CN107419199A - A kind of stanniferous soft magnetic iron-based nano-amorphous alloy and preparation method thereof - Google Patents

A kind of stanniferous soft magnetic iron-based nano-amorphous alloy and preparation method thereof Download PDF

Info

Publication number
CN107419199A
CN107419199A CN201710520958.7A CN201710520958A CN107419199A CN 107419199 A CN107419199 A CN 107419199A CN 201710520958 A CN201710520958 A CN 201710520958A CN 107419199 A CN107419199 A CN 107419199A
Authority
CN
China
Prior art keywords
alloy
stanniferous
amorphous alloy
soft magnetic
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710520958.7A
Other languages
Chinese (zh)
Other versions
CN107419199B (en
Inventor
陈晓阳
张扬
代巧
范振敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University of Technology
Original Assignee
Jiangsu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu University of Technology filed Critical Jiangsu University of Technology
Priority to CN201710520958.7A priority Critical patent/CN107419199B/en
Publication of CN107419199A publication Critical patent/CN107419199A/en
Application granted granted Critical
Publication of CN107419199B publication Critical patent/CN107419199B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/02Amorphous alloys with iron as the major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/008Ferrous alloys, e.g. steel alloys containing tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32Ferrous alloys, e.g. steel alloys containing chromium with boron
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147Alloys characterised by their composition
    • H01F1/153Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147Alloys characterised by their composition
    • H01F1/153Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147Alloys characterised by their composition
    • H01F1/153Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341Preparation processes therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets

Abstract

The invention belongs to magnetic metal material technical field, more particularly to a kind of stanniferous soft magnetic iron-based nano-amorphous alloy and preparation method thereof, the alloy adds a small amount of Sn to prepare on the basis of Fe (Mo, Nb, Cr) (P, C, B, Si) Amorphous Alloy, and preparation method comprises the following steps:(1) melting;(2) quick solidification;(3) anneal.Between iron tin bianry alloy has very wide phase separation region on composition, tin element is added in Fe-based amorphous alloy, is easily formed phase separation structure, Fu Tie areas and Pin Tie areas are formed in microstructure.The uneven distribution of ferro element, the nucleation rate of α Fe phases can be improved in annealing process, and limit growing up for α Fe crystal grain so that formed nano-amorphous alloy after non-crystaline amorphous metal annealing, obtain high saturation magnetization, while keep low coercivity.

Description

A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof
Technical field
The invention belongs to magnetic metal material technical field, and in particular to a kind of stanniferous soft magnetic iron base nanometer crystal-non- Peritectic alloy and preparation method thereof.
Background technology
Fe-based amorphous alloy is the novel magnetic metal material that recent decades develop, and has typical soft magnetism special Sign, including high saturation magnetization and low coercivity etc., there is sizable use value and be widely applied prospect.Iron The magnetic property of base noncrystal alloy is relevant with composition, by changing the species and content of alloying element, can adjust Fe-based amorphous conjunction The magnetic property of gold.More appropriate alloy proportion is found, is one of approach for obtaining high magnetic characteristics Fe-based amorphous alloy.But iron-based is non- Peritectic alloy composition is various, it is difficult to there is the composition proportion criterion of the optimization magnetic property of universality.Increase iron content is currently known, Saturation magnetization can be effectively improved, but iron content increases the decline that may cause amorphous formation ability.Other alloy members The validity of influence of the element to Fe-based amorphous magnetic property is limited in the non-crystaline amorphous metal of some special components, without pervasive Property.Except changing composition, process annealing is carried out to Fe-based amorphous alloy, can also optimize its magnetic property within the specific limits, especially It is that effect is more apparent in terms of reducing coercivity.But the improvement of this method is limited, the magnetic property of alloy can not be made to be dashed forward The lifting of broken property.
The method of another effectively lifting Fe-based amorphous alloy soft magnet performance is to prepare nanocrystalline and amorphous composite alloy. Generate that ferromagnetic α-Fe are nanocrystalline in Fe-based amorphous alloy, the overall saturation of alloy is improved using α-Fe high magnetic intensity The intensity of magnetization.Also, the region between nanocrystalline is still non-crystaline amorphous metal, so its coercivity still may remain in reduced levels. This nanocrystalline and amorphous alloy is due to the saturation magnetization close to traditional rolling silicon steel sheet and far below silicon steel sheet Coercivity, silicon steel sheet is substituted and has been widely used in transformer fe core material.
The preparation of iron based nano crystal-non-crystaline amorphous metal is typically that non-crystaline amorphous metal is annealed, and brings it about crystallization, is analysed Go out α-Fe crystal grain.By the control to annealing process, the quantity and volume of the crystal of precipitation can be regulated and controled.The volume of α-Fe crystal grain Smaller, quantity is more, and the saturation magnetization of alloy is higher.But the nanocrystalline limited amount for formation of annealing is in alloy The nucleation rate of α-Fe phases.Increase nucleation rate, can be by toward defect is introduced in amorphous, forming core core being caused, to increase crystalline phase Forming core point quantity, specific method include non-crystaline amorphous metal is irradiated etc. with high-power electron beam or neutron beam.But these sides Method cost is high, and efficiency is low, is not suitable for producing in enormous quantities.Therefore, it is necessary to seek a kind of increase α of new low-cost high-efficiency- The method that Fe phases are formed, to prepare iron based nano crystal-non-crystaline amorphous metal of more high magnetic characteristics.
The content of the invention
Invention broadly provides a kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof, pass through A small amount of tin element is added in the alloy, number of nuclei of the increase α-Fe phases in annealing process, is received to obtain more α-Fe Meter Jing, the lifting significant effect to soft magnet performance.Its technical scheme is as follows:
A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy, it is by Fe, Mo, Nb, Cr, Sn, P, C, B and Si structure Into formula be FeaMobNbcCrdSnePfCgBhSiiAlloy, wherein a, b, c, d, e, f, g, h and i is respectively each self-corresponding original Sub- degree, and 70≤a≤85,0≤b≤10,0≤c≤10,0≤d≤10,0 < e≤5,0≤f≤20,0≤g≤ 20th, 0≤h≤20,0≤i≤20, and 75≤a+b+c+d+e≤90,10≤f+g+h+i≤25, a+b+c+d+e+f+g+h+i= 100。
The content of tin element is different according to the composition of Fe-based amorphous alloy in the alloy and otherwise varied, the original of tin element Son is more excessive than unsuitable, should ensure that tin element is generally evenly distributed in the alloy, and keeps the nascent Crystallization Phases of non-crystaline amorphous metal Still it is α-Fe.
The nanocrystalline principle of high density can be formed in the alloy to be, iron tin binary alloy has very wide on composition Phase separation region between, also, the element such as P, C, B, Si can further expand its phase separation region.Therefore, in Fe-based amorphous conjunction Tin element is added in gold, is easily formed phase separation structure, Fu Tie areas and Pin Tie areas are formed in microstructure.Fu Tie areas therein α-Fe embryos is easily formed, and then develops into α-Fe nanocrystals.Meanwhile the caused Fu Tiequ that is separated, its area size Generally in nanoscale, during α-Fe crystal grain is grown up, the diffusion length of ferro element is limited, and the α-Fe of formation are nanocrystalline to be not easy Grow up.So in stanniferous Fe-based amorphous alloy, substantial amounts of α-Fe grain nucleations, and can limitation α-Fe crystal grain can be formed Size.
A kind of preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy, comprises the following steps:
(1) according to formula ratio preparation raw material, then mixed;
(2) raw material prepared is subjected to melt back in smelting furnace, until obtaining the uniform foundry alloy of composition;
(3) by foundry alloy remelting, then by casting, quenching method or get rid of band method carry out quick solidification be made it is block or thin The non-crystaline amorphous metal of banding;
(4) non-crystaline amorphous metal is annealed, annealing temperature is higher than 10-50 DEG C of amorphous alloy crystallization start temperature, annealing Time is 60-600s, obtains stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy.
Preferably, in step (2) in melting or step (3) during remelting, first vacuumize and be re-filled with inert gas and protected, First it will be evacuated to 10 in smelting furnace-3Below Pa, inert gas is re-filled with to 0.02MPa is more than and carries out melting.
Preferably, casting is specifically that foundry alloy is placed in electric arc furnaces or induction furnace and melted, then in step (3) Block is frozen into suction or penetrating cooling mould, obtains non-crystaline amorphous metal.
Preferably, quenching method is specifically that foundry alloy is sealed in vacuum tube in step (3), by vacuum tube and female conjunction After gold is heated to foundry alloy fusing together, block is frozen into coolant of quenching, obtains non-crystaline amorphous metal.
Preferably, it is specifically that foundry alloy is placed in the porose crucible in bottom that band method is got rid of in step (3), will after fusing Foundry alloy liquid is sprayed onto at a high speed on the chill roll of rotation, and quick solidification forms strip, obtains non-crystaline amorphous metal.
Preferably, annealing temperature is 400-700 DEG C in step (4).
Using such scheme, the present invention has advantages below:
(1) by introducing phase separation element on the basis of Fe- (Mo, Nb, Cr)-(P, C, B, Si) Amorphous Alloy Sn, the microstructure with phase separation structure is formed in non-crystaline amorphous metal, that is, Fu Tie areas and Pin Tie areas are formed, so as to increase α-Fe The mutually number of nuclei in annealing process, and growing up for α-Fe crystal grain is limited, high saturation magnetization is obtained, while keep low Coercivity, the lifting positive effect to soft magnet performance;
(2) noble element is free of in alloying component of the present invention, raw material used in alloy melting to purity requirement not Height, the raw material of technical purity can be used to be prepared, cost of material is low., can be and alloy preparation method of the present invention is succinct Realized in common device, easily apply and promote in the industrial production.
Embodiment
Experimental method in following examples is conventional method unless otherwise required, involved experiment reagent and material Material is routine biochemistry reagent and material unless otherwise required.
A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy, it is by Fe, Mo, Nb, Cr, Sn, P, C, B and Si structure Into formula be FeaMobNbcCrdSnePfCgBhSiiAlloy, wherein a, b, c, d, e, f, g, h and i is respectively each self-corresponding original Sub- degree, and 70≤a≤85,0≤b≤10,0≤c≤10,0≤d≤10,0 < e≤5,0≤f≤20,0≤g≤ 20th, 0≤h≤20,0≤i≤20, and 75≤a+b+c+d+e≤90,10≤f+g+h+i≤25, a+b+c+d+e+f+g+h+i= 100。
The preparation method of above-mentioned stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy, it comprises the following steps:
(1) according to formula ratio preparation raw material, then mixed;
(2) raw material prepared is subjected to melt back in smelting furnace, first vacuumizes during melting and be re-filled with inert gas and enter Row protection, i.e., first will be evacuated to 10 in smelting furnace-3Below Pa, inert gas is re-filled with to 0.02MPa is more than and carries out melting, directly To obtaining the uniform foundry alloy of composition;
(3) by foundry alloy remelting, then foundry alloy is placed in electric arc furnaces or induction furnace by casting and melted, then Block amorphous alloy is frozen into suction or penetrating cooling mould, or foundry alloy is sealed in vacuum tube by quenching method, will After vacuum tube and foundry alloy are heated to foundry alloy fusing together, block amorphous alloy is frozen into coolant of quenching, or by getting rid of Foundry alloy is placed in the porose crucible in bottom by band method, is sprayed onto foundry alloy liquid at a high speed on the chill roll of rotation, soon after fusing Rapid hardening solid is into strip non-crystaline amorphous metal;
(4) non-crystaline amorphous metal is annealed, annealing temperature is higher than 10-50 DEG C of amorphous alloy crystallization start temperature, annealing Temperature is 400-700 DEG C, annealing time 60-600s, obtains stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy.
Embodiment 1
According to Fe72Mo3Sn1P8.7C7.0B5Si3.3Alloying component the atomic percent of each element is converted into quality percentage Dispensing is carried out than after.The raw material includes pure element simple substance and its intermediate alloy, and the purity of raw material will in general industry purity In asking, total atomic percent of impurity is no more than 2% in alloy.
It is placed in after above-mentioned raw materials are mixed in quartz ampoule, is put into the induction coil in vaccum sensitive stove and carries out melting.First 10 will be evacuated in stove-3Below Pa, heated after being re-filled with 0.04MPa high-purity argon gas.Melting 6 times is repeated, obtains composition Uniform foundry alloy, alloy surface is clean and metal luster.
Non-crystaline amorphous metal block is prepared with casting, it is consistent when the control of furnace atmosphere is with melting.Foundry alloy is placed in bottom In porose quartz ampoule, hole diameter about 1mm, quartz ampoule being placed in induction coil, quartz ampoule upper end connects with outside argon gas, The pressure of external argon gas is higher 0.03MPa than the pressure of argon gas in stove;After alloy melting, connecting valve is opened, makes outside argon gas Into quartz ampoule, aluminium alloy is sprayed into copper mold, diameter 3mm shaft-like non-crystaline amorphous metal is made.XRD inspections are carried out to alloy sample Survey, only " steamed bun peak " occur in the XRD spectrums measured, without sharp diffraction maximum, it was demonstrated that the sample is non-crystaline amorphous metal.
The T of the non-crystaline amorphous metal is measured using DSCxTemperature.Non-crystaline amorphous metal is encapsulated in vitreosil pipe, annealing temperature is set 520 DEG C are set to, annealing time 180s.XRD detections are carried out to the sample after annealing, find the diffraction of α-Fe phases wherein occur Peak.Observed under transmission electron microscope, it is seen that intensive α-Fe crystal grain is formed in sample, size is no more than 20nm.Pass through comprehensive physical property Measuring system (PPMS) carries out magnetic property detection to the sample after annealing, it is known that its saturation magnetization is more than 1.4T, than not adding Enter the Fe of tin73Mo3P8.7C7.0B5Si3.3Non-crystaline amorphous metal saturation magnetization is higher by 0.2T, and coercivity remains at below 5A/m.
Embodiment 2
According to Fe75.0Sn1.0C7.0Si3.3B5.0P8.7Alloying component the atomic percent of each element is converted into quality hundred Divide and than then carry out dispensing.The raw material includes pure element simple substance and its intermediate alloy, and the purity of raw material is in general industry purity In it is required that, total atomic percent of impurity is no more than 2% in alloy.
It is placed in after above-mentioned raw materials are mixed in quartz ampoule, is put into the induction coil in vaccum sensitive stove and carries out melting.First 10 will be evacuated in stove-3Below Pa, heated after being re-filled with 0.05MPa high-purity argon gas.Melting 5 times is repeated, obtains composition Uniform foundry alloy, alloy surface is clean and metal luster.
Amorphous alloy ribbon is prepared using band method is got rid of:Alloy pig is placed in the foraminate quartz ampoule in bottom, hole diameter About 1mm, quartz ampoule is placed in induction coil, quartz ampoule upper end connects with outside argon gas, and the pressure of external argon gas is than argon in stove The high 0.03MPa of pressure of gas;After alloy melting, connecting valve is opened, outside argon gas is entered quartz ampoule, aluminium alloy is sprayed onto The cooling roller surface of rotation, the rotating speed of chill roll is 30m/s, and aluminium alloy solidifies to form wide 2mm, thick 26 μm alloy thin band.It is right Alloy thin band carries out XRD detections, only " steamed bun peak " occurs in the XRD spectrums measured, without sharp diffraction maximum, it was demonstrated that the strip is non- Peritectic alloy.
The T of the non-crystaline amorphous metal is measured using DSCxTemperature.Amorphous thin ribbon is encapsulated in vitreosil pipe and annealed, temperature 540 DEG C of degree, it is incubated 240s.XRD detections are carried out to the strip after annealing and confirm that Crystallization Phases therein are α-Fe.Under transmission electron microscope Observation, it is seen that after annealing in strip the size of α-Fe crystal grain in below 30nm.Magnetic is carried out to the strip after annealing by PPMS It can detect, it is possible to find its saturation magnetization is more than 1.6T, than not stanniferous Fe76.0C7.0Si3.3B5.0P8.7Non-crystaline amorphous metal is satisfied About 0.1T is higher by with the intensity of magnetization, while coercivity is maintained at below 2A/m.
Embodiment 3
According to Fe72Mo5Cr2Sn0.5P12C7B1Si0.5Alloying component the atomic percent of each element is converted into quality hundred Divide and than then carry out dispensing.The raw material includes pure element simple substance and its intermediate alloy, and the purity of raw material is in general industry purity In it is required that, total atomic percent of impurity is no more than 2% in alloy.
It is placed in after above-mentioned raw materials are mixed in quartz ampoule, is put into the induction coil in vaccum sensitive stove and carries out melting.First 10 will be evacuated in stove-3Below Pa, heated after being re-filled with 0.04MPa high-purity argon gas.Melting 6 times is repeated, obtains composition Uniform foundry alloy, alloy surface is clean and metal luster.
Non-crystaline amorphous metal block is prepared using quenching method:Foundry alloy is sealed in vacuum tube by alloy pig, by vacuum tube and After foundry alloy is heated to foundry alloy fusing together, diameter 1.5mm block is frozen into coolant of quenching.Alloy thin band is carried out XRD is detected, and only " steamed bun peak " occurs in the XRD spectrums measured, without sharp diffraction maximum, it was demonstrated that the strip is non-crystaline amorphous metal.
The T of the non-crystaline amorphous metal is measured using DSCxTemperature.Amorphous thin ribbon is encapsulated in vitreosil pipe and annealed, temperature 640 DEG C of degree, it is incubated 120s.XRD detections are carried out to the strip after annealing and confirm that Crystallization Phases therein are α-Fe.Under transmission electron microscope Observation, it is seen that after annealing in strip the size of α-Fe crystal grain in below 30nm.Magnetic is carried out to the strip after annealing by PPMS It can detect, it is possible to find its saturation magnetization is more than 1.5T, than not stanniferous Fe72.5Mo5Cr2P12C7B1Si0.5Non-crystaline amorphous metal Saturation magnetization is higher by about 0.1T, while coercivity is maintained at below 2A/m.
Embodiment 4
According to Fe78Nb1Cr2Sn2P11B5Si1Alloying component the atomic percent of each element is converted into mass percent After carry out dispensing.The raw material includes pure element simple substance and its intermediate alloy, and the purity of raw material is in general industry purity requirement Interior, total atomic percent of impurity is no more than 2% in alloy.
It is placed in after above-mentioned raw materials are mixed in quartz ampoule, is put into the induction coil in vaccum sensitive stove and carries out melting.First 10 will be evacuated in stove-3Below Pa, heated after being re-filled with 0.04MPa high-purity argon gas.Melting 6 times is repeated, obtains composition Uniform foundry alloy, alloy surface is clean and metal luster.
Non-crystaline amorphous metal block is prepared with casting, it is consistent when the control of furnace atmosphere is with melting.Foundry alloy is placed in bottom In porose quartz ampoule, hole diameter about 1mm, quartz ampoule being placed in induction coil, quartz ampoule upper end connects with outside argon gas, The pressure of external argon gas is higher 0.03MPa than the pressure of argon gas in stove;After alloy melting, connecting valve is opened, makes outside argon gas Into quartz ampoule, aluminium alloy is sprayed into copper mold, diameter 2mm shaft-like non-crystaline amorphous metal is made.XRD inspections are carried out to alloy sample Survey, only " steamed bun peak " occur in the XRD spectrums measured, without sharp diffraction maximum, it was demonstrated that the sample is non-crystaline amorphous metal.
The T of the non-crystaline amorphous metal is measured using DSCxTemperature.Non-crystaline amorphous metal is encapsulated in vitreosil pipe, annealing temperature is set 520 DEG C are set to, annealing time 180s.XRD detections are carried out to the sample after annealing, find the diffraction of α-Fe phases wherein occur Peak.Observed under transmission electron microscope, it is seen that intensive α-Fe crystal grain is formed in sample, size is no more than 20nm.Pass through comprehensive physical property Measuring system (PPMS) carries out magnetic property detection to the sample after annealing, it is known that its saturation magnetization is more than 1.4T, than not adding Enter the Fe of tin80Nb1Cr2P11B5Si1Non-crystaline amorphous metal saturation magnetization is higher by 0.2T, and coercivity remains at below 5A/m.
Embodiment 5
According to Fe70Nb9Sn1P12C3B5Alloying component that the atomic percent of each element is converted into mass percent is laggard Row dispensing.The raw material includes pure element simple substance and its intermediate alloy, and the purity of raw material is in general industry purity requirement Can, total atomic percent of impurity is no more than 2% in alloy.
It is placed in after above-mentioned raw materials are mixed in quartz ampoule, is put into the induction coil in vaccum sensitive stove and carries out melting.First 10 will be evacuated in stove-3Below Pa, heated after being re-filled with 0.04MPa high-purity argon gas.Melting 6 times is repeated, obtains composition Uniform foundry alloy, alloy surface is clean and metal luster.
Amorphous alloy ribbon is prepared using band method is got rid of:Alloy pig is placed in the foraminate quartz ampoule in bottom, hole diameter About 1mm, quartz ampoule is placed in induction coil, quartz ampoule upper end connects with outside argon gas, and the pressure of external argon gas is than argon in stove The high 0.03MPa of pressure of gas;After alloy melting, connecting valve is opened, outside argon gas is entered quartz ampoule, aluminium alloy is sprayed onto The cooling roller surface of rotation, the rotating speed of chill roll is 30m/s, and aluminium alloy solidifies to form wide 2mm, thick 20 μm alloy thin band.It is right Alloy thin band carries out XRD detections, only " steamed bun peak " occurs in the XRD spectrums measured, without sharp diffraction maximum, it was demonstrated that the strip is non- Peritectic alloy.
The T of the non-crystaline amorphous metal is measured using DSCxTemperature.Amorphous thin ribbon is encapsulated in vitreosil pipe and annealed, temperature 540 DEG C of degree, it is incubated 240s.XRD detections are carried out to the strip after annealing and confirm that Crystallization Phases therein are α-Fe.Under transmission electron microscope Observation, it is seen that after annealing in strip the size of α-Fe crystal grain in below 30nm.Magnetic is carried out to the strip after annealing by PPMS It can detect, it is possible to find its saturation magnetization is more than 1.7T, than not stanniferous Fe70Nb9Sn1P12C3B5The saturation magnetic of non-crystaline amorphous metal Change intensity and be higher by about 0.2T, while coercivity is maintained at below 3A/m.
It will be apparent to those skilled in the art that technical scheme that can be as described above and design, make other various Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention Within.

Claims (8)

  1. A kind of 1. stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy, it is characterised in that:It is by Fe, Mo, Nb, Cr, Sn, P, C, the formula that B and Si is formed is FeaMobNbcCrdSnePfCgBhSiiAlloy, wherein a, b, c, d, e, f, g, h and i be respectively respective Corresponding atom percentage content, and 70≤a≤85,0≤b≤10,0≤c≤10,0≤d≤10,0 < e≤5,0≤f≤ 20th, 0≤g≤20,0≤h≤20,0≤i≤20, and 75≤a+b+c+d+e≤90,10≤f+g+h+i≤25, a+b+c+d+e+f + g+h+i=100.
  2. 2. stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 1, it is characterised in that:The iron-based The nascent Crystallization Phases of nanocrystalline and amorphous alloy are α-Fe.
  3. 3. a kind of preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy as claimed in claim 1, its feature exist In:Comprise the following steps:
    (1) according to formula ratio preparation raw material, then mixed;
    (2) raw material prepared is subjected to melt back in smelting furnace, until obtaining the uniform foundry alloy of composition;
    (3) by foundry alloy remelting, then by casting, quenching method or get rid of band method and carry out quick solidification block or thin ribbon shaped is made Non-crystaline amorphous metal;
    (4) non-crystaline amorphous metal is annealed, annealing temperature is higher than 10-50 DEG C of amorphous alloy crystallization start temperature, annealing time For 60-600s, stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy is obtained.
  4. 4. the preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 3, its feature exist In:In step (2) in melting or step (3) during remelting, first vacuumize and be re-filled with inert gas and protected, i.e., first by smelting furnace Inside it is evacuated to 10-3Below Pa, inert gas is re-filled with to 0.02MPa is more than and carries out melting.
  5. 5. the preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 3, its feature exist In:Casting is specifically in step (3), and foundry alloy is placed in electric arc furnaces or induction furnace and melted, and then sucks or sprays into and be cold But block is frozen into mould, obtains non-crystaline amorphous metal.
  6. 6. the preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 3, its feature exist In:Quenching method is specifically that foundry alloy is sealed in vacuum tube in step (3), and vacuum tube and foundry alloy are heated to together After foundry alloy fusing, block is frozen into coolant of quenching, obtains non-crystaline amorphous metal.
  7. 7. the preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 3, its feature exist In:It is specifically that foundry alloy is placed in the porose crucible in bottom, is sprayed onto foundry alloy liquid after fusing that band method is got rid of in step (3) At a high speed on the chill roll of rotation, quick solidification forms strip, obtains non-crystaline amorphous metal.
  8. 8. the preparation method of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy according to claim 3, its feature exist In:Annealing temperature is 400-700 DEG C in step (4).
CN201710520958.7A 2017-06-30 2017-06-30 A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof Active CN107419199B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710520958.7A CN107419199B (en) 2017-06-30 2017-06-30 A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710520958.7A CN107419199B (en) 2017-06-30 2017-06-30 A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107419199A true CN107419199A (en) 2017-12-01
CN107419199B CN107419199B (en) 2019-11-12

Family

ID=60426863

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710520958.7A Active CN107419199B (en) 2017-06-30 2017-06-30 A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107419199B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109342309A (en) * 2018-11-26 2019-02-15 辽宁科技大学 A kind of experimental rig and test method of simulated marine corrosion environment
CN110098029A (en) * 2018-01-30 2019-08-06 Tdk株式会社 Non-retentive alloy and magnetic part
CN112342476A (en) * 2020-10-21 2021-02-09 江苏大磁纳米材料有限公司 Hydrogen-containing iron-based amorphous alloy and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007182594A (en) * 2006-01-04 2007-07-19 Hitachi Metals Ltd Amorphous alloy thin strip, nano-crystalline soft magnetic alloy, and magnetic core composed of nano-crystalline soft magnetic alloy
JP2012136770A (en) * 2010-12-10 2012-07-19 Nec Tokin Corp Fe-BASED NANO-CRYSTALLINE ALLOY POWDER AND METHOD FOR PRODUCING THE SAME, AND DUST CORE AND METHOD FOR MANUFACTURING THE SAME
CN102732811A (en) * 2012-06-21 2012-10-17 四川大学苏州研究院 High-saturated magnetization intensity Fe-based amorphous nanocrystalline soft magnetic alloy and its preparation method
CN104561841A (en) * 2013-10-25 2015-04-29 上海瀚涛纳米科技有限公司 High-saturation-magnetization iron-base amorphous nanocrystal soft magnetic alloy and preparation method thereof
CN104934179A (en) * 2014-05-27 2015-09-23 安泰科技股份有限公司 Fe-based nanocrystalline soft magnetic alloy with strong amorphous forming ability and preparing method of Fe-based nanocrystalline soft magnetic alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007182594A (en) * 2006-01-04 2007-07-19 Hitachi Metals Ltd Amorphous alloy thin strip, nano-crystalline soft magnetic alloy, and magnetic core composed of nano-crystalline soft magnetic alloy
JP2012136770A (en) * 2010-12-10 2012-07-19 Nec Tokin Corp Fe-BASED NANO-CRYSTALLINE ALLOY POWDER AND METHOD FOR PRODUCING THE SAME, AND DUST CORE AND METHOD FOR MANUFACTURING THE SAME
CN102732811A (en) * 2012-06-21 2012-10-17 四川大学苏州研究院 High-saturated magnetization intensity Fe-based amorphous nanocrystalline soft magnetic alloy and its preparation method
CN104561841A (en) * 2013-10-25 2015-04-29 上海瀚涛纳米科技有限公司 High-saturation-magnetization iron-base amorphous nanocrystal soft magnetic alloy and preparation method thereof
CN104934179A (en) * 2014-05-27 2015-09-23 安泰科技股份有限公司 Fe-based nanocrystalline soft magnetic alloy with strong amorphous forming ability and preparing method of Fe-based nanocrystalline soft magnetic alloy

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110098029A (en) * 2018-01-30 2019-08-06 Tdk株式会社 Non-retentive alloy and magnetic part
CN110098029B (en) * 2018-01-30 2020-10-13 Tdk株式会社 Soft magnetic alloy and magnetic component
CN109342309A (en) * 2018-11-26 2019-02-15 辽宁科技大学 A kind of experimental rig and test method of simulated marine corrosion environment
CN109342309B (en) * 2018-11-26 2024-02-27 辽宁科技大学 Test device and test method for simulating marine corrosion environment
CN112342476A (en) * 2020-10-21 2021-02-09 江苏大磁纳米材料有限公司 Hydrogen-containing iron-based amorphous alloy and preparation method thereof
CN112342476B (en) * 2020-10-21 2022-05-20 江苏大磁纳米材料有限公司 Hydrogen-containing iron-based amorphous alloy and preparation method thereof

Also Published As

Publication number Publication date
CN107419199B (en) 2019-11-12

Similar Documents

Publication Publication Date Title
Fan et al. Soft magnetic properties in Fe84− xB10C6Cux nanocrystalline alloys
Makino et al. FeSiBP bulk metallic glasses with high magnetization and excellent magnetic softness
CN101650999A (en) Fe-based amorphous or nanocrystalline soft magnetic alloy and preparation method thereof
CN107393673B (en) Iron-based amorphous nanocrystalline magnetically soft alloy and preparation method thereof
CN110306130B (en) Fe-Si-B-P-Cu-Nb amorphous nanocrystalline magnetically soft alloy with high iron content and preparation method thereof
CN110387500B (en) High-magnetic-induction high-frequency iron-based nanocrystalline magnetically soft alloy and preparation method thereof
Fan et al. Crystallization behavior and magnetic properties in High Fe content FeBCSiCu alloy system
CN110541116B (en) Crystallization-controllable iron-based nanocrystalline magnetically soft alloy
CN107419199B (en) A kind of stanniferous soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof
CN109930080B (en) Copper-free nanocrystalline magnetically soft alloy and preparation method thereof
CN106917042A (en) A kind of high frequency high magnetic flux density Fe-based nanocrystalline magnetically soft alloy and preparation method thereof
CN115478218B (en) Large-size high-saturation magnetic induction intensity iron-based amorphous alloy and preparation method thereof
CN106636982B (en) A kind of Fe-based amorphous alloy and preparation method thereof
CN115386811A (en) High-saturation-magnetic-induction-strength tough iron-based amorphous nanocrystalline strip and preparation method thereof
Zheng et al. Enhanced Ms of Fe-rich Fe-B-Cu amorphous/nanocrystalline alloys achieved by annealing treatments
CN105002447B (en) Method for improving glass forming ability of Fe-Si-B-P series block amorphous alloy
CN105400998A (en) Ni-Mn-Ga alloy ribbon and preparation method thereof
CN107419200B (en) A kind of soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof containing manganese
CN107236911A (en) A kind of Fe-based amorphous alloy
CN106906431A (en) A kind of Fe-based amorphous alloy and preparation method thereof
CN111101076A (en) Iron-based nanocrystalline magnetically soft alloy
CN112877613B (en) Iron-based amorphous soft magnetic alloy and preparation method and application thereof
CN115482986A (en) High-magnetic-induction 200-micron-grade iron-based amorphous magnetically soft alloy strip and preparation method thereof
JPS581183B2 (en) High magnetic permeability amorphous alloy with high magnetic flux density and large squareness ratio
Makino et al. Fe-metalloids bulk glassy alloys with high Fe content and high glass-forming ability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant