CN1642400A - Electric wave absorber and manufacturing method of the same - Google Patents

Abstract

The radio wave absorbent comprises a resin and an amorphous soft ferrite alloy having Fe groups, wherein the alloy has 25K or more of a temperature difference([Delta]Tx) of a supercooling liquid. The temperature difference is expressed as an equation [Delta]Tx=Tx-Tg, wherein Tx is a crystallization initiating temperature, and Tg is a glass transition temperature. The resin is any one of fluorine type thermoplastic elastomer, fluorinated polyolefin resin, perfluoroalkoxy resin, fluorinated ethylenepropylene copolymer, polyimide resin and epoxy resin. The imaginary part([mu]'') of complex permeability is increased in high frequency band such as 100MHz-several GHz, thereby having excellent electromagnetic shielding effect in high frequency band.

Description

The manufacture method of wave absorber and wave absorber

Technical field

The present invention relates to wave absorber and its manufacture method, the electric wave that particularly relates to 100MHz～number GHz frequency band shields effective wave absorber.

Background technology

With mobile phone and subnotebook PC is that the portable electronic machine of representative is being popularized.Recently, report has the problem that is considered to the Electromagnetic Interference that portable electronic machine causes in the aircraft etc., in a part, has forbidden the use of the portable electronic machine in the aircraft.In addition, report has the malfunction of the Medical Instruments that mobile phone causes, some places have stipulated to forbid in the hospital use of mobile phone.

No matter be aircraft or Medical Instruments, malfunction all can produce the significant impact that concerns human life, so importantly prevent radiation that does not need electric wave and generation in the e-machine.Particularly prevent to become key subjects from what the high frequency of generations such as portable electronic machine and mobile phone did not need electric wave.

In order do not need to suppress electric wave, the imaginary part μ of the plural permeability in the advantageous applications service band " show the wave absorber of big value; and as such wave absorber, having proposed soft magnetic alloy powder is tabular wave absorber with binding material solidified formings such as resins.

The imaginary part μ of described plural permeability " be in high-frequency region; in the frequency band of hundreds of MHz～number GHz, show great permeability; the electromagnetic interference that becomes wave absorber suppresses the numerical value of the index of effect, this imaginary part μ " high more, it is excellent more that electromagnetic interference suppresses effect.It should be noted that in the frequency band below hundreds of MHz, the real part μ ' of plural permeability shows greatly.

That is, if operating frequency is increased, then initial real part μ ' shows greatly, if frequency further increases, then when real part μ ' descends, imaginary part μ " increase, in the frequency band of hundreds of MHz～number GHz, become imaginary part μ " show greatly and concern.

In addition, real part μ ' and imaginary part μ " very big frequency be the eigenvalue in the material separately, therefore, be necessary suitably to select the material of wave absorber according to the wave frequency that will shield.

The wave absorber that is made of described soft magnetic alloy powder can form very thin, so can be applied in the miniature instrument, but in the frequency band of hundreds of MHz～number GHz, " be roughly below 5; even height also is below 10, existence can't fully obtain the problem that electromagnetic interference suppresses effect to imaginary part μ.For example, as the wave absorber that has soft magnetic alloy powder to constitute in the past, knownly soft magnetic alloy powders such as Fe-Al-Si alloy and Fe-Ni alloy are configured as tabular wave absorber by binding materials such as fluororesin, but in these wave absorbers, do not heat-treat after tabular being configured as, so can't relax the stress that when being shaped, acts on the soft magnetic alloy powder, can't improve the imaginary part μ of described plural permeability ".

For the stress that fully carries out soft magnetic alloy powder relaxes, for example in the Fe-Al-Si alloy, be necessary about 800 ℃, to heat-treat, but under such high temperature, binding material is the fluororesin thermal decomposition, so heat treatment self is impossible situation.

Summary of the invention

The present invention proposes in view of described problem, and its purpose is: " height, the electromagnetic wave in the high-frequency region suppresses the wave absorber of effect excellence to be provided in the broad range of frequency band of hundreds of MHz～number GHz the imaginary part μ of plural permeability.

The object of the invention is in addition: be provided at the plural magnetic permeability mu in the high-frequency region of 1GHz～10GHz, and " height, the electromagnetic wave in high-frequency region like this suppresses the wave absorber of effect excellence.

In order to realize described purpose, the present invention has adopted following structure.

Wave absorber of the present invention is characterised in that: (wherein, Tx is a crystallization start temperature, and Tg is a vitrification point with Δ Tx=Tx-Tg.) the temperature interval Δ Tx of the subcooled liquid represented of formula is the above Fe noncrystal non-retentive alloy of base of 25K and mixed with resin, solidified forming, described resin is any one in fluorine analog thermoplastic synthetic rubber, fluoro vistanex, perfluoro alkoxy resin, fluoroethylenepropyl.ne copolymer, polyimide resin, the epoxy resin.

In addition, the described resin fluorine analog thermoplastic synthetic rubber of peroxide cure type preferably.

Temperature interval Δ Tx is that the above noncrystal non-retentive alloy of Fe base of 25K has excellent soft magnetic characteristic, in addition, because be the high material of permeability, so brought into play good electric wave absorbability.

In addition, the noncrystal soft magnetic alloy powder of Fe base is by insulation resin, the impedance of wave absorber self improves, in view of the above, suppressed the generation of overcurrent, can in the scope of broadness, improve the imaginary part μ of the plural permeability in the frequency band of hundreds of MHz～number GHz ", the electromagnetic wave that can improve in the high-frequency region suppresses effect.

When resin is made of in fluorine analog thermoplastic synthetic rubber, fluoro vistanex, perfluoro alkoxy resin, the fluoroethylenepropyl.ne copolymer any one, can obtain soft material as wave absorber.For example, can obtain the soft wave absorber or the such deformable soft wave absorber of rolled lead of plate rubber shape.In view of the above, when utilizing as laminal wave absorber, have following feature: need not select the place of pasting, can simply be close to the form fit in the place of pasting, sticking operation becomes simply, and it is easy that sticking operation self also becomes.In addition,, also can paste the material of cut-out easily, install and become easy when cutting off, when pasting, can cutting off with scissors easily.Therefore, can easily install or stick on the inner surface of the shielded box of little case shape, little case.

In addition, the present invention is characterized in that in order to realize described purpose: the noncrystal non-retentive alloy of described Fe base comprises Fe, transition metal and B.Be the noncrystal non-retentive alloy of Fe base more than the 25K promptly, preferably comprise Fe, transition metal and B as temperature interval Δ Tx.

The present invention is characterized in that in order to realize described purpose: the noncrystal non-retentive alloy of described Fe base comprises at least a above semimetallic elements among P, C, the Si.Be the noncrystal non-retentive alloy of Fe base more than the 25K promptly, preferably comprise at least a above semimetallic elements among P, C, the Si as temperature interval Δ Tx.

The present invention is characterized in that in order to realize described purpose: the content of the noncrystal non-retentive alloy of described Fe base is 40～55 volume %.

If for resin,, then in the high-frequency region of purpose, can obtain desirable electric wave absorption characteristic for the content of the noncrystal non-retentive alloy of the Fe of described scope base.

In the present invention, it is characterized in that: the transition metal that comprises in the noncrystal non-retentive alloy of described Fe base is one or more the element that is selected among Cr, Mo, W, V, Nb, Ta, Ti, zr, Hf, Pt, Pd, the Au.Be the noncrystal non-retentive alloy of Fe base more than the 25K promptly, preferably comprise more than at least a in these transition elements as temperature interval Δ Tx.

In the present invention, preferably comprise the noncrystal non-retentive alloy of described Fe base with pulverulence, the average grain diameter of described powder is 1～80 μ m preferably, and thickness is 0.1～5 μ m.

If the average grain diameter of powder and thickness setting in described scope, then can obtain the good wave absorber of electric wave absorption characteristic easily in high-frequency region.

If the thickness of the powder particle of platypelloid type and average grain diameter are in described scope, then because the impedance of wave absorber self increase, suppressed the generation of overcurrent, the counter magnetic field of platypelloid type particle self does not become too small in addition, suppressed μ ', in view of the above, the imaginary part μ in the GHz frequency band " raises, can improve electromagnetic wave and suppress effect.

In the present invention, the length-width ratio of preferred described powder is more than 1, below 800.In the present invention, more preferably the length-width ratio of described powder is more than 5, the scope below 300.

According to this wave absorber, because described noncrystal non-retentive alloy is made of the high platypelloid type particle of length-width ratio, so compare with the situation that length-width ratio is little, the impedance of wave absorber self raises, suppressed the generation of overcurrent, " raise, the electromagnetic wave that can improve in this frequency band suppresses effect to imaginary part μ in the GHz frequency band.

According to this wave absorber, because the length-width ratio of platypelloid type particle is more than 1,,, suppressed the generation of overcurrent, the μ of GHz frequency band and " become more than 5, suppress effect so can improve electromagnetic wave so the impedance of wave absorber self increases preferably more than 5.

In addition, because length-width ratio just now is below 800, preferably below 300, so the counter magnetic field of flat particle self does not become too small, in view of the above, suppressed the real part μ ' of the plural permeability in the low frequency region, and imaginary part μ " becomes more than 5, suppresses effect so can improve electromagnetic wave.

In addition, wave absorber of the present invention is foregoing wave absorber, it is characterized in that: the plural permeability imaginary part μ among the 1GHz " is more than 5.In addition, more preferably the plural permeability imaginary part μ among the 1GHz " is more than 10.

According to this wave absorber, because the plural permeability imaginary part μ among the 1GHz " be more than 5, more preferably more than 10, so the electromagnetic wave that can improve in the GHz frequency band suppresses effect.

In addition, wave absorber of the present invention is foregoing wave absorber, it is characterized in that: density is 3.0g/cm ³More than, the containing ratio of the noncrystal soft magnetic alloy powder of described Fe base is more than the 30 volume %, below the 80 volume %.

According to this wave absorber, because density is 3.0g/cm ³More than, so filled the noncrystal non-retentive alloy of Fe base thick and fast, do not produce the gap to each other at the flat particle that constitutes powder, in view of the above, the μ in the GHz frequency band " improves, can improve electromagnetic wave and suppress effect.

In addition, because the containing ratio of the noncrystal soft magnetic alloy powder of Fe base is more than the 30 volume %, suppress effect so can effectively bring into play electromagnetic wave, in addition, because the containing ratio of the noncrystal soft magnetic alloy powder of Fe base is below the 80 volume %, descend so can prevent the impedance of the wave absorber that powder overstockedization each other causes, can effectively bring into play electromagnetic wave and suppress effect.

Wave absorber of the present invention is foregoing wave absorber, it is characterized in that: the powder particle of the noncrystal non-retentive alloy of described Fe base is covered by waterglass.

According to this wave absorber, because the powder particle of platypelloid type is covered by waterglass, so improved particle insulating properties each other, the impedance of wave absorber self further improves, can further improve the μ in the high-frequency region ", can improve electromagnetic wave and suppress effect.

In addition, wave absorber of the present invention is foregoing wave absorber, it is characterized in that: the noncrystal non-retentive alloy of described Fe base, wherein (, Tx is a crystallization start temperature, and Tg is a vitrification point with Δ Tx=Tx-Tg.) the temperature interval Δ Tx of the subcooled liquid represented of formula is more than the 25K, comprises more than one element and the Fe among P, C, Si, the B, by with noncrystal be the organizational composition of principal phase mutually.

According to this wave absorber, the noncrystal soft magnetic alloy powder of Fe base is made of the metallic glass alloys with sub-cooled liquid temperature interval delta T x, this metallic glass alloys is compared with non-retentive alloy in the past, real part μ ' the height of plural number permeability, so by this alloy powderization, add binding material, improve insulating properties, manifested the high imaginary part μ that reflects this real part μ ' thus ", can improve electromagnetic wave and suppress effect.

In addition, wave absorber of the present invention is foregoing wave absorber, it is characterized in that:

Behind described Fe noncrystal soft magnetic alloy powder of base and the mixing of described binding material, the solidified forming, heat-treat in the scope more than the Curie-point temperature (Tc) of described noncrystal non-retentive alloy, below the crystallization start temperature (Tx).

According to this wave absorber, relaxed the distortion of wave absorber by heat treatment, so magnetostrictive influence reduces, in view of the above, the imaginary part μ of plural permeability " improves, can improve electromagnetic wave and suppress effect.

Resin particularly of the present invention has thermal endurance, so can heat-treat behind solidified forming with the noncrystal non-retentive alloy of Fe base, in view of the above, has fully relaxed stress, the imaginary part μ of plural permeability and " has improved, brought into play excellent electric wave absorbability.

The noncrystal non-retentive alloy of described Fe base is preferably represented by following composition formula:

Fe _{100-x-y-z-w-t}M _xP _yC _zB _wSi _t

Wherein, M is one or more the element of selecting from Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, Au, x, y, z, w, the t of expression ratio of components are 0.5 atom %≤x≤8 atom %, 2 atom %≤y≤15 atom %, 0 atom %＜z≤8 atom %, 1 atom %≤w≤12 atom %, 0 atom %≤t≤8 atom %, the atom % of 70 atom %≤(100-x-y-z-w-t)≤79.

In addition, in described composition formula, y, z, w, the t that preferably represents described ratio of components satisfies the relation of atom % of 17 atom %≤(x+y+z+w+t)≤29.5.

In described composition formula, x, the y, z, w, the t that more preferably represent described ratio of components satisfy 1 atom %≤x≤4 atom %, 4 atom %≤y≤14 atom %, 0 atom %＜z≤6 atom %, 2 atom %≤w≤10 atom %, 2 atom %≤t≤8 atom %, the relation of atom % of 72 atom %≤(100-x-y-z-w-t)≤79.

In addition, in described composition formula, x, the y, z, w, the t that more preferably represent described ratio of components satisfy 1 atom %≤x≤3 atom %, 6 atom %≤y≤11 atom %, 1 atom %＜z≤4 atom %, 4 atom %≤w≤9 atom %, 2 atom %≤t≤7 atom %, the relation of atom % of 73 atom %≤(100-x-y-z-w-t)≤79.

The manufacture method of wave absorber of the present invention is characterised in that: mix, behind the solidified forming, heat-treat with the heat treatment temperature below the above 773K of 573K the noncrystal soft magnetic alloy powder of Fe base with by the binding material that fluorine analog thermoplastic synthetic rubber constitutes.

Manufacture method according to this wave absorber, because act on the distortion on the wave absorber when having relaxed solidified forming, diminish so magnetostrictive influence subtracts, in view of the above by heat treatment, the imaginary part μ of plural number permeability " improves, can make the wave absorber that electromagnetic wave suppresses the effect excellence.

In addition, after mixing the noncrystal non-retentive alloy of Fe base with by the binding material that fluorine analog thermoplastic synthetic rubber constitutes, the temperature-curable below the above 773K with 573K is heat-treated when being shaped.

According to the manufacture method of this wave absorber, because can in solidified forming, handle out,, reduce magnetostriction so can omit manufacturing process, improve the imaginary part μ of plural permeability ", can obtain the wave absorber that electromagnetic wave suppresses the effect excellence.

In addition, the manufacture method of wave absorber of the present invention is foregoing manufacture method, it is characterized in that: comprise among P, C, Si, the B more than one element and the molten alloy quench cooled of Fe, formation comprises the Fe base amorphous alloy powder of spherical particle, the noncrystal soft magnetic alloy powder of this Fe base is dropped in the pulverizing mill, mix by pulverizing, obtain the noncrystal soft magnetic alloy powder of described Fe base based on flat particle with 10 minutes～16 hours scope.

It should be noted that molten alloy is in order to improve noncrystal formation energy and corrosion resistance, can add respectively Al and Ga any one or two kinds element X or be selected from the metallic element of the element R that one or more the element among Cr, Mo, the V constitutes.

According to the manufacture method of this wave absorber, Fe base amorphous alloy powder is dropped in the pulverizing mill, mix by pulverizing with described condition, can obtain the noncrystal soft magnetic alloy powder of Fe base based on platypelloid type particle with suitable length-width ratio.

Description of drawings

Fig. 1 be expression be applicable to make use among the present invention comprise the amorphous alloy powder of spherical particle the time gases at high pressure sprayer unit (sprayer unit) a structure example analyse and observe ideograph.

Fig. 2 is that expression consists of Fe ₇₇Al ₁P _9.23C _2.2B _7.7Si _2.87X-ray diffraction result's the curve chart of the noncrystal soft magnetic alloy powder of Fe base.

Fig. 3 consists of Fe ₇₇Al ₁P _9.23C _2.2B _7.7Si _2.87The curve chart of DSC curve of the noncrystal soft magnetic alloy powder of Fe base.

Fig. 4 is the SEM photo of the noncrystal non-retentive alloy of Fe base before the expression pulverizing mill is handled.

Fig. 5 carries out the SEM photo that pulverizing mill is handled the noncrystal non-retentive alloy of Fe base after 1 hour.

Fig. 6 carries out the SEM photo that pulverizing mill is handled the noncrystal non-retentive alloy of Fe base after 2 hours.

Fig. 7 carries out the SEM photo that pulverizing mill is handled the noncrystal non-retentive alloy of Fe base after 4 hours.

Fig. 8 carries out the SEM photo that pulverizing mill is handled the noncrystal non-retentive alloy of Fe base after 8 hours.

Fig. 9 is the imaginary number magnetic permeability mu of lamellar sample of expression embodiment 1 " the curve chart of frequency characteristic.

Figure 10 is the expression effective permeability μ ' of embodiment 4 and imaginary number magnetic permeability mu " the curve chart of frequency characteristic.

Figure 11 is the expression effective permeability μ ' of embodiment 5 and imaginary number magnetic permeability mu " the curve chart of frequency characteristic.

The explanation of symbol.

Among the figure: 1-high-pressure water spray device; 2-motlten metal crucible; 3-water spray device; The 4-chamber; The 5-molten alloy; 6-motlten metal nozzle; 7-imports stream; 8-water injection nozzle; 10-water under high pressure; 21,31,41-dust core; The g-High-Pressure Water; The p-point of spraying; θ-water jet angle.

Embodiment

Below, with reference to the embodiment of description of drawings wave absorber of the present invention.

A form of wave absorber of the present invention is (wherein, Tx is a crystallization start temperature, and Tg is a vitrification point with Δ Tx=Tx-Tg.) the temperature interval Δ Tx of the subcooled liquid represented of formula is above Fe noncrystal non-retentive alloy of base and mixed with resin of 25K, solidified forming is tabular.Resin used herein can be selected fluorine analog thermoplastic synthetic rubber, fluoro vistanex, perfluoro alkoxy resin, fluoroethylenepropyl.ne copolymer, polyimides, epoxy resin, in these resins, the fluorine analog thermoplastic synthetic rubber of peroxide cure type, from the processability aspect, preferred especially.In addition, also can use the resin of excellent heat resistances such as silicone resin.

The fluorine analog thermoplastic synthetic rubber of this peroxide cure type, be to make crosslinked the forming of fluorine analog thermoplastic synthetic rubber by crosslinking agent, can use that compression set is little, excellent heat resistance, proportion for for example be about 1.9, elongation for example is about 190%, the about 76 (ML of Mooney viscosity ₁₊₁₀: 100 ℃) etc. the material of characteristic.

In addition, in the wave absorber just now,, can also add the lubricant that constitutes by aluminum stearate except the noncrystal non-retentive alloy of Fe base with as the resin of binding material.

Just now wave absorber, because the noncrystal soft magnetic alloy powder of Fe base is with the resin solidified forming as binding material, therefore form the noncrystal soft magnetic alloy powder of Fe base and be dispersed in the structure of resin inside, so become constitute the noncrystal soft magnetic alloy powder of Fe base each particle by the structure of insulation resin.

Like this, noncrystal soft magnetic alloy powder is by the binding material insulation of resin, so the impedance of wave absorber self is increased, in view of the above, suppressed the generation of overcurrent, can in the scope of broadness, improve the imaginary part μ of the plural permeability in the frequency band of hundreds of MHz～number GHz " (below, being expressed as imaginary number magnetic permeability mu "), the electromagnetic wave that can improve in the high-frequency region suppresses effect.

In wave absorber just now, in using the wave absorber of described resin as binding material, the imaginary number magnetic permeability mu among the 1GHz " is more than 5, is more preferably more than 10." be more than 5 or more than 10, then the electromagnetic wave in the frequency band of GHz suppresses the effect raising to if imaginary number magnetic permeability mu, can shield high-frequency electric wave effectively, so be preferred.In addition,, can obtain soft wave absorber, can obtain, use the wave absorber of the power of finger tip with regard to flexible form as plate rubber by selecting soft resin.

In addition, described resin is except improving the impedance of wave absorber, the noncrystal soft magnetic alloy powder that also bonds, the shape of maintenance wave absorber.Fluorine analog thermoplastic synthetic rubber also shows sufficient elasticity in wave absorber inside, shows 1 * 10 even for example use ^-6～50 * 10 ^-6The noncrystal soft magnetic alloy powder of magnetostriction constant the time, also can relax distortion, can relax the internal stress of wave absorber, can improve the imaginary number magnetic permeability mu ".

It should be noted that if add the lubricant that is made of aluminum foil stearate in described resin, then filled noncrystal soft magnetic alloy powder thick and fast, the density of wave absorber improves.In view of the above, imaginary number magnetic permeability mu " improves.

The noncrystal soft magnetic alloy powder of Fe base mainly comprises the platypelloid type particle, and this platypelloid type particle is that length-width ratio (major diameter/thickness) is the scope below 800 more than 1.Particularly, the thickness of particle is 0.1～5 μ m (preferred 1～2 μ m), and major diameter is the scope of 1～80 μ m (preferred 2～80 μ m).

The Fe noncrystal soft magnetic alloy powder of base is owing to be made of than higher platypelloid type particle length-width ratio, so compare with the situation that length-width ratio is little, the impedance of wave absorber self improves, suppressed the generation of overcurrent, " further improve, the electromagnetic wave of this frequency band suppresses effect and improves imaginary number magnetic permeability mu in the GHz frequency band.

Particularly, if the length-width ratio of platypelloid type particle is more than 1, just suppressed the generation of overcurrent, the impedance of wave absorber self increases, the imaginary number magnetic permeability mu of GHz frequency band, and " become easily more than 6, in view of the above, the electromagnetic wave of wave absorber suppresses effect and improves.

If the length-width ratio of platypelloid type particle is more than 10, just further suppressed the generation of overcurrent, the impedance scaling up of wave absorber self increases, the imaginary number magnetic permeability mu of GHz frequency band, and " become more than 10 easily; in view of the above, the electromagnetic wave of wave absorber suppresses effect and improves.

The upper limit of preferred length-width ratio is below 800.Length-width ratio has then been kept the connecting airtight property of flat particle and resin if below 800, owing to flat interparticle gap reduces, and also can guarantee flat interparticle insulating properties, so the imaginary number magnetic permeability mu, and " become easily more than 6, electromagnetic wave suppresses effect and improves.

More preferably the upper limit of length-width ratio is below 300.Length-width ratio is if below 300, then kept the connecting airtight property of flat particle and resin,, and also can guarantee flat interparticle insulating properties owing to flat interparticle gap reduces, therefore " become easily more than 10, electromagnetic wave suppresses effect and further improves the imaginary number magnetic permeability mu.

The density of preferred wave absorber is 3.0g/cm ³More than.If density is 3.0g/cm ³More than, then filled the noncrystal soft magnetic alloy powder of Fe base thick and fast, flat interparticle gap reduces, and in view of the above, " become easily more than 10, electromagnetic wave suppresses effect and improves the imaginary number magnetic permeability mu in the GHz frequency band.

The density of wave absorber is high more good more, if but become too high, then flat particle-filled overstocked, the impedance of wave absorber descends, and overcurrent takes place, the imaginary number magnetic permeability mu and " descends.Therefore, preferably the upper density limit of wave absorber is set at 6.5g/cm ³Below.

The containing ratio of the noncrystal soft magnetic alloy powder of Fe base in the preferred wave absorber is more than the 30 volume %, below the 80 volume %.If the containing ratio of the noncrystal soft magnetic alloy powder of Fe base is that then the amount of magnetic is abundant more than the 30 volume %, can effectively brings into play electromagnetic wave and suppress effect.In addition, if containing ratio below 80 volume %, then alloy powder contacts with each other, impedance can not descend, can be reliably the imaginary number magnetic permeability mu " maintains very highly, can effectively bring into play electromagnetic wave and suppress effect.

The containing ratio of resin is the remaining part of removing the noncrystal soft magnetic alloy powder of Fe base.

When adding lubricant, be to add in the scope below the 5 weight % more than the 0.1 weight % with respect to wave absorber preferably.

In addition, can cover described flat particle with waterglass.If cover described flat particle with waterglass, then particle insulating properties to each other further improves, and the impedance of wave absorber further improves, and can further improve the imaginary number magnetic permeability mu in the high-frequency region ", can improve electromagnetic wave and suppress effect.

The noncrystal non-retentive alloy of Fe base of the present invention is principal component with Fe, constitutes mutually by comprising the noncrystal of P, C, B at least.In addition, this alloy is that (wherein, Tx is a crystallization start temperature, and Tg is a vitrification point with Δ Tx=Tx-Tg.) the temperature interval Δ Tx of the subcooled liquid represented of formula is the above alloy of 25K.

The noncrystal non-retentive alloy of Fe base of the present invention, on the basis that makes noncrystal powder, fully keep necessary noncrystal formation energy, and with Fe-Al-Ga-C-P-Si-B class alloy phase ratio in the past, can improve magnetic characteristic, and when adopting the water spray method, can obtain the corrosion resistance of water-fast spray-on process as the quench cooled method.In addition,, also amorphization can be carried out,, high saturation magnetization and low core loss can be realized simultaneously so can reduce cost even do not add Ga.

The noncrystal non-retentive alloy of Fe of the present invention base has the Fe that shows magnetic, have noncrystal formation can semimetallic elements such as P, C, B, so with noncrystal be principal phase mutually in, shown excellent soft magnetic characteristic.In addition, except P, C, B, can also add Si.

In addition, can add M (elements of one or more among Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au), improve corrosion resistance.

This noncrystal non-retentive alloy is the metallic glass alloys that shows the temperature interval Δ Tx of the subcooled liquid more than the 25K, according to composition, it is above and then have the above remarkable temperature interval of 50K to have Δ Tx and be a 30K, in addition, about soft magnetism, has excellent characteristic in room temperature.

The noncrystal non-retentive alloy of Fe base of the present invention contains the more Fe of the ferromagnetism of manying element than Fe-Al-Ga-C-P-Si-B class alloy in the past, so show high saturation.

In addition, the noncrystal non-retentive alloy of Fe base of the present invention because whole tissue is noncrystal completely phase, so when heat-treating under the condition in appropriateness, do not separate out the crystalline solid phase, can relax internal stress, further improves soft magnetic characteristic.

In addition, the noncrystal soft magnetic alloy powder of Fe base of the present invention that quench cooled obtains by the water spray method can show and the equal or higher saturation magnetization of making of the gas atomization method of noncrystal soft magnetic alloy powder in the past.

The molten alloy (alloy of molten condition) that uses in the manufacturing of the noncrystal soft magnetic alloy powder of Fe base uses the material with Fe noncrystal non-retentive alloy same composition of base or roughly the same composition.In this molten alloy, as mentioned above, comprise have P, the noncrystal formation of C, B can element, and Δ Tx is more than the 25K.Therefore, when pulverizing by the water spray method, when cooling off molten alloy (alloy of molten condition), cooling rate being delayed and gas atomization method equal extent.That is, even allow cooling rate delay, crystallization can not take place, can form noncrystal phase easily yet.In addition, by the cooling rate of cooling during molten alloy controlled to the degree that fully acts at molten alloy upper surface tension force, can obtain closely spherical, that is, and the noncrystal soft magnetic alloy powder that surface coefficient is little.Therefore, necessitate even be difficult to also can form under the slow cooling rate of oxidation amorphous described alloy composition.

As an example of the noncrystal soft magnetic alloy powder of Fe of the present invention base, the temperature interval Δ Tx of the subcooled liquid of representing with Δ Tx=Tx-Tg is more than the 25K, can list the material of representing with following composition formula.

Fe _{100-x-y-z-w-t}M _xP _yC _zB _wSi _t

Wherein, M is one or more the transition elements that is selected among Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au, x, y, z, w, the t of expression ratio of components are 0.5 atom %≤x≤8 atom %, 2 atom %≤y≤15 atom %, 0 atom %＜z≤8 atom %, 1 atom %≤w≤12 atom %, 0 atom %≤t≤8 atom %, the atom % of 70 atom %≤(100-x-y-z-w-t)≤79.

Y, z, w, the t of the expression ratio of components in the described composition formula of the noncrystal non-retentive alloy of being represented by described composition formula in addition, of Fe base preferably satisfies the relation of atom % of 17 atom %≤(x+y+z+w+t)≤29.5.

Below, illustrate that the composition of the noncrystal non-retentive alloy of Fe base of the present invention limits reason.At first, Fe is the element that produces magnetic, is necessary element in the noncrystal non-retentive alloy of Fe base of the present invention.If improve the ratio of components of Fe, just can improve the saturation magnetization σ s of the noncrystal non-retentive alloy of Fe base.

The addition of Fe is preferably below the above 79 atom % of 70 atom %, more preferably below the above 79 atom % of 72 atom %, more preferably below the above 78 atom % of 73 atom %.When the addition of Fe is lower than 70 atom %, then saturation magnetization σ s drops to and is lower than 150 * 10 ^-6So Wbm/kg is undesirable.In addition, if the addition of Fe surpasses 79 atom %, then represent alloy noncrystal formation can the Tg/Tm of degree become and be lower than 0.57, noncrystal formation can descend, so undesirable.It should be noted that Tm is the fusing point of alloy.

In addition, if the addition of Fe is more than the 76 atom %, then can make the saturation magnetization σ s of alloy is 170 * 10 ^-6More than the Wbm/kg, if more than the 77 atom %, can make the saturation magnetization σ s of alloy is 180 * 10 ^-6More than the Wbm/kg.

In addition, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf can form non-dynamic oxidation film on the surface of alloy powder, can improve the corrosion resistance of alloy powder.In these elements, to the tool effect of raising of corrosion resistance is Cr.In the water spray method, when the molten alloy direct contact water, can prevent the generation (visual level) of the rust that in the dry run of alloy powder, produces.In addition, these elements can add separately, also can come compound interpolation with two or more combinations.For example, can carry out compound interpolation with the combination of Mo, V and Mo, Cr and V, Cr and Cr, Mo, V etc.In these elements, Mo, V are poorer slightly than the corrosion resistance of Cr, but in order to improve noncrystal formation energy, select these elements as required.In addition, surpass 8 atom % if be selected from the addition of the element among Cr, Mo, W, V, Nb, the Ta, then magnetic characteristic (saturation magnetization) descends.

In addition, in the element that adopts as the element M in the described composition formula, it can be that Zr, Hf are the highest that glass forms.Because the oxidizability of Ti, Zr, Hf is strong, thus these elements added if surpass 8 atom %, in case in atmosphere, dissolve the alloy powder raw material, then motlten metal oxidation in the raw material dissolving, magnetic characteristic (saturation magnetization) descends in addition.

In addition, be selected from the effect that one or more precious metal among Pt, Pd, the Au also can be obtained the corrosion resistance that improves alloy by interpolation, by these precious metal elements being distributed to the surface of alloy powder, corrosion resistance improves.In addition, can add these precious metal elements separately, or add with the element combinations that described Cr etc. has an effect that improves corrosion resistance.Described precious metal element is not owing to mix mutually with Fe, so if surpassing 8 atom % adds, then glass forms and can descend, magnetic characteristic (saturation magnetization) also descends in addition.In order to make the noncrystal non-retentive alloy of Fe base have corrosion resistance, the addition of described M is necessary for more than the 0.5 atom %.

Therefore, the M in the composition formula is one or more the element that is selected among Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au, and preferred especially the use is selected among Cr, Mo, W, V, Nb, the Ta one or more.The ratio of components x of described M is preferably below the above 8 atom % of 0.5 atom %, is preferably the above 4 atom % of 1 atom %, more preferably the above 3 atom % of 1 atom %.

C, P, B and Si are the elements that improves noncrystal formation energy, by add these elements in Fe and described M, become polynary series, compare with 2 yuan of serial situations having only Fe and described M, can stably form noncrystal phase.Particularly P and Fe have eutectic composition at low temperature (about 1050 ℃), thus whole tissue become noncrystal phase, and manifest the temperature interval Δ Tx of subcooled liquid easily.In addition, if add P and Si simultaneously, then the temperature interval Δ Tx of subcooled liquid becomes bigger, and noncrystal formation can increase, and can creating conditions when obtaining noncrystal single-phase organizing relax on more easy direction.

The ratio of components y of P when not adding Si is preferably more than the 2 atom % below the 15 atom %, more preferably below the above 14 atom % of 4 atom %, most preferably is below the above 11 atom % of 6 atom %.When the addition of P is lower than 2 atom %, can't obtain noncrystal non-retentive alloy, if surpass 15%, then saturation magnetization descends.If the ratio of components y of P is described scope, then manifest the temperature interval Δ Tx of subcooled liquid, the noncrystal formation of alloy can improve.

In addition, if add Si, then thermal stability improves, so preferably add more than the 2 atom %.In addition, if the addition of Si surpasses 8 atom %, then fusing point rises.Therefore, the ratio of components t of Si is preferably below the above 8 atom % of 0 atom %, more preferably below the above 8 atom % of 2 atom %, more preferably below the above 7 atom % of 2 atom %.

In addition, when the addition less than 2 atom % of B, be difficult to obtain the noncrystal non-retentive alloy of Fe base, if surpass 12 atom %, then fusing point rises.Therefore, the ratio of components w of B is preferably below the above 12 atom % of 1 atom %, more preferably below the above 10 atom % of 2 atom %, most preferably is below the above 9 atom % of 4 atom %.

In addition, if add C, then thermal stability improves, so preferably add more than the 1 atom %.In addition, if the addition of C surpasses 8 atom %, then fusing point rises.Therefore, the ratio of components z of C is preferably below the above 8 atom % of 0 atom %, more preferably below the above 6 atom % of 0 atom %, more preferably below the above 4 atom % of 1 atom %.

And the total ratio of components (y+z+w+t) of these semimetallic elements C, P, B and Si is below the above 29.5 atom % of 17 atom %, more preferably below the above 26 atom % of 18 atom %, more preferably below the above 25 atom % of 18 atom %.If the total ratio of components of semimetallic elements surpasses 29.5 atom %, then the ratio of components of Fe descends relatively, and saturation magnetization σ s descends, so be unfavorable.If the total ratio of components of semimetallic elements is lower than 17 atom %, then noncrystal formation can descend, and is difficult to obtain noncrystal homogeneous structure.

In addition, when the ratio of components of Fe is 76 atom % when above, be made as below the above 24 atom % of 18 atom % by the total ratio of components (y+z+w+t) that makes semimetallic elements C, P, B and Si, can make the saturation magnetization σ s of alloy powder is 170 * 10 ^-6More than the Wbm/kg.

When the ratio of components of Fe is 77 atom % when above, be that can make the saturation magnetization σ s of alloy powder is 180 * 10 below the above 23 atom % of 18 atom % by the total ratio of components (y+z+w+t) that makes semimetallic elements C, P, B and Si ^-6More than the Wbm/kg.

In addition, in the noncrystal soft magnetic alloy powder of Fe base of the present invention, can comprise the Ge of 4 atom % in the described composition.

In described composition arbitrarily, in the present invention, the temperature interval Δ Tx that can obtain subcooled liquid is more than the 25K, according to composition, can obtain more than the 35K.

In addition, except the element of representing with described composition, can also comprise unavoidable impurities.

After the melting, by based on single roller or two roller quench cooled method, again by spin processes or solution extraction in the liquid, perhaps by gas atomization method or water spray method, or pass through injection moulding method, as different shapes such as bulk, band shape, thread like body, powder, made the noncrystal non-retentive alloy of Fe base of the present invention.

Particularly with respect to well-known noncrystal non-retentive alloy strip is in the past pulverized the powder that constitutes of laminar particle, in the present invention, by described gas atomization method or water spray method, can obtain by being shaped as the alloy powder that torulose particle constitutes.

The described noncrystal non-retentive alloy of forming of Fe base by the water spray method obtains at room temperature has magnetic, in addition, has shown good magnetic by heat treatment.Therefore, the material as having excellent soft magnetic characteristic becomes for the useful material of various application.It should be noted that, if the additional disclosure manufacture method, then according to the size of the composition of alloy, the means that are used to make and goods, shape etc., the cooling rate that decision is fit to, but usually can be with 1～10 ⁴K/s is a standard.And, in fact, can be by confirming whether to separate out in the glassy phase (glassy phase) Fe as crystalline phase ₃B, Fe ₂B, Fe ₃P decides.

Below, an example by the noncrystal non-retentive alloy of water spray manufactured Fe base of the present invention is described.The water spray method is meant in air atmosphere, by with the above-mentioned Fe noncrystal non-retentive alloy same composition of base or roughly form the molten alloy that constitutes equally and nebulize in indoor spraying with water under high pressure, described molten alloy pulverizing, quench cooled, make the noncrystal non-retentive alloy of torulose Fe base.

Fig. 1 is that expression is applicable to the profile schema diagram based on an example of the high-pressure water spray device in the alloy powder manufacturing of water spray method.This high-pressure water spray device 1 is that main body constitutes with motlten metal crucible 2, water spray device 3 and chamber 4.This high-pressure water spray device 1 is configured in the air atmosphere.Filled molten alloy 5 in the inside of motlten metal crucible 2.In addition, be provided with the coil 2a of heater block in motlten metal crucible 2, heating and melting alloy 5 keeps molten condition.And, being provided with motlten metal nozzle 6 in the bottom of motlten metal crucible 2, molten alloy 5 drips to the inside of chamber 4 from motlten metal nozzle 6.

Water spray device 3 is configured in the below of motlten metal crucible 2.In this water spray device 3, be provided with the water injection nozzle 8 that water imports the top ends of stream 7 and this importing stream 7.

Water under high pressure 10 by not shown liquid force (forcing) pump (pressure-producing part) pressurization imports to water injection nozzle 8 by importing stream 7, becomes High-Pressure Water g from this nozzle 8 to 4 inside, chamber, spraying.4 inside forms the air atmosphere identical with the surrounding atmosphere of high-pressure water spray device 1 in the chamber.Chamber 4 pressure inside remain on about 100kPa, and temperature remains on ambient temperature in addition.

When manufacturing comprised the noncrystal soft magnetic alloy powder of Fe base of torulose particle, the molten alloy 5 that at first is filled in the motlten metal crucible 2 dripped in chamber 4 from motlten metal nozzle 6.Simultaneously, from the water injection nozzle 8 inject high pressure water 10 of water spray device 3.The water under high pressure 10 that sprays becomes High-Pressure Water g, arrives the described motlten metal that drips, and collides at spraying point p and motlten metal, makes the motlten metal atomizing, carries out quench cooled simultaneously and solidifies, and forms by the described noncrystal nearly globular powder of forming that constitutes mutually.These nearly globular powders are stored in the bottom of chamber 4 with water.

Here, the degree of the cooling rate of molten alloy for fully acting at molten alloy upper surface tension force.The cooling rate of molten alloy according to the composition of alloy, become the suitable cooling rates of decision such as particle diameter of the alloy powder of purpose, but can make 1～10 ⁴Scope about K/s is as standard.And, in fact, also can be by confirming whether to have obtained near near spherical and in glassy phase (glassyphase), whether separate out Fe as crystalline phase ₃B, Fe ₂B, Fe ₃P etc. decide mutually.

Then, in air atmosphere,,, obtain having the spherical or torulose noncrystal soft magnetic alloy powder of regulation average grain diameter these powder classifications after these nearly globular powder dryings.

When by the noncrystal soft magnetic alloy powder of the torulose Fe base of water spray manufactured, expulsion pressure, injection flow, molten alloy flow etc. by control water, the cooling rate of control molten alloy, in addition, temperature or viscosity, atomizing point (atomizing point distance) etc. by control water injection nozzle fracture width, water injection nozzle angle of inclination, water jet angle, molten alloy, control is created conditions, and can obtain the particle diameter of several μ m～100 tens of μ m.

And, the amorphous alloy powder of obtaining is like this dropped in the pulverizing mill, mix by pulverizing with 10 minutes～16 hours scope, obtain the noncrystal non-retentive alloy of described Fe base based on flat particle.

Pulverizing mixing based on pulverizing mill is preferably carried out with 10 minutes～16 hours scope, is more preferably 4～8 hours scope.

If pulverized the incorporation time less than 10 minutes, then because flattening is insufficient, so having the length-width ratio can't make the platypelloid type particle is the tendency 10 or more for example more than 1, surpasses 16 hours if pulverize incorporation time, then the length-width ratio of platypelloid type particle is above more than 800.

Can heat-treat the alloy powder of obtaining as required.By heat-treating, relaxed the alloy internal stress, can further improve the soft magnetic characteristic of the noncrystal non-retentive alloy of Fe base.Heat treatment temperature Ta is preferably in the scope more than the Curie temperature Tc of alloy, below the vitrification point Tg.If heat treatment temperature Ta is lower than Curie temperature Tc, then can't obtain raising effect, so undesirable based on heat treated soft magnetism characteristic.In addition, if heat treatment temperature Ta surpasses vitrification point Tg, then separate out the crystalline solid phase in the alloy structure easily, soft magnetic characteristic might descend, so undesirable.

In addition, heat treatment time preferably fully relaxes the internal stress of alloy, and the scope that does not have crystalline solid to separate out mutually, for example is preferably 30～300 minutes scope.

Then, in the noncrystal soft magnetic alloy powder of described Fe base, add and mix fluorine analog thermoplastic synthetic rubber, add lubricant as required, this mixture solidified forming under temperature more than the room temperature or the temperature below the above 573K of 323K, form tabular, heat treatment temperature below the above 773K of 573K is heat-treated again, obtains wave absorber of the present invention.

It should be noted that, in wave absorber of the present invention, as utilizing form, be preferably formed tabular, but be not limited to shape is formed tabular.Can certainly be processed into other shapes such as mesh-shape, bag shape.

According to described method, be added to the distortion on the wave absorber when having relaxed lamellar be shaped, so magnetostrictive influence reduces in view of the above, the imaginary part μ of plural permeability by heat treatment " improve, can obtain the wave absorber that electromagnetic wave suppresses the effect excellence,

It should be noted that the temperature when using fluorine analog thermoplastic synthetic rubber to be cured shaping as binding material is temperature more than the room temperature or the scope below the above 573K of 323K preferably.When the temperature when solidified forming was lower than room temperature, because temperature is insufficient, so can't be shaped described mixture solidified, so undesirable, if temperature surpasses 623K, then during solidified forming, fluorine analog thermoplastic synthetic rubber might ooze out, so undesirable.In addition,, preferably under near the temperature the room temperature, be cured shaping, but for solidified forming more reliably, preferably the temperature-curable more than 323K is shaped in order to shorten man-hour.

In addition, the heat treatment temperature when using fluorine analog thermoplastic synthetic rubber to be cured shaping as binding material is the scope below the above 773K of 573K preferably, is more preferably the following scope of the above 723K of 623K.Be more preferably below the above crystallization start temperature Tx of Curie temperature Tc of metallic glass alloys.

When heat treatment temperature was lower than 573K, temperature was insufficient, so can't relax the internal stress of wave absorber, can't improve the imaginary number magnetic permeability mu ", so undesirable.In addition, if heat treatment temperature surpasses 773K, so the then possible crystallization of the noncrystal non-retentive alloy of Fe base is undesirable.

In addition, as method for distinguishing, in the noncrystal soft magnetic alloy powder of described Fe base, add and mix fluorine analog thermoplastic synthetic rubber, add lubricant as required, by heat-treating in the shaping of the temperature-curable below the above 623K of 573K, also can obtain wave absorber of the present invention.

According to this method, because heat-treat tabular the time with being configured as, thus can omit manufacturing step, and reduce magnetostriction, and can improve permeability imaginary part μ ", can obtain the wave absorber that electromagnetic wave suppresses the effect excellence.

It should be noted that when also adding lubricant except fluorine analog thermoplastic synthetic rubber, preferred consolidation is shaped and heat treated temperature is the following scope of the above 623K of 573K.When if temperature is lower than 573K, temperature is insufficient, thus can't be shaped described mixture solidified, and can't relax the internal stress of wave absorber, and can't improve the imaginary number magnetic permeability mu ", so undesirable.In addition, if surpass 623K, then fluorine analog thermoplastic synthetic rubber might ooze out, and the possible crystallization of metal alloy glass, so undesirable.

An example as solidified forming device used herein can use the discharge plasma sintering equipment.The discharge plasma sintering equipment is to clip between upper punch and the low punch under the state of the thing that is formed, pulse current is flow through on one side, thing on one side can solidified forming be formed, and then by continuing that pulse current is flow through, the device that can heat-treat simultaneously, also be that the device that present inventors use, an example of this structure are documented in the specification of the special 2000-79062 of hope grade when the noncrystal soft magnetic alloy powder of this kind of solidified forming Fe base.

This discharge plasma sintering equipment is a following apparatus, promptly, be configured in to vacuumize maybe and can be adjusted into the indoor of inert gas atmosphere, in vacuum or inert gas atmosphere, one side applying pulse electric current, use on one side low punch the thing that the is formed purpose temperature that is rapidly heated, keeping under the non-crystal state, directly can press molding.

Handle by above press molding, can obtain the wave absorber that the Fe that comprises a platypelloid type particle noncrystal soft magnetic alloy powder of base and resin solidification are shaped and form.In addition, can obtain except these and also add lubriation material and the wave absorber that forms.

As additive method, the noncrystal soft magnetic alloy powder of Fe base, resin, solvent, form cream,, form film carrying out drying behind this cream of coating on the basis material, again to this thin film cladding cream, by repeating drying, form polylayer forest, this polylayer forest is carried out hot pressing, become thin plate, obtain wave absorber of the present invention by heat treatment again.

It should be noted that, when using fluorine analog thermoplastic synthetic rubber, preferably use oxolane,, preferably in cream, add crosslinking agent for crosslinked fluorine analog thermoplastic synthetic rubber as solvent as resin.In addition, carrying out being used for crosslinked hot pressing again after the hot pressing.

Be used for crosslinked hot pressing and preferably under the pressure of the following degree of the above 50MPa of temperature, 30MPa below the above 488K of 388K, carry out, be used for crosslinked hot pressing and preferably under the pressure of the following degree of the above 50MPa of temperature, 30MPa below the above 503K of 403K, carry out.

Also can carry out the hot pressing of crosslinkedization simultaneously with thin plateization.

According to this method, by adjusting the stacked number of times of film, can control the thickness of wave absorber, can obtain thinner wave absorber.In addition,, form wave absorber,, do not need can prevent from the leakage of electric wave so also can seamlessly form wave absorber for the portable electronic machine of complicated shape owing to can on the framework of portable electronic machine, directly apply cream.

In by the wave absorber of obtaining as mentioned above, use the elastomeric wave absorber of fluorine analog thermoplastic, the imaginary number magnetic permeability mu in 1GHz and " be more than 5, become the wave absorber that electromagnetic wave suppresses the effect excellence as resin.

[embodiment]

The characteristic of the noncrystal soft magnetic alloy powder of embodiment 1:Fe base

With Fe and Al, Fe-C alloy, Fe-P alloy, B and Si is raw material, difference weighing ormal weight, and making becomes Fe ₇₇Al ₁P _9.23C _2.2B _7.7Si _2.87Ratio of components, in decompression Ar atmosphere, these raw materials dissolvings, make blank with high-frequency induction heating apparatus.

This blank is put into the motlten metal crucible of gas atomization with the gases at high pressure sprayer units, be heated to 1300 ℃, dissolving is dripped from the motlten metal nozzle of motlten metal crucible, and from gas sprayer with 100kg/cm ²The pressure injection argon gas stream, it is vaporific making molten alloy, by in the indoor gas atomization method that makes vaporific molten alloy quench cooled, obtains the Fe base amorphous alloy powder (atomized powder) that the following spherical particle of particle diameter 62 μ m constitutes.Here the Fe base amorphous alloy powder of obtaining is the following powder of particle diameter 62 μ m, and substantial average grain diameter is about 30 μ m, also comprises the thinner spherical particle than 30 μ m.In addition, why making particle diameter is below the 62 μ m, is because by being below the 62 μ m, can obtain non-crystal alloy powder easilier.

Then, the Fe base amorphous alloy powder that comprises described spherical particle is dropped in the pulverizing mill, pulverize under the condition in 1,2,4,8 hours processing times and mix, making spherical particle is the platypelloid type particle, has obtained the noncrystal soft magnetic alloy powder of Fe base of the present invention.

It about processing time 4 hours the noncrystal soft magnetic alloy powder of Fe base based on pulverizing mill; carry out the parsing of crystal structure by X-ray diffraction method; and measure (Differential scanning caloriemetry: the differential scanning calorimetry), measured vitrification point Tg and crystallization start temperature Tx by DSC.Fig. 2 has represented the result of X-ray diffraction just now, and Fig. 3 represents the result that DSC measures.

The outward appearance of having observed the particle that comprises in the alloy powder by scanning electron microscope (SEM).Expression SEM photograph in Fig. 4～Fig. 8.Fig. 4 is that Fig. 5 was to be 1 hour in the processing time before pulverizing mill was handled, and Fig. 6 is to be 2 hours in the processing time, and Fig. 7 is to be 4 hours in the processing time, and Fig. 8 is to be 8 hours in the processing time.

As shown in Figure 2, the X-ray diffraction pattern of the noncrystal soft magnetic alloy powder of obtaining as can be known of Fe base is wide pattern, and whole tissue is based on mutually noncrystal.

In addition, as shown in Figure 2, from the DSC curve of the noncrystal soft magnetic alloy powder of Fe base as can be known, vitrification point Tg is 774K (501 ℃), and crystallization start temperature Tx is 811K (538 ℃), if find the solution Δ Tx from this result, then is 37K.

From above result as can be known, the noncrystal soft magnetic alloy powder of obtaining of Fe base has the above Δ Tx of 25K, and is based on noncrystal metallic glass alloys mutually.

Then, as shown in Figure 4, the particle that comprises in the amorphous alloy powder (spray powder) before pulverizing mill is handled is that length-width ratio is roughly 1 spherical particle.If with pulverizing mill this spherical particle is pulverized and to be mixed, then as Fig. 5～shown in Figure 8, be accompanied by the process in processing time, flattening, length-width ratio raising.Be the platypelloid type particle after 8 hours processing times shown in Figure 8, become thickness 1～2 μ m, particle major diameter 20～50 μ m, length-width ratio 10～50 scopes the platypelloid type particle.

One of embodiment 2: the characteristic of wave absorber ()

The plate tensile sample of embodiment 1～3

Identical with the situation of embodiment 1, by the gas atomization method, obtained by Fe ₇₇Al ₁P _9.23C _2.2B _7.7Si _2.87The amorphous alloy powder (atomized powder) that constitutes of spherical particle.

Then, the amorphous alloy powder that comprises described spherical particle is dropped in the pulverizing mill, under the condition in 4 hours processing times, making spherical particle is acicular particles or platypelloid type particle, has obtained the noncrystal soft magnetic alloy powder of Fe base.The noncrystal soft magnetic alloy powder screening of the Fe that obtains base for by below the particle diameter 105 μ m and the powder that constitutes of the acicular particles of length-width ratio 50, below the particle diameter 63m and the powder of the powder of length-width ratio 30, particle diameter 63～105 μ m and length-width ratio 20～50.

Then, each alloy powder 68.9 weight portion after the screening, fluorine analog thermoplastic synthetic rubber (the big LG-912 (registered trade mark) that Daikin Industries company makes) 25.0 weight portions, oxolane 4.7 weight portions, crosslinking agent (DCP1.0 weight portion, triallyl isocyanurate 1.0 weight portions) mix, form cream.

Then, use medicator, each cream is coated on the PET film, formed film by drying.For the film of obtaining,, obtained polylayer forest by carrying out coating, the drying of cream repeatedly.

For the polylayer forest of obtaining, under the condition of 433K, pressure 39MPa, carry out hot pressing, thin plateization, carry out hot pressing, crosslinked with the condition of 453K, pressure 39MPa.Like this, just made the preceding lamellar sample of heat treatment of embodiment 1～3.

About the lamellar sample before the heat treatment, drop in infrared ray video picture (image) stove, in nitrogen current atmosphere, heat up with 40K/ minute ratio, carry out 30 minutes heat treatment at 673K, made the lamellar sample after the heat treatment of embodiment 1～3.

The lamellar sample of embodiment 4

With Fe and Cr, Fe-C alloy, Fe-P alloy, B and Si is raw material, difference weighing ormal weight, and making becomes Fe _74.43Cr _1.96P _9.04C _2.16B _7.54Si _4.87Ratio of components, in decompression Ar atmosphere, these raw materials dissolvings, make blank with high-frequency induction heating apparatus.

This blank is put into aqueous vapor spraying shown in Figure 1 motlten metal crucible with the gases at high pressure sprayer unit, be heated to 1300 ℃, dissolving, drip from the motlten metal nozzle of motlten metal crucible, and from aqueous vapor sprayer shown in Figure 1 with inject high pressure water, it is vaporific making molten alloy, by in the indoor water spray method that makes vaporific molten alloy quench cooled, obtains the Fe base amorphous alloy powder (atomized powder) that the following spherical particle of particle diameter 62 μ m constitutes.Here the Fe base amorphous alloy powder of obtaining is the following powder of particle diameter 62 μ m, and substantial average grain diameter is about 12 μ m, also comprises the thinner spherical particle than 12 μ m.In addition, why making particle diameter is below the 62 μ m, is because by being below the 62 μ m, can obtain non-crystal alloy powder easilier.

Then, the material that has added aluminum foil stearate in comprising the Fe base amorphous alloy powder of described spherical particle is dropped in the pulverizing mill, under the condition in 12 hours processing times, pulverize and mix, by making spherical particle is the platypelloid type particle, has obtained the noncrystal soft magnetic alloy powder of Fe base of the present invention.

Then mix silicone resin (XE-B8951 that silicone company of GE Toshiba makes) in the alloy powder of obtaining, making becomes cream.

Then, use medicator, the cream of obtaining is coated on the PET film, formed film by drying.For the film of obtaining,, obtained thin plate by carrying out coating, the drying of cream repeatedly.

Under the condition of 423K, pressure 39MPa, carry out hot pressing for the thin plate of obtaining, carry out thin plateization.Like this, made the lamellar sample of embodiment 4.

The lamellar sample of embodiment 5

Except silicone resin is the SE9140 of DOREYCORNING SLICONE company manufacturing, made the plate tensile sample of embodiment 5 similarly to Example 4.

Comparative example 1 and 2 plate tensile sample

Identical with the situation of embodiment 1, by the gas atomization method, obtained and consisted of Fe ₇₇Al ₁P _9.23C _2.2B _7.7Si _2.87The amorphous alloy powder (atomized powder) that constitutes of spherical particle.

Then, the amorphous alloy powder that comprises described spherical particle is dropped in the pulverizing mill, pulverize under the condition in 4 hours processing times and mix, making spherical particle is acicular particles or platypelloid type particle, has obtained the noncrystal soft magnetic alloy powder of Fe base.Is the noncrystal soft magnetic alloy powder screening of the Fe base of obtaining below the particle diameter 63 μ m and the powder of powder, particle diameter 63～105 μ m and the length-width ratio 200～50 of length-width ratio 30.

Then, with the mixed polyvinyl chloride of 40 volume %,, fix in each alloy powder after screening, obtained the plate tensile sample of comparative example 1 and 2 with colding pressing at 100 ℃ of hot formings.It should be noted that, in described polyvinyl chloride, include the chlorinated paraffin wax of plasticizer with 20% ratio.

About embodiment 1～3 and comparative example 1, obtain the particle diameter of the noncrystal soft magnetic alloy powder of Fe base and length-width ratio, the density of plate tensile sample, the imaginary number magnetic permeability mu of 1GHz respectively ".Table 1 has been represented the result.In addition, about the wave absorber of embodiment 1, Fig. 9 has represented mensuration frequency and imaginary number magnetic permeability mu " relation.

It should be noted that the imaginary number magnetic permeability mu " mensuration be to cut out test film from plate tensile sample, with impedance method (materials used analyzer), in the frequency band of 1MHz～1.8GHz, measure.

About embodiment 4 and 5, obtain containing ratio, the containing ratio of aluminum foil stearate and the effective permeability μ ' and the imaginary number magnetic permeability mu of 1GHz of thin plate density, lamella thickness, the noncrystal soft magnetic alloy powder of Fe base ".Table 2 has been represented the result.In addition, about the wave absorber of embodiment 4 and 5, Figure 10 and Figure 11 have represented mensuration frequency and effective permeability μ ' and imaginary number magnetic permeability mu " relation.

[table 1]

[table 2]

As shown in table 1, about the plate tensile sample of embodiment 1～3, before and after heat treatment, the imaginary number magnetic permeability mu " increases.In embodiment 1, by heat treatment, the imaginary number magnetic permeability mu " increases by 27%, in embodiment 2 and embodiment 3, increases by 30% respectively.Like this, by after thin plateization, heat-treating, can " improve the imaginary number magnetic permeability mu about 20～30%, can obtain excellent wave absorber.

And in comparative example 1 and 2, much at one value that the imaginary number magnetic permeability mu " has shown the imaginary number magnetic permeability mu with embodiment 2 and 3 "., because the polyvinyl chloride that uses as binding material has burnt,, can't further improve the imaginary number magnetic permeability mu about 120 ℃ " so the heat treatment of the plate tensile sample of comparative example 1 and 2 is impossible.

It should be noted that,, imaginary number magnetic permeability mu about embodiment 4 and 5 as table 2, Figure 10 and shown in Figure 11 " be 14.6, obtained with the embodiment 2 of table 1 or 3 heat treated sample is arranged almost with the imaginary number magnetic permeability mu of degree ".This silicone resin that is considered to use has elasticity, so have the little characteristic of hardening stress, because this characteristic, the internal stress that remains in the noncrystal soft magnetic alloy powder of Fe base reduces.That is, the internal stress that remains in the alloy powder reduces, and has eliminated magnetostrictive influence, and the soft magnetism characteristic of the noncrystal soft magnetic alloy powder of Fe base improves the imaginary number magnetic permeability mu and " improves.

Experimental example 3: the characteristic of wave absorber (two)

Identical with the situation of experimental example 4, by the water spray method, obtained Fe-Cr-P-C-B (Si) the amorphous alloy powder (atomized powder) of class.

Then, the material that has added aluminum foil stearate in comprising the amorphous alloy powder of described spherical particle is dropped in the pulverizing mill, pulverize under the condition in 12 hours processing times and mix, making spherical particle is acicular particles or platypelloid type particle, has obtained the noncrystal soft magnetic alloy powder of Fe base.

Then, hybrid silicone in each alloy powder (SE9140 that DOREY CORNING SLICONE company makes), making becomes cream.

Then, use medicator, each cream is coated on the PET film, formed film by drying.For the film of obtaining,, obtained thin plate by carrying out coating, the drying of cream repeatedly.

Under the condition of 423K, pressure 39MPa, carry out hot pressing for the thin plate of obtaining, carry out thin plateization.Like this, made plate tensile sample.

Plate tensile sample is dropped in the infrared ray development stove, in nitrogen current atmosphere, heat up, carry out 30 minutes heat treatment, made the wave absorber after the heat treatment of embodiment 6～13 at 673K with 40K/ minute ratio.

About embodiment 6～13, effective permeability μ ' and the imaginary number magnetic permeability mu of the geomery of the powder particle after obtaining pulverizing mill and handling, containing ratio (volume %), plate density, plate thickness and the 1GHz of the noncrystal soft magnetic alloy powder of the base of the Fe in the thin plate ".Table 3 has been represented the result.

As shown in table 3, about embodiment 6～13, effective permeability μ ' becomes 14.2～17.1 scope, and in addition, the imaginary number magnetic permeability mu " becomes 14.2～14.9 scope, all shown excellent soft magnetic characteristic, have excellent electromagnetic wave and suppress effect.This is considered to because use the rubber-like silicone resin as resin, and has carried out sufficient heat treated cause.

[table 3]

As mentioned above, according to wave absorber of the present invention, possessing temperature interval Δ Tx is the above noncrystal non-retentive alloy of Fe base of 25K, because described alloy is the high material of permeability, has brought into play the electric wave absorbability.

In addition, the noncrystal soft magnetic alloy powder of Fe base is by insulation resin, improved the impedance of wave absorber self, in view of the above, suppressed the generation of overcurrent, can in the scope of broadness, improve the imaginary part μ of the plural permeability in the frequency band of hundreds of MHz～number GHz ", the electromagnetic wave that can improve in the high-frequency region suppresses effect.

Resin is in fluorine analog thermoplastic synthetic rubber, fluoro vistanex, perfluoro alkoxy resin, the fluoroethylenepropyl.ne copolymer any one when constituting, and can obtain soft wave absorber.

In addition, when resin is silicone resin, also can obtain excellent imaginary number permeability.

Table 1

	The alloy particle diameter	The containing ratio of non-retentive alloy	Heat treatment	Density (g/cm 3)	Imaginary number magnetic permeability mu "
						Embodiment 1	Below the 105 μ m	40 volume %	Do not have	3.0	?4.48
Have	3.0	?5.68
			Embodiment 2	Below the 105 μ m	40 volume %				Do not have	3.2	?10.76
Have	3.2	?13.99
						Embodiment 3	Below 63～105 μ m	40 volume %	Do not have	3.0	?11.61
Have	3.0	?15.09
			Comparative example 1	Below the 105 μ m	40 volume %				Do not have	3.3	?10.76
Comparative example 2	Below 63～105 μ m	40 volume %				Do not have	3.2	?11.61

Table 2

	The containing ratio of alloy (volume %)	Aluminum foil stearate containing ratio (quality %)	Plate density (g/cm 3)	Plate thickness (mm)	?μ′ ?(1GHz)	??μ″ ??(1GHz)
							Embodiment 4	?45	?5	?3.205	?0.091	?17.2	??14.6
Embodiment 5	?45	?5	?3.055	?0.194	?14.7	??14.6

Table 3

	Alloy composition	Shape length-width ratio after grinding			Alloy powder containing ratio (volume %)	Plate density (g/cm 3)	Plate thickness (mm)	??μ′ ??(1GHz)	??μ″ ??(1GHz)
										Thickness	Major diameter	The length ratio
		Embodiment 6	?Fe 75Cr 2P 13C 5B 5	0.1～1μm									10～50μm	20～100	?45％	2.9	?0.15	??14.9	??14.2
Embodiment 7	?Fe 73.4Cr 1.96P 12.74C 4.8B 7				0.1-1μm	10～50μm	20～100	?45％	3.0	?0.16	??15.1	??14.7
		Embodiment 8	?Fe 76.21Cr 1.98P 9.14C 2.18B 7.62Si 3.87	0.1～1μm									10～50μm	20～100	?45％	2.9	?0.15	??15.5	??14.4
Embodiment 9	?Fe 73.84Cr 2.5P 9.04C 2.16B 7.54Si 4.87				0.1～1μm	10～50μm	20～100	?45％	2.9	?0.15	??15.7	??14.5
		Embodiment 10	?Fe 72.39Cr 4P 9.04C 2.16B 7.54Si 4.87	0.1～1μm									10～50μm	20～100	?45％	2.8	?0.16	??14.2	??13.9
Embodiment 11	?Fe 74.43Mo 1.96P 9.04C 2.16B 7.54Si 4.87				0.1～1μm	10～50μm	20～100	?45％	2.9	?0.15	??14.8	??14.2
		Embodiment 12	?Fe 76.19V 1P 9.14C 2.18B 7.62Si 3.87	0.1～1μm									10～50μm	20～100	?45％	3.0	?0.17	??17.1	??14.7
Embodiment 13	?Fe 74.99Cr 1.4P 9.04C 2.16B 7.54Si 4.87				0.1～1μm	10～5μm	20～100	?45％	2.9	?0.16	??15.3	??14.9

Claims (21)

1. wave absorber is characterized in that:

Is the temperature interval Δ Tx of the subcooled liquid of representing with Δ Tx=Tx-Tg formula the noncrystal non-retentive alloy of Fe base more than the 25K and mixed with resin, solidified forming; described resin is any one in fluorine analog thermoplastic synthetic rubber, fluoro vistanex, perfluoro alkoxy resin, fluoroethylenepropyl.ne copolymer, polyimide resin, the epoxy resin; wherein; Tx is a crystallization start temperature, and Tg is a vitrification point.

2. wave absorber according to claim 1 is characterized in that:

Described resin is the fluorine analog thermoplastic synthetic rubber of peroxide cure type.

3. wave absorber according to claim 1 is characterized in that:

The noncrystal non-retentive alloy of described Fe base comprises Fe, transition metal and B.

4. wave absorber according to claim 3 is characterized in that:

The noncrystal non-retentive alloy of described Fe base comprises at least a above semimetallic elements among P, C, the Si.

5. wave absorber according to claim 1 is characterized in that:

The content of the noncrystal non-retentive alloy of described Fe base is 40～55 volume %.

6. wave absorber according to claim 1 is characterized in that:

The transition metal that comprises in the noncrystal non-retentive alloy of described Fe base is one or more the element that is selected among Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au.

7. wave absorber according to claim 1 is characterized in that:

Comprise the noncrystal non-retentive alloy of described Fe base with pulverulence, the average grain diameter of described powder is 1～80 μ m, and thickness is 0.1～5 μ m.

8. wave absorber according to claim 7 is characterized in that:

The length-width ratio of described powder is more than 1, below 800.

9. wave absorber according to claim 7 is characterized in that:

The length-width ratio of described powder is more than 5, the scope below 300.

10. wave absorber according to claim 1 is characterized in that:

The imaginary part μ of the plural permeability among the 1GHz " be more than 5.

11. wave absorber according to claim 1 is characterized in that:

The imaginary part μ of the plural permeability among the 1GHz " be more than 10.

12. wave absorber according to claim 1 is characterized in that:

Density is 3.0g/cm ³More than, the containing ratio of the noncrystal soft magnetic alloy powder of described Fe base is more than the 30 volume %, below the 80 volume %.

13. wave absorber according to claim 7 is characterized in that:

The powder particle of the noncrystal non-retentive alloy of described Fe base is covered by waterglass.

14. wave absorber according to claim 1 is characterized in that:

The noncrystal non-retentive alloy of described Fe base comprises more than one element and the Fe among P, C, Si, the B, by with noncrystal be the organizational composition of principal phase mutually.

15. wave absorber according to claim 14 is characterized in that:

Behind described Fe noncrystal soft magnetic alloy powder of base and the mixing of described binding material, the solidified forming, heat-treat in the scope more than the Curie-point temperature Tc of described noncrystal non-retentive alloy, below the crystallization start temperature Tx.

16. wave absorber according to claim 14 is characterized in that:

The noncrystal non-retentive alloy of described Fe base is represented by following composition formula:

Fe _{100-x-y-z-w-t}M _xP _yC _zB _wSi _t

Wherein, M is one or more the element that is selected among Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au, and x, y, z, w, the t of expression ratio of components is the atom % of 0.5 atom %≤x≤8 atom %, 2 atom %≤y≤15 atom %, 0 atom %＜z≤8 atom %, 1 atom %≤w≤12 atom %, 0 atom %≤t≤8 atom %, 70 atom %≤(100-x-y-z-w-t)≤79.

17. wave absorber according to claim 16 is characterized in that:

Y, z, w, the t that represents described ratio of components satisfies the relation of atom % of 17 atom %≤(x+y+z+w+t)≤29.5.

18. wave absorber according to claim 16 is characterized in that:

X, y, z, w, the t that represents described ratio of components satisfies the relation of atom % of 1 atom %≤x≤4 atom %, 4 atom %≤y≤14 atom %, 0 atom %＜z≤6 atom %, 2 atom %≤w≤10 atom %, 2 atom %≤t≤8 atom %, 72 atom %≤(100-x-y-z-w-t)≤79.

19. wave absorber according to claim 16 is characterized in that:

X, y, z, w, the t that represents described ratio of components satisfies the relation of atom % of 1 atom %≤x≤3 atom %, 6 atom %≤y≤11 atom %, 1 atom %＜z≤4 atom %, 4 atom %≤w≤9 atom %, 2 atom %≤t≤7 atom %, 73 atom %≤(100-x-y-z-w-t)≤79.

20. the manufacture method of a wave absorber is characterized in that:

Mix, behind the solidified forming, heat-treat the noncrystal soft magnetic alloy powder of Fe base with by the binding material that fluorine analog thermoplastic synthetic rubber constitutes with the heat treatment temperature below the above 773K of 573K.

21. the manufacture method of wave absorber according to claim 20 is characterized in that:

Comprise among P, C, Si, the B more than one element and the molten alloy quench cooled of Fe, formation comprises the Fe base amorphous alloy powder of spherical particle, the noncrystal soft magnetic alloy powder of this Fe base is dropped in the pulverizing mill, mix by pulverizing, obtain the noncrystal soft magnetic alloy powder of described Fe base based on flat particle with 10 minutes～16 hours scope.

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