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, W atoms of elements % content is 0.001～0.05.
16. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, B atoms of elements % is 7～16.
17. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, B atoms of elements % content is 8～15.
18. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Si atoms of elements % is 5～13.
19. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Si atoms of elements % content is 6～12.
20. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, P atoms of elements % is 0.01～5.
21. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, P atoms of elements % content is 0.01～3.
22. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, C atoms of elements % is 0.02～2.
23. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, C atoms of elements % content is 0.01～1.5.
24. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that, Si is partly or entirely replaced by at least a element among the Ga below the 5 atom %, Ge, As, Pb, Te, the N.
25. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that Fe is partly replaced by at least a element among the V below the 2.5 atom %, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, Pb, Y, Au, Cu, Tl, Cr, Mo, Nb, Zr, Hf, Be, the Bi.
26. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that Fe is partly replaced by Ni and/or Co below the 15 atom %.
27. an iron base amorphous magnetically-soft alloy strip is characterized in that this iron base amorphous magnetically-soft alloy strip processed by each described iron base amorphous magnetically-soft alloy among the claim 1-26.
28. an iron base amorphous soft-magnetic alloy powder is characterized in that this iron base amorphous soft-magnetic alloy powder processed by each described iron base amorphous magnetically-soft alloy among the claim 1-26.
29. an iron core that is used for motor is characterized in that iron core processed by each described iron base amorphous magnetically-soft alloy among the claim 1-26.
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