CN101935812A - Iron-based amorphous soft magnetic alloy with high saturation magnetic induction and preparation method thereof - Google Patents
Iron-based amorphous soft magnetic alloy with high saturation magnetic induction and preparation method thereof Download PDFInfo
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Abstract
The invention provides iron-based amorphous soft magnetic alloy with high saturation magnetic induction and a preparation method thereof. The alloy is characterized by being melted and prepared by adopting high-pressure N2 as a protective atmosphere, , the atom percentage composition of the alloy satisfies the relation: FeSiaBbPcCdNeMf, wherein M is Mn or/and Cr, subscripts from a to f in the relation express atom percentage and satisfy the following conditions that a is not less than 0.02 and is less than 20, b is not less than 1 and is less than 20, c is not less than 0.002 and is not more than 8, d is not less than 0.002 and is not more than 10, e is not less than 0.001 and is not more than 3, f is not less than 0.002 and is not more than 4, and a+b+c+d+e+f is not more than 20; and the balance is Fe and inevitable impurities. The soft magnetic alloy has the advantages of full elimination of stress during annealing, high saturation magnetic induction, high initial permeability and the like. The alloy has the saturation magnetic induction of above 1.65T and the initial permeability of above 20 thousand after annealing.
Description
Technical field
The present invention relates to the magnetic functional material field, particularly a kind of iron base amorphous magnetically-soft alloy of high saturated magnetic induction.
Background technology
After amorphous soft magnetic material comes out, especially iron-based non-crystalline alloy, there are resistivity height, magnetic permeability height and the loss characteristics of very low (only be equivalent to oriented silicon steel 1/3～1/5), compare with silicon steel in addition, technology is simple, need not specially process, therefore be considered to make the desirable core material of supply 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 stacking factor and saturation induction density are relatively low.The B of crystalline state oriented silicon steel for example
sValue is about 2T, and typical Fe-based amorphous alloy Fe
78Si
9B
13B
sValue is 1.56T.During magnetics,, often wish that the saturation induction density of these devices is higher in preparation in addition, because this means reducing or the reduction of exciting power of plant bulk as transformer core, motor rotor and magnetic switch etc.For stacking factor, method in common is to improve strip surface quality, for example homogeneity of surface smoothness and thickness of strip.But because amorphous band itself is thinner, only be tens microns, the potentiality that make stacking factor promote are limited.
And for the latter, numerous researchist'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 the alloy, costs an arm and a leg, and is not suitable for industrial magnetic product.In addition, disclose a kind of non-crystalline 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 this alloy is bigger and too crisp, can't use in practice.Hitachi Metals is the Fe-Si-B-C alloy that discloses a kind of HB1 by name during the Chinese patent application of CN1721563A is announced at publication number, its saturation induction density is at 1.64T, but its preparation process adopts the method for carburizing, and this has improved production cost undoubtedly, has reduced the controllability of quality product.
Chinese patent CN1124362C has announced that a kind of expression formula is the five metamember alloys of Fe-Si-B-C-P, and wherein the atom % of Fe is 82 to 90.But studies show that when the atom % of iron is higher than 82 and be added with when have the C element of non-negative enthalpy of mixing with other yuan, the amorphous formation ability of alloy becomes very poor, is difficult to prepare the good amorphous alloy ribbon of template.
Chinese patent application CN101194039 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, adopts the alloy material that contains N to smelt, is difficult to reach the stable control of N content in the amorphous thin ribbon, and the quality of alloy is relatively poor relatively.
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 approximate impurity form, can't bring into play the effect that P can improve amorphous formation ability, improve Fe content.Therefore the saturation induction density of alloy is also low, and this is difficult to satisfy the requirement of power device to high saturated magnetic induction.
U.S. Pat 5626690 has been announced a kind of FeSiBP (C) element that initiatively adds the P element, but all alloy Fe content that exemplify are all at 80 atom % and following, and Si content is higher than 10 atom %, P content is lower than 2 atom %, this makes its saturation induction density be limited to about 1.5T, is difficult to satisfy the requirement of power device to high saturated magnetic induction.
Japanese patent application JP2008-248380 has announced the quaternary non-crystaline amorphous metal of a kind of FePBAlSi, but its P too high levels, more than 8 atom %.Studies show 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, lack the iron base amorphous magnetically-soft alloy and the goods thereof of high saturated magnetic induction and excellent combination property in the market, so still there are the needs to the iron base amorphous magnetically-soft alloy that has high saturated magnetic induction and excellent over-all properties concurrently in this area.
Summary of the invention
The purpose of this invention is to provide that a kind of composition is reasonable in design, amorphous formation ability is strong, saturation induction density is high, the iron base amorphous magnetically-soft alloy of excellent combination property.
The contriver is at weak point of the prior art; a kind of Fe-based amorphous alloy of the N of containing element has been proposed; its composition mentality of designing is that FePC with large-amorphous forming capacity is as mother alloy; require an amount of interpolation to have according to the planner and have the Mn of negative enthalpy of mixing or/and the Cr element with other yuan; and the common element Si and the B that add the preparation amorphous, protect technology such as melting, nitrogen protection fast quenching to prepare the iron base amorphous magnetically-soft alloy of excellent performance by high pressure nitrogen.
The atom % composition of the iron base amorphous magnetically-soft alloy of high saturated magnetic induction of the present invention satisfies relational expression:
FeSi
aB
bP
cC
dN
eM
f
Wherein M is that Mn is or/and Cr, and the subscript a to f in the above-mentioned relation formula represents atom % and meets the following conditions: 0.02≤a＜20,1≤b＜20,0.002≤c≤8,0.002≤d≤10,0.001≤e≤3,0.002≤f≤4, and a+b+c+d+e+f≤20, all the other are Fe and unavoidable impurities.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 0.1≤a＜18, and more preferably 2≤a＜16.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 2≤b≤16, and more preferably 3≤b≤15.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 0.02≤c≤8, and more preferably 0.2≤c≤6.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 0.02≤d≤6, and more preferably 0.1≤d≤3.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 0.001≤e≤2, and more preferably 0.01≤e≤2.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, preferred 0.02≤f≤3, and more preferably 0.2≤f≤3.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, Fe can partly be substituted by at least a element that is selected among Al, Sn, Ge, Ga, Nb, Zr, Hf, Mo, W, V, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, As, Sb, Bi and the Y below the 5 atom %.
In the atom % of iron base amorphous magnetically-soft alloy of the present invention component relationship formula, Fe can partly be substituted by Ni below the 15 atom % and/or Co.
Iron base amorphous magnetically-soft alloy according to the present invention is after annealing process annealing, and its saturation induction density is more than 1.60T, preferably more than 1.65T; Initial permeability is more than 1.5 ten thousand, preferably more than 20,000.
The present invention also provides the method for preparing described iron base amorphous magnetically-soft alloy, and the method comprising the steps of:
(a) supply raw materials, and prepare burden according to above-mentioned alloy composition;
(b) the molten alloy raw material forms uniform molten steel under nitrogen protection, and furnace cooling becomes master alloy ingot;
(c) master alloy ingot is fused into molten steel, under nitrogen protection, adopts single-roller method, thereby obtain the iron base amorphous magnetically-soft alloy of ribbon form the molten steel chilling.
In above-mentioned preparation method, the nitrogen pressure that uses in the melting step (b) is preferably 0.1-5MPa, and the nitrogen pressure in the described step (c) is preferably 0.03-3MPa.
In above-mentioned preparation method, used smelting temperature is preferably 1350-1500 ℃ in the melting step (b).
In above-mentioned preparation method, the roller rotating speed in the step (c) is 18～30m/s, and spray band temperature is preferably 1200～1400 ℃.
Embodiment
The feature of the alloy of high saturated magnetic induction of the present invention is that the atom % composition of this alloy satisfies relational expression:
FeSi
aB
bP
cC
dN
eM
f
Subscript a to f in this relational expression represents atom % and meets the following conditions:
0.02≤a＜20,1≤b＜20,0.002≤c≤8,0.002≤d≤10,0.001≤e≤3,0.002≤f≤4, and a+b+c+d+e+f≤20, all the other are Fe and unavoidable impurities.
N is considered to the amorphous thin ribbon harmful element in when casting always, this be because N easily with molten steel in elements such as Al, Ti, Zr form nitride inclusion, promote crystallization, so always attempt to reduce the content of N element.Yet N is the element that certainly exists in the material, be difficult to eradicate, and the reserves of N element is abundant, if the N element effectively can be utilized, maximize favourable factors and minimize unfavourable ones, and may have new result.Yet under atmospheric environment, the solid solubility of N in molten steel is but very low, and N also can escape from molten steel in condensation process.Therefore, the industrial smelting mother alloy that contains N adopts high-tension apparatus more.
In the present invention, at first adopt pure iron, silicon, graphite cast iron, ferro-boron, ferrophosphorus and nitrogenize ferromanganese or/and raw materials such as chromium nitrides, (Cr, composition expression formula Mn) is prepared burden according to FeSiBPCN-.Adopt high-temperature high-pressure reaction kettle or other High Temperature High Pressure smelting equipments, under nitrogen protection, raw material is smelted into the uniform FeSiBPCN-of component (Cr, Mn) master alloy ingot.Then, again at N
2Spray band under the protection.Particularly, with FeSiBPCN-(Cr, Mn) alloy pig places spray band crucible, carries out the induction heating fusing; N
2Be with moment in spray, fully contact with the molten steel of at the uniform velocity extruding, (0.03～3MPa) makes N element and nitrogen partial pressure in the molten steel keep balance, so be prepared into FeSiBPCN-(Cr, Mn) the amorphous band alloy that contains expection N content under nitrogen protection.Adopt this special preparation technology, we find, the detrimental action of N element for example easily forms and is mingled with, promotes crystallization etc. all to obtain effective inhibition.And find also that through subsequent survey the N element is at the inner uniform distribution of amorphous thin ribbon, and N content is very approaching with the expection composition.
The internal stress of the initial permeability of amorphous alloy and saturation magnetostriction coefficient and alloy in close relations can be expressed as:
M wherein
sBe the saturation magnetization of alloy, λ
sBe saturation magnetostriction coefficient, K
uBe induced magnetic anisotropy, σ represents the internal stress that alloy is suffered.Because molten steel is after being cast as amorphous thin ribbon, there is very big internal stress in alloy, and the magneticanisotropy that is produced by magnetostriction-stress coupling becomes the chief component of the anisotropic of inducting.This anisotropy is expressed as:
M
sAnd λ
sFor the proper property index of non-retentive alloy, in close relations with material itself, and be subjected to the influence of subsequent technique little.Combined type (1) and formula (2) as can be known, the initial permeability μ of alloy
iAlmost the quadratic power with internal stress is inversely proportional to, therefore, and initial permeability μ
iBe subjected to the alloy internal stress influence bigger.
Although amorphous band in heat treatment process, raises with temperature, internal stress can obtain discharging K gradually
uAlso can correspondingly reduce, but because amorphous thin ribbon is to get off from high-temperature fusant state chilling, the existence of cast inside stress and microstructure ununiformity, and the mechanical stress of introducing in the following process process adopt the annealed method in fact to be difficult to eliminate fully.This also is the major reason that the soft magnetic performance of general industry amorphous product is lower than the laboratory product.Therefore, if the non-crystaline amorphous metal internal stress can be discharged fully, then be expected the soft magnetic performance of alloy is further improved.The most popular method of measuring the annealing effect is, the changing value r/r ' of the effectively lax radius of strip sample before and after the measurement that employing is proposed by Luborsky is annealed, wherein r is the tightly radius on the pipe of strip sample, and r ' is the effectively lax radius of sample after shifting out pipe after the annealing.Fully by lax, then the value of r/r ' levels off to 1 as stress.In addition, adopting holding furnace annealing to improve the method for non-crystaline amorphous metal soft magnetic performance, has been must obligato operation in the suitability for industrialized production.Existing amorphous iron core all is placed in the holding furnace and anneals, and soaking time is many at 60～90 minutes, and for big iron core, the time that needs can be longer.And for the industrialized production of paying attention to efficient, in the shortening heat treatment time, can improve heat treatment efficiency effectively.
Yet, the contrast component testing, we are surprised to find, and the employing aforesaid method carries out the interpolation of N element and contains the preparation of N amorphous alloy strips, can improve physicals well.At first, we find that when thermal treatment, the adding of N more helps the abundant release of stress, and destressing is more thorough.For example, the measuring method that adopts Luborsky to propose is carried out the stress relaxation recruitment evaluation, finds to contain r/r ' value (0.83～0.89) height that or not N alloy of the r/r ' value (0.90～0.99) of N alloy than the following acquisition of same process, and the annealing time that needs is shorter.This is very favorable for suitability for industrialized production.In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, N atoms of elements % will satisfy: 0.001≤N≤3, preferred range are 0.001≤N≤2, and the scope that is more preferably is 0.01≤N≤2.This is when being lower than 0.001 atom % because of N content, and its effect that improves destressing effect, shortening annealing time can't manifest.When if N content is higher than 3 atom %, then too high to the high-tension apparatus requirement of nitriding, be difficult to realize.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, M comprises at least a among Cr, the Mn, and M atom % will satisfy following condition: 0.002≤M≤4, and preferred range is 0.02≤M≤3, and the scope that is more preferably is 0.2≤M≤3.In the present invention, add Mn and Cr unit and have very important meaning.At first be to consider from starting material sources angle, nitrogenize ferromanganese and chromium nitride are the compound nitrogenous sources of the easiest acquisition, are fit to the N element is added in the iron alloy.Secondly, in the metallurgic product that contains Cr and Mn, N can obtain high solid solubility.Therefore, Cr and/or Mn element are the elements that can not lack among the present invention.Because the M element is non-ferromagnetic elements, when content surpasses 4 atom %, can reduce the saturation induction density of alloy.And the M constituent content is when being less than 0.002 atom %, and the raising amorphous formation ability of M element, the effect that improves N content and then improve comprehensive soft magnetic performance are difficult to bring into play.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, B atoms of elements % will satisfy: 1≤B＜20, preferred range are 2≤B≤16, and the scope that is more preferably is 3≤B≤15.When B content was higher than 20 atom %, ferromagnetic element content reduced relatively, caused the saturation induction density of alloy to reduce.And B content is when being lower than 1 atom %, and the thermostability of alloy descends and amorphous formation ability descends.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, Si atoms of elements % will satisfy: 0.02≤Si＜20, preferred range are 0.1≤Si＜18, and preferred scope is 2≤Si＜16.Studies show that too high Si content can reduce the saturation induction density of alloy when zero absolute temperature.From the prepared angle, when Si content was higher than 20 atom %, the molten steel viscosity rose, and caused alloy spray band difficulty.When Si content is lower than 0.02 atom %, be difficult to bring into play the effect that the Si element improves thermostability, improves amorphous formation ability.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, P atoms of elements % will satisfy: 0.002≤P≤8, preferred range are 0.02≤P≤8, and preferred scope is 0.2≤P≤6.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.Therefore when P content during greater than 8 atom %, it is very low that the saturation induction density of alloy can be fallen.And P content is difficult to bring into play the effect that the P element improves the amorphous formation ability of alloy during less than 0.002 atom %, is difficult to reach the purpose that improves the Fe constituent content, improves the saturation induction density of alloy.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, the content of C element is wanted suitably, and with P content under the suitable condition of ratio, can improve the soft magnetic performance of alloy.C atoms of elements % will satisfy: 0.002≤C≤10, preferred range are 0.02≤C≤6, and the scope that is more preferably is 0.1≤C≤3, and when C content during greater than 10 atom %, the amorphous formation ability variation of alloy, soft magnetic performance descends and is difficult to preparation.And when C content was lower than 0.002 atom %, it improved amorphous formation ability and is difficult to obtain performance with the effect that reduces the wastage.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, Fe can partly be substituted by at least a element among Al, Sn below the 5 atom %, Ge, Ga, Nb, Zr, Hf, Mo, W, V, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, As, Sb, Bi, Y, the N.When these constituent contents were higher than 5 atom %, the full magnetic induction density of alloy reduced and the cost of alloy rises.
In the Fe-based amorphous alloy of high saturated magnetic induction of the present invention, Fe can partly be substituted by Ni below the 15 atom % and/or Co.
In the Fe-based amorphous alloy of high saturation induction intensity of the present invention, surplus is made of Fe except that above-mentioned element, wherein may contain a spot of impurity element, and as S, O etc., but the total weight percent of all impurity elements is less than 0.5%.
In the preparation method of the Fe-based amorphous alloy of high saturation induction intensity of the present invention compared with prior art, has special design.Promptly under the high pressure nitrogen atmosphere protection, adopt induction furnace to carry out the mother alloy melting, adopt single-roller method or double roller therapy under nitrogen protection, to be prepared into amorphous band then.Difference and gas shield in the past, the purpose of this nitrogen protection has two: the one, under certain pressure, in molten steel, carry out nitriding, suppress original nitrogen element escape in the molten steel simultaneously; The 2nd, in order to obtain the soft magnetic performance of special improvement.
Adopt the prepared product of Fe-based amorphous alloy of the present invention to compare, have that composition is reasonable in design, soft magnetic performance is good and characteristics such as stable preparation process with prior art products.The over-all properties of FeSiBPCNM amorphous soft-magnetic alloy of the present invention is better than the prior art alloy, is characterized in: iron base amorphous magnetically-soft alloy of the present invention has high saturation induction density; Iron base amorphous magnetically-soft alloy of the present invention has the excellent comprehensive soft magnetic performance; The characteristics that destressing was thorough, production efficiency is high when iron base amorphous magnetically-soft alloy of the present invention had annealing.
Below by specific embodiment the features and advantages of the present invention are illustrated.
Embodiment 1
According to the composition range of Fe-based amorphous alloy of the present invention, we have done a series of experiments.Prepare burden according to composition of the present invention, at the N of 1MPa
2Carry out mother alloy under the pressure and be smelted into ingot.Again at the N of 0.5MPa
2Protection down is heated to 1400 ℃ with master alloy ingot, adopts single-roller method to prepare wide 10 ± 0.1mm, the thickness amorphous thin ribbon at 28-30 μ m with the roller speed of 25m/s.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, through 380 ℃ of isothermal annealings 40 minutes, the soft magnetic performance that measures was listed in table 1 with iron core.The saturation induction density B of alloy
sAdopting vibrating sample magnetometer (VSM) to measure, is the saturation induction density B of the magnetic induction density of 10000A/m size as alloy with magnetic field
sSY 8232 B-H testers are adopted in the loss measurement of alloy, and test condition is magnetic strength 1.4T, and frequency is 50Hz, is designated as P
14/50The coercive force H of alloy
cWith initial permeability μ
iAdopt B-H magnetic hysteresis loop tester to record.The anneal assessment of destressing relaxing effect of the measuring method that employing is proposed by previously described Luborsky.
The composition of table 1 alloy of the present invention and magnetic property
As can be seen from Table 1, the saturation induction density B of amorphous alloy of the present invention
sHigher, more than 1.65T reaches.The initial permeability μ of alloy of the present invention
iMainly concentrate on more than 20,000, and loss P
14/50Then at 0.32W/kg and following.In order to contrast conveniently, listed composition, the alloy composition outside the present invention and their soft magnetic performance of multiple existing alloy in the table 2.Contrast table 2 and table 1 as can be seen, the saturation induction density of existing alloying constituent is generally lower, for example the 1-7 in the table 2 number and 12-18 alloy.In addition, though the 8-11 alloy in the table 2 has higher saturation induction density (more than 1.70T), weak point is very obvious, i.e. coercive force and loss is all bigger, and magnetic permeability is low.11-18 alloy in the table 2 is because of adding Co, Ni, Mo etc., and is with high costs, suppressed its application potential as industrial magnetic product.Except high saturation induction density, contrast table 1 and table 2 it can also be seen that, with existing alloy phase ratio, the initial permeability of alloy of the present invention is higher, and loss is lower.Therefore, we can say that alloy of the present invention has good comprehensive soft magnetic performance, is better than existing soft magnetic materials.
In addition, alloy of the present invention not only has better soft magnetic performance, and is shortening annealing time, also having very big advantage aspect enhancing productivity.By the Comparative Examples of the embodiment of table 1 and table 2 as can be seen, follow the performance of the outer alloy (19-29 alloy in the table 2) of existing soft magnetic materials and the present invention to compare, the destressing effect r/r ' value (0.90～0.99) that contains the N alloy obviously is better than not containing the r/r ' value (0.83～0.89) of N alloy, also obviously is better than existing soft magnetic materials (0.83～0.88).This shows as in production operation, is obtaining under the identical destressing state, and the annealing time that needs is shorter.Commercially available Fe
78Si
9B
13The annealing time that amorphous alloy strips obtains excellent soft magnetic performance is about 60 minutes, and the annealing time of amorphous alloy strips of the present invention acquisition excellent properties only is 30～40 minutes.
Be it can also be seen that by embodiment in the table 1 and the Comparative Examples among the table 2 be accompanied by and contain the more excellent destressing effect of N composition, its initial permeability also obviously is better than not containing the composition of N, loss is also lower.Material preparation process of the present invention and method are adopted in this explanation, and the existence of N element has special destressing effect, can obtain good soft magnetic performance, are one of main innovate point of the present invention.
The composition and the magnetic property of the existing alloy of table 2
Embodiment 2
According to the composition range of Fe-based amorphous alloy of the present invention, we have done a series of experiments.Prepare burden according to alloy composition of the present invention, at the N of 2MPa
2Carrying out mother alloy under the pressure smelts.Again at the N of 0.35MPa
2Protection is down with master alloy ingot melting to 1400 ℃, and adopts single-roller method to prepare wide 10 ± 0.1mm, the thickness amorphous thin ribbon at 28-30 μ m with the roller speed of 26m/s.With thin coiled stock coiled external diameter is that 20mm, internal diameter are the iron core of 16mm.Under argon shield, through 380 ℃ of isothermal annealings 30 minutes, the soft magnetic performance index that measures was shown in Table 1 with iron core.The saturation induction density B of alloy
sAdopting vibrating sample magnetometer (VSM) to measure, is the saturation induction density B of the magnetic induction density of 10000A/m size as alloy with magnetic field
sSY 8232 B-H testers are adopted in the loss measurement of alloy, and test condition is magnetic strength 1.4T, and frequency is 50Hz, is designated as P
14/50The coercive force H of alloy
cWith initial permeability μ
iAdopt B-H magnetic hysteresis loop tester to record.The anneal assessment of destressing relaxing effect of the measuring method that employing is proposed by previously described Luborsky.
The composition of table 3 alloy of the present invention and magnetic property
As can be seen from Table 3, after adopting the partly alternative Fe element of at least a element among a spot of Co, Ni, Al, Sn, Ge, Ga, Nb, Zr, Hf, Mo, W, V, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, As, Sb, Bi and the Y, the soft magnetic performance of alloy and the kind of substituted element are closely related, but still can keep good soft magnetic performance, even B is for example arranged under the condition that part Fe replaced by the Ni element
sValue is still more than 1.60T reaches.Initial permeability μ
iAlso mainly concentrate on more than 20,000, and loss P
14/50Then remain on 0.31W/kg and following.
Though adopt above-mentioned element to replace, the partial properties index of alloy descends, and the destressing effect of alloy of the present invention is still very obvious.By the Comparative Examples of alloy of the present invention in the table 3 and table 2 as can be seen, compare with the performance of the outer composition of the present invention with existing soft magnetic materials, the destressing effect r/r ' value (0.90～0.99) that contains the N alloy is better than not containing the r/r ' value (0.83～0.89) of N alloy, also obviously is better than existing soft magnetic materials (0.83～0.88).This shows as in production operation, is obtaining under the identical destressing state, and the annealing time that needs is shorter.
FeSiBPCNM alloy of the present invention, higher saturation induction density and initial permeability are not only arranged, and lower coercivity and loss are arranged, add up stress thoroughly, the production efficiency high, can be referred to as the iron base amorphous magnetically-soft alloy of the high saturated magnetic induction of excellent combination property.
Claims (15)
1. the iron base amorphous magnetically-soft alloy of a high saturated magnetic induction, the atom % that it is characterized in that this alloy are formed and are satisfied relational expression:
FeSi
aB
bP
cC
dN
eM
f
Wherein M is Mn or/and Cr, and the subscript a to f in the above-mentioned relation formula represents atom % and meets the following conditions:
0.02≤a＜20,1≤b＜20,0.002≤c≤8,0.002≤d≤10,0.001≤e≤3,0.002≤f≤4, and a+b+c+d+e+f≤20, all the other are Fe and unavoidable impurities.
2. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 0.1≤a＜18, and more preferably 2≤a＜16.
3. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 2≤b≤16, and more preferably 3≤b≤15.
4. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 0.02≤c≤8, and more preferably 0.2≤c≤6.
5. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 0.02≤d≤6, and more preferably 0.1≤d≤3.
6. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 0.001≤e≤2, and more preferably 0.01≤e≤2.
7. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that 0.02≤f≤3, and more preferably 0.2≤f≤3.
8. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that Fe is partly substituted by at least a element that is selected among Al, Sn, Ge, Ga, Nb, Zr, Hf, Mo, W, V, Ta, Ti, Re, platinum family element, rare earth element, Ag, Zn, In, As, Sb, Bi and the Y below the 5 atom %.
9. iron base amorphous magnetically-soft alloy according to claim 1 is characterized in that Fe is partly substituted by Ni below the 15 atom % and/or Co.
10. according to each described iron base amorphous magnetically-soft alloy among the claim 1-9, it is characterized in that this alloy after annealing process annealing, its saturation induction density is more than 1.60T, and preferably more than 1.65T; Initial permeability is more than 1.5 ten thousand, and preferably more than 20,000.
11. preparation is as the method for each described iron base amorphous magnetically-soft alloy among the claim 1-10, the method comprising the steps of:
(a) supply raw materials, and prepare burden according to the alloy composition expression formula of claim 1-10;
(b) the molten alloy raw material becomes uniform molten steel under nitrogen protection, and furnace cooling becomes master alloy ingot;
(c) master alloy ingot is fused into molten steel, and under nitrogen protection, adopts single-roller method, thereby obtain the iron base amorphous magnetically-soft alloy of ribbon form the molten steel chilling.
12. method according to claim 11, the pressure that it is characterized in that the high pressure nitrogen in the step (b) is 0.1-5MPa.
13. method according to claim 11 is characterized in that the nitrogen gas pressure in the step (c) is 0.03-3MPa.
14. method according to claim 11 is characterized in that the used smelting temperature in the step (b) is 1350～1500 ℃.
15. method according to claim 11 is characterized in that the roller rotating speed in the step (c) is 18～30m/s, spray band temperature is 1200～1400 ℃.
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