CN109930080A - A kind of no copper nanocrystallite magnetically soft alloy and preparation method thereof - Google Patents
A kind of no copper nanocrystallite magnetically soft alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of no copper nanocrystallite magnetically soft alloy, chemical formula FeaSibBcPdCeNif, a, b, c, d, e, f are respectively the corresponding atomic percent of each element, 75≤a≤86,2≤b≤4,8≤c≤14,1≤d≤3,0.5≤e≤1,0≤f≤20, and a+b+c+d+e+f=100.Rationally, amorphous formation ability is strong, and crystallization temperature section is big, and comprehensive soft magnet performance is excellent for above-mentioned no copper nanocrystallite magnetically soft alloy ingredient design.The invention also discloses a kind of preparation methods of above-mentioned no copper nanocrystallite magnetically soft alloy, comprising: commercially available alloy raw material is obtained alloy pig by progress melting, cooling after molecular formula ingredient；Alloy strip steel rolled stock will be prepared using single-roller rapid quenching with quenching after the melting of obtained alloy pig；Obtained alloy strip steel rolled stock is obtained into the no copper nanocrystallite magnetically soft alloy in 400~550 DEG C of annealing.The preparation method is simple and efficient, reproducibility is high, is suitble to large-scale production.
Description
Technical field
The present invention relates to soft magnetic materials technical fields, and in particular to a kind of no copper nanocrystallite magnetically soft alloy and its preparation side
Method.
Background technique
Since developing a series of Fe based amorphous nano magnetically soft alloy material, amorphous and nanocrystalline soft magnetic alloy material
Material is just greatly paid attention to and in-depth study, with high saturated magnetic induction, high magnetic permeability, low-loss and low rectifys
The features such as stupid power, and it is widely used in motor, the fields such as transformer and electromagnetic sensor.Wherein, FINEMET alloy system due to
Its synthesis soft magnet performance is preferable, has obtained good application.If alloying component is Fe73.5Si13.3B9Nb3Cu1FINEMET close
Gold, saturation induction density (Bs) it is 1.24T.However, compare with silicon steel, the saturation induction of FINEMET alloy system
Intensity is not high, makes it under identical operating condition using needing more volume.Further, since precious metal element such as Nb's adds
Add, lead to that it is expensive, this greatly limits its application ranges.
Currently, under electronics miniaturization and the development trend of using energy source sustainability, market urgent need one
Kind has the magnetically soft alloy material of high saturated magnetic induction.For Fe base nanometer crystal magnetically soft alloy material, saturation is improved
Magnetic induction intensity it is necessary to improving nanocrystalline α-Fe (Si) the mutually amount of precipitation in noncrystal substrate phase as much as possible.At the same time, it is
Guarantee that alloy material has excellent synthesis soft magnet performance, it is necessary to guarantee in noncrystal substrate that crystallite dimension is smaller and uniformly point
Cloth is in noncrystal substrate.There are two types of the method for acquisition high saturated magnetic induction is general, one is improve Fe element in the alloy
Specific gravity, and then improve saturation induction density；Another kind is using heat treatment process appropriate, and refinement α-Fe (Si) is nanocrystalline
Grain and promote it to be uniformly distributed in noncrystal substrate, and then improve saturation induction density.
The patent specification of Publication No. CN101796207A discloses a kind of Fe-M-Si-B-Cu amorphous alloy, nanometer
Crystalline state non-retentive alloy and magnetic core, at least one of M Ti, V, Zr, Nb, Mo, Hf, Ta and W, the crystalline state nanometer magnetically soft alloy
With easy heat treatment condition and excellent processability.But the Fe content of the alloy is lower to lead to its saturation
Magnetic induction intensity is 1.24T, needs to be further increased.
The patent specification of Publication No. CN102732811A discloses a kind of Fe-based amorphous nanometer of Fe-Si-B-P-Cu-X
Brilliant magnetically soft alloy and preparation method thereof, one of X Al, Cr, Mn, Ti or more than one.The saturation induction of the alloy is strong
Degree is 1.56~1.84T, but its coercivity is larger, such as Fe85Al1Cu0.5Si3.5B6P4The coercivity of alloy is greater than 18A/m, the conjunction
Golden coercivity and other soft magnet performances need to be further increased.
It is soft that the patent specification of Publication No. CN102808140A discloses a kind of Fe-Si-B-P-Cu-M iron based nano crystal
Permalloy material, one of M Co, Mo, Cr and Y, saturation induction density can reach 1.6~1.75T, however, the conjunction
The addition of Co and Y limits it and produces in enormous quantities and be widely applied so that the cost of raw material of alloy increases in gold.
The patent specification of Publication No. CN106834930A discloses a kind of compatible with the high impurity of high magnetic flux density
Property Fe-Si-B-P-C-Cu-M iron-base nanometer crystal alloy, wherein M be raw material in impurity or unobvious change alloy property
Trace additives.Alloy Fe content can reach 85.75at.%, saturation induction density 1.83T.But be free of
The alloy of Cu compares, this contains Cu alloy since the addition of Cu causes amorphous formation ability lower, and the preparation of band is more difficult.Greatly
The addition of amount nonmagnetic elements Cu can reduce the specific gravity of ferromagnetic element in the alloy, be unfavorable for obtaining higher saturation induction
Intensity, these disadvantages limit the preparation and its extensive use of the alloy.
It is soft that the patent specification of Publication No. CN106756643A discloses a kind of Fe-Si-B-P-Cu-C amorphous nano-crystalline
Magnetic alloy and preparation method thereof, the alloy iron content is high, has high saturated magnetic induction, can reach 1.95T.But this is non-
Brilliant nano-crystal soft magnetic alloy coercivity is larger, coercivity 28A/m, and synthesis soft magnet performance is poor.The amorphous nano peritectic alloy
Synthesis soft magnet performance need to be improved.
In above-mentioned cupric nano-crystal soft magnetic alloy, by adjusting alloying component and heat treatment process, change to a certain extent
It has been apt to the soft magnet performance of nanometer crystal alloy.But these alloys there is problems: addition precious metal element such as Co, Y, Nb
Deng the cost for increasing alloy preparation.In addition, the coercivity and saturation induction density of these magnetically soft alloys are difficult to realize the two
Between balance, comprehensive performance need to be advanced optimized.
In order to improve the amorphous formation ability and saturation induction density of alloy, it is necessary to subtract in nanometer crystal alloy exploitation
The introducing of few nonmagnetic elements and copper.Under normal conditions, the nano-crystal soft magnetic alloy of preferable soft magnet performance, alloy to be obtained
Crystallization temperature section (temperature range between the first crystallization peak and the second crystallization peak) should be wider, be conducive to it is subsequent heat at
Reason processing.On the other hand, wider crystallization warm area can promote precipitation mutually in noncrystal substrate phase of α-Fe and inhibit Fe2B and
Fe3The formation of the hard magnetic phases such as B.
The Fe-M-B nano-crystal soft-magnetic that the patent specification of Publication No. EP0430085A2 discloses a kind of not cupric closes
Gold, M therein be Ti, Zr, Hf, V, Nb, Mo, Ta, W, one of Mn or more than one.Its crystallization volume fraction is greater than
50%, crystallite dimension is less than 50nm.Alloy saturation induction density with higher, can reach 1.9T.But this is free of
The preparation process of copper nanocrystallite alloy is more difficult, can just prepare alloy strip steel rolled stock, pole under conditions of copper roller revolving speed is greater than 65m/s
Big limits the mass production and its extensive use of the alloy.
The patent specification of Publication No. EP0429022A2 discloses a kind of Co-Fe-M-B nano-crystal soft-magnetic of not cupric
Alloy, M therein be Ti, Zr, Hf, V, Nb, Mo, Ta, Cr, W, one of Mn or more than one.The alloy has more larger
Crystallization volume fraction, up to 50%.Due to the addition of precious metal element, so that the preparation cost of the alloy increases, and the conjunction
The amorphous formation ability of gold has to be optimized.
In conclusion high saturated magnetic induction should be realized, while alloy being required to have both good amorphous formation energy again
Power and craftsmanship are difficult to realize only by raising Fe content and prior heat treatment process.It is current for how breaking through above-mentioned bottleneck
Urgent problem to be solved in Fe-based nanocrystalline magnetically soft alloy material research.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of no copper nanocrystallite magnetically soft alloy, ingredient designs
Rationally, amorphous formation ability is strong, and crystallization temperature section is big, and comprehensive soft magnet performance is excellent.
A kind of no copper nanocrystallite magnetically soft alloy, chemical formula FeaSibBcPdCeNif, a, b, c, d, e, f are respectively each element
Corresponding atomic percent, 75≤a≤86,2≤b≤4,8≤c≤14,1≤d≤3,0.5≤e≤1,0≤f≤20, and a+b+
C+d+e+f=100.
To obtain high saturated magnetic induction, it is necessary to assure the Fe element in alloy containing high level.However, Fe element
Too high levels certainly will cause alloy amorphous Forming ability to decline.In alloy of the invention, Fe constituent content meets high saturation magnetic induction
Answer the requirement of intensity Yu high amorphous formation ability.Preferably, Fe content is 75.5≤a≤85.5, can get higher saturation magnetic
Induction.
In order to further increase the saturation induction density and amorphous formation ability of alloy, traditional nanocrystalline forming core element
The introducing of Cu element can reduce the amorphous formation ability and surface quality of strips of alloy strip steel rolled stock.Therefore, nanocrystalline in the present invention
The brilliant indispensable Cu element of Conventional nano is eliminated in design of alloy, to improve the processing property and saturation magnetic of alloy
Induction.
For the heat of mixing between Si element and Fe element not as good as B, the height of P element and Fe element, excessively addition can reduce alloy
Interaction between system randomness and element, causes amorphous formation ability to decline.Preferably, 1.5≤b≤3 can be improved
The amorphous formation ability of alloy.
B element is amorphous formation element, and very few addition can reduce alloy amorphous Forming ability, and excessively addition can reduce alloy
Saturation induction density.Preferably, the amorphous formation ability of alloy can be improved in 9≤c≤11.
P element can be ostracised out from α-Fe crystal grain, and be deposited in around crystal boundary, play inhibition work to growing up for crystal grain
With the amorphous formation ability of alloy can be increased by being properly added P element.But content increases will lead to the full of alloy too much
It is reduced with magnetic induction intensity.
C element and the effect of B and P are different, and C can be enriched on the boundary of nanocrystal and amorphous, package α-Fe crystal grain into
Row growth.The addition of C can improve amorphous formation ability, improve the surface quality of alloy strip steel rolled stock, but a large amount of additions will lead to instead
Alloy strip steel rolled stock curling.
Ni is a kind of ferromagnetic element, and saturation induction density will not be substantially reduced by being properly added.In addition, heat treated
The addition of Cheng Zhong, Ni can promote the forming core of α-Fe, but a large amount of additions can reduce amorphous formation ability and saturation induction density.
Preferably, the content of Ni element is 1≤f≤10, and the thermal stability of alloy can be improved.
Preferably, the no copper nanocrystallite magnetically soft alloy is prepared by alloy strip steel rolled stock short annealing, and described moves back
For the temperature of fire in the crystallization temperature section of the alloy strip steel rolled stock, heating rate is 300~400 DEG C/s, and the time of annealing is 2
~60 seconds, in the heating rate and annealing time, the forming core rate of α-Fe was big, can get high saturation induction density.
It is highly preferred that the time of the annealing is 3~20 seconds, in the annealing time, can get low coercivity and
High magnetic conductivity.
Best annealing conditions are 500 DEG C of annealing temperature, and annealing time 12s can be obtained under the annealing temperature and annealing time
Obtain the optimal no copper nanocrystallite magnetically soft alloy of comprehensive performance.
There are a large amount of iron atom clusters in the alloy strip steel rolled stock, and described is annealed by being quickly heated to
One crystallization temperature or more makes iron atom cluster have little time to grow up in temperature-rise period, then keeps the temperature in a very short period of time, makes
It obtains iron atom cluster uniformly to grow up simultaneously, obtain compared with little crystallite size without copper nanocrystallite magnetically soft alloy.
First crystallization temperature is the FCTA temprature that α-Fe is precipitated.
The microstructure without copper nanocrystallite magnetically soft alloy is the α-Fe (Si) of noncrystal substrate and body-centered cubic structure
Nanocrystal two-way coupling structure.
The average grain size of described α-Fe (Si) the nanocrystalline crystal grain is 16~21nm.
The saturation induction density without copper nanocrystallite magnetically soft alloy be 1.72~1.87T, coercivity be 7.9~
Magnetic conductivity under 13.5A/m, 1kHz frequency is 8000~10000.
The soft magnet performance without copper nanocrystallite magnetically soft alloy is excellent and cheap, green energy conservation, has good
Application prospect can be widely applied to the technical fields such as distribution transformer, servo motor and high-precision sensor.
The present invention also provides the preparation methods without copper nanocrystallite magnetically soft alloy described in one kind, pass through no Nb, Zr, Mo etc.
Thick atom element and without copper design of alloy, introduces Ni element, improves the thermal stability of alloy, and obtain big crystallization temperature
Spend the alloy strip steel rolled stock in section and high amorphous formation ability.The preparation method is simple and efficient, reproducibility is high, is suitble to large-scale production.
A kind of preparation method without copper nanocrystallite magnetically soft alloy, comprising:
(1) commercially available alloy raw material is obtained into alloy pig by progress melting, cooling after molecular formula ingredient；
(2) alloy strip steel rolled stock will be prepared using single-roller rapid quenching with quenching after the melting of obtained alloy pig；
(3) obtained alloy strip steel rolled stock is obtained in 400~550 DEG C of annealing described without copper nanocrystallite magnetically soft alloy.
In step (1), the melting is in nitrogen or rare gas atmosphere protection, 0.05~0.08Pa of absolute vacuum degree
Under the conditions of carry out, make alloy raw material be uniformly mixed.Alloy melting is carried out, under inert gas shielding and condition of high vacuum degree to avoid molten
Oxidation and the volatilization of element occur for liquid.
In step (2), it is preferable that the roller speed of the single-roller rapid quenching with quenching is greater than 20m/s, to prepare completely amorphous alloy
Band.Surface crystallization will not occur for alloy strip steel rolled stock of the critical speed higher than 20m/s or more, and prepared alloy strip steel rolled stock is intact
Non crystalline structure, after heat treatment be precipitated nano particle crystallite dimension it is small, soft magnet performance is optimal.
Preferably, the alloy strip steel rolled stock with a thickness of 22~28 μm, the alloy strip steel rolled stock under the thickness is shown more preferably
Soft magnet performance.
The alloy strip steel rolled stock has high amorphous formation ability, big crystallization temperature section and high thermal stability.
The crystallization temperature section refers to that α-Fe starts the temperature being precipitated and forms the temperature range of FeB compound, described
Alloy strip steel rolled stock crystallization temperature section be 400~542 DEG C.
The crystallization temperature section span is greater than 140 DEG C, can effectively inhibit the formation of FeB phase, promotes the analysis of α-Fe
Out.
There are a large amount of iron atom clusters in the alloy strip steel rolled stock, and described is annealed by being quickly heated to
One crystallization temperature or more makes iron atom cluster have little time to grow up in temperature-rise period, then keeps the temperature in a very short period of time, makes
It obtains iron atom cluster uniformly to grow up simultaneously, obtain compared with little crystallite size without copper nanocrystallite magnetically soft alloy.
Preferably, the size of the iron atom cluster in the alloy strip steel rolled stock is 2~5nm.
In step (3), it is preferable that the annealing carries out under nitrogen or rare gas atmosphere protection, to avoid alloy
Surface oxidation occurs during heat treatment for band, adversely affects to soft magnet performance.
Preferably, the annealing temperature is in the crystallization temperature section of the alloy strip steel rolled stock.The temperature of the annealing
Degree is 400~542 DEG C.It anneals in the temperature range, can get the soft magnetic materials of α-Fe phase and amorphous phase double structure,
It may also suppress the formation of hard magnetic phase such as FeB chemical compound simultaneously, the formation of the FeB chemical compound can deteriorate the soft magnet performance of alloy.
It is furthermore preferred that the temperature of the annealing is 470~520 DEG C.Within this temperature range, it can get superior soft
Magnetic property, such as low coercivity, high magnetic conductivity.
Preferably, the heating rate of the annealing is 300~400 DEG C/s, and the time of annealing is 2~60 seconds.In the liter
In warm rate and annealing time, the forming core rate of α-Fe is big, can get high saturation induction density.It is highly preferred that described
The time of annealing is 3~20 seconds, in the annealing time, can get low coercivity and high magnetic conductivity.
Best annealing conditions are 500 DEG C of annealing temperature, and annealing time 12s can be obtained under the annealing temperature and annealing time
Obtain the optimal no copper nanocrystallite magnetically soft alloy of comprehensive performance.
Compared with prior art, the present invention major advantage includes:
(1) compared with amorphous alloy, the alloy strip steel rolled stock of no copper nanocrystallite magnetically soft alloy of the invention has big crystallization temperature
Section is unfavorable for the precipitation of the second phase, is conducive to that the tiny nanocrystalline crystal grain of α-Fe of crystal grain is precipitated during heat treatment.
(2) compared with cupric nanometer crystal alloy, no copper nanocrystallite magnetically soft alloy ingot of the invention has high amorphous formation energy
Power can prepare the alloy strip steel rolled stock of completely amorphous state structure under conditions of roller speed is greater than 20m/s.
(3) by it is appropriate be rapidly heated heat treatment after obtain without copper nanocrystallite magnetically soft alloy, can obtain excellent, stabilization
Soft magnet performance, have the up to saturation induction density of 1.87T, high Effective permeability and low-coercivity, market can be solved
Upper cupric nanometer crystal alloy application limitation as brought by its low amorphous formation ability and poor magnetic property.
(4) alloy strip steel rolled stock of the invention has wider heat treatment temperature section, and optimum annealing temperature section is up to 50 DEG C.
Soaking time section is not more than 60 seconds, greatly improves the efficiency of alloy preparation, reduces the consumption of the energy in heat treatment process.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) figure of the alloy strip steel rolled stock of Examples 1 to 2；
Fig. 2 is differential scanning calorimeter (DSC) curve graph of the alloy strip steel rolled stock of Examples 1 to 3；
Fig. 3 is that short annealing 12 seconds and comparative example 2 exist at different temperatures for the alloy strip steel rolled stock of embodiment 1 and comparative example 1
Under different temperatures after common annealing 3min, the variation diagram of coercivity annealing temperature；
Fig. 4 is measuring without copper nanocrystallite magnetically soft alloy when impressed field is 1A/m for embodiment 1,3 and 4 and comparative example 1
Magnetic conductivity curve graph varying with frequency；
Fig. 5 is the hysteresis loop and saturation induction density without copper nanocrystallite magnetically soft alloy of embodiment 1；
Fig. 6 is the alloy strip steel rolled stock (a) of embodiment 1 and transmission electron microscope photo and electronics without copper nanocrystallite magnetically soft alloy (b)
Diffraction images.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
Examples 1 to 4 and comparative example 1~3
Examples 1 to 4 and comparative example 1~3 it is as shown in table 1 without copper nanocrystallite magnetically soft alloy ingredient.
Examples 1 to 4 is similar with the preparation method of comparative example 1~3, and steps are as follows:
Step 1: by purity be respectively 99.95% Fe, 99.99% Si, 99.5% B, 99.99% Ni,
99.95% Fe3P, 99.95% FeC carries out ingredient by the molecular formula of table 1.
Step 2: the alloy raw material prepared in step 1 being put into the alumina crucible cleaned out, and it is molten to be put into induction
In furnace, then start to vacuumize, until when vacuum degree is no more than 0.001Pa.To prevent element in fusion process from waving
Hair, being filled with argon gas makes vacuum degree not less than 0.05Pa.After alloy melts completely, 10min is kept the temperature, is thoroughly mixed alloy
It is even.Then molten alloy ingot is poured into cooling 30 minutes in copper mold, obtains the uniform alloy pig of ingredient.
Step 3: the alloy pig that step 2 melting obtains being crushed, and broken alloy pig is packed into lower ending opening aperture
Then quartz ampoule to be placed in Casting Equipment induction coil in the quartz ampoule of 0.2~0.4mm, after alloy molten, by alloy
Liquid is sprayed onto rotary copper roller, prepares alloy strip steel rolled stock using single-roller rapid quenching with quenching, alloy strip steel rolled stock is with a thickness of 22~28 μm.
The revolving speed of the rotary copper roller of embodiment 1 is respectively 25m/s and 40m/s；When higher than critical speed 25m/s, it can prepare
The alloy strip steel rolled stock of non crystalline structure out.The revolving speed of the rotary copper roller of embodiment 2 is respectively 20m/s and 40m/s；Higher than critical speed
When 20m/s, the alloy strip steel rolled stock of non crystalline structure can be prepared.Embodiment 3~4, the rotary copper roller of comparative example 1~3 revolving speed be
40m/s, the alloy strip steel rolled stock under the revolving speed are non crystalline structure.
Step 4: step 3 alloy strip steel rolled stock obtained is cut into the band of 80mm long, be then placed in quick anneal oven into
Row heat treatment obtains no copper nanocrystallite magnetically soft alloy.In annealing process, being passed through argon gas prevents sample oxidation.By item when short annealing
Band is directly contacted with pre-heated two heating plates up and down.It the annealing temperature of Examples 1 to 4 and comparative example 1~3 and is moving back
Annealing time at fiery temperature is as shown in table 1.The heat treatment mode of the alloy strip steel rolled stock of comparative example 2~3 is true using tradition routine
The heat treatment of blank pipe formula annealing furnace.
Alloying component, thermodynamic parameter and the method for annealing of 1 Examples 1 to 4 of table and comparative example 1~3
Tx1: the first crystallization temperature, the α-Fe precipitated phase in corresponding diagram 2；
Tx2: the second crystallization temperature, the compound in corresponding diagram 2 is precipitated, such as iron boron hard magnetic phase；
ΔTx=Tx2-Tx1；
Ta: annealing temperature；
ta: the annealing time of alloy strip steel rolled stock at an annealing temperature；
RA: short annealing；
NA: conventional annealing.
The criterion of 1 amorphous formation ability of test case
Amorphous formation ability and microstructure to the alloy strip steel rolled stock of Examples 1 to 2 using X-ray diffraction method (XRD) into
Row characterization, as a result as shown in Figure 1.The result shows that amorphous can be prepared when copper roller critical speed is 25m/s in embodiment 1
The alloy strip steel rolled stock of structure.In embodiment 2, copper roller critical speed be 20m/s when alloy strip steel rolled stock XRD the result shows that, the alloy
Strip surface has slight crystallization.In Examples 1 to 2, when roller speed is 40m/s, alloy strip steel rolled stock is completely amorphous structure.
The analysis of 2 alloy thermal stability of test case
Examples 1 to 4 prepares wide 1mm, thick 26 μm of alloy strip steel rolled stock by single-roller rapid quenching with quenching, is then cut into 80mm's long
Band.DSC measures the thermodynamic parameter of the alloy strip steel rolled stock of Examples 1 to 4, such as Curie temperature Tc, the first crystallization temperature Tx1With
Two crystallization temperature Tx2, measured with differential scanning calorimetry, heating rate is 40 DEG C/min.In Examples 1 to 3, Ni element
Addition greatly improve the thermal stability of alloy, as shown in Fig. 2, plus increase between the heat-treatment zone of Ni alloy, to improve non-
The thermal stability of crystal phase.Obtaining annealing region from DSC curve is 400~542 DEG C, is moved back in the temperature range
Fire, can get the soft magnetic materials of α-Fe phase and amorphous phase double structure, while may also suppress the shape of hard magnetic phase such as FeB chemical compound
At the formation of the FeB chemical compound can deteriorate the soft magnet performance of alloy.
3 alloy nano crystallization process condition of test case and soft magnet performance
In the present embodiment 1~4 without copper nanocrystallite magnetically soft alloy, using a kind of heat treatment process of short annealing.At heat
Reason process carries out in argon gas, and for alloy strip steel rolled stock directly with pre-heated two contact heater plates, annealing time is from sample and adds
Hot plate contact start timing.The coercivity H without copper nanocrystallite magnetically soft alloy after heat treatmentcIt is measured using DC B-H instrument；
Magnetic permeability μеIt is measured using impedance analyzer；Saturation induction density BsIt is measured using vibrating specimen magnetometer；As a result
As shown in Fig. 3,4,5 and table 2.
Alloying component, phase structure and the soft magnet performance of 2 Examples 1 to 4 of table and comparative example 1~2
Bs: saturation induction density；μе: the Effective permeability under 1kHz；Hc: coercivity.
The result shows that the addition of Ni element can be such that the coercivity of nanometer crystal alloy reduces, it is reduced to from original 13.5A/m
7.9A/m, as shown in table 2.At the same time, via the heat treatment condition of optimization, Ni element can make alloy still keep excellent
Different, stable soft magnet performance, saturation induction density reach 1.72~1.79T, and Effective permeability is up to 10000.So this reality
It applies feasible and high-efficient without copper nanocrystallite magnetically soft alloy heat treatment condition in example, has excellent performance, be conducive to industrial metaplasia
It produces.
The sample morphology of embodiment 1 is observed by transmission electron microscope microscope, as shown in Figure 6.It can be with
It obtains such as grain size and distribution information and passes through electron diffraction analysis Sample crystals structure.The electron diffraction pattern of amorphous is
It is made of several concentric loops, what is be distributed on nanocrystalline electronic diffraction ring is the α-Fe crystal grain of BCC structure.It can be with from Fig. 6 a
See, the elementide of many of alloy strip steel rolled stock, the size of elementide is 2~5nm.After annealing, elementide is grown up, and is obtained
The nanocrystalline crystal grain of α-Fe for being 16~21nm to tiny crystal grain, as shown in Figure 6 b.
The alloy strip steel rolled stock of Examples 1 to 4 and comparative example 1~3 is prepared under identical conditions, real through XRD diffraction analysis
Applying the alloy strip steel rolled stock in example 1~4 and comparative example 1~3 is non crystalline structure.It is further examined by transmission electron microscope (TEM)
Analysis is surveyed, crystal phase is not precipitated in the alloy strip steel rolled stock in comparative example 1-3, and be precipitated in the alloy strip steel rolled stock of embodiment 1 having a size of 2~
The elementide of 5nm, as shown in Figure 6 a.Comparative example 1 is identical with heat treatment condition with the preparation process of embodiment 4, all for
Short annealing；Coercivity in comparative example 1 is larger (142A/m), and the coercivity in embodiment 4 is lower (7.9A/m).Comparative example
2 is identical with the alloying component of embodiment 1, but comparative example 2 uses traditional normative heat treatment method, and coercivity is larger
(100A/m), and the coercivity in embodiment 1 is lower (13.5A/m).
In conclusion the amorphous formation ability of alloy strip steel rolled stock of the invention is strong, thermal stability is high；At can be by fast speed heat
Science and engineering skill prepare have both high saturation induction density and excellent soft magnet performance without copper nanocrystallite magnetically soft alloy, the present invention couple
The preparation for developing high amorphous formation ability and high-performance iron Based Nanocrystalline Alloys has great importance.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of no copper nanocrystallite magnetically soft alloy, which is characterized in that chemical formula FeaSibBcPdCeNif, a, b, c, d, e, f difference
For the corresponding atomic percent of each element, 75≤a≤86,2≤b≤4,8≤c≤14,1≤d≤3,0.5≤e≤1,0≤f≤
20, and a+b+c+d+e+f=100.
2. no copper nanocrystallite magnetically soft alloy according to claim 1, which is characterized in that 1≤f≤10.
3. no copper nanocrystallite magnetically soft alloy according to claim 1 or 2, which is characterized in that the no copper nanocrystallite is soft
The microstructure of magnetic alloy is α-Fe (Si) nanocrystal two-way coupling structure of noncrystal substrate and body-centered cubic structure, described
The average grain size of α-Fe (Si) nanocrystalline crystal grain is 16~21nm.
4. no copper nanocrystallite magnetically soft alloy according to claim 1 or 2, which is characterized in that the no copper nanocrystallite is soft
The saturation induction density of magnetic alloy is 1.72~1.87T, and coercivity is 7.9~13.5A/m, and the magnetic conductivity under 1kHz frequency is
8000~10000.
5. the preparation method without copper nanocrystallite magnetically soft alloy described in a kind of any claim according to claim 1~4, packet
It includes:
(1) alloy raw material is obtained into alloy pig by progress melting, cooling after molecular formula ingredient；
(2) alloy strip steel rolled stock will be prepared using single-roller rapid quenching with quenching after the melting of obtained alloy pig；
(3) obtained alloy strip steel rolled stock is obtained in 400~550 DEG C of annealing described without copper nanocrystallite magnetically soft alloy.
6. the preparation method of no copper nanocrystallite magnetically soft alloy according to claim 5, which is characterized in that the melting exists
It is carried out under conditions of nitrogen or rare gas atmosphere protection, 0.05~0.08Pa of absolute vacuum degree；
The annealing carries out under nitrogen or rare gas atmosphere protection.
7. the preparation method of no copper nanocrystallite magnetically soft alloy according to claim 5, which is characterized in that single roller is fast
The roller speed for method of quenching is greater than 20m/s.
8. the preparation method of no copper nanocrystallite magnetically soft alloy according to claim 5, which is characterized in that the alloy strip
The crystallization temperature section of material is 400~542 DEG C.
9. the preparation method of no copper nanocrystallite magnetically soft alloy according to claim 5, which is characterized in that the alloy strip
The size of iron atom cluster in material is 2~5nm.
10. the preparation method of no copper nanocrystallite magnetically soft alloy according to claim 5, which is characterized in that the annealing
Temperature be 470~520 DEG C, the heating rate of the annealing is 300~400 DEG C/s, and the time of annealing is 2~60 seconds.
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| CN111101076A (en) * | 2019-12-27 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Iron-based nanocrystalline magnetically soft alloy |
| CN113035484A (en) * | 2021-03-01 | 2021-06-25 | 青岛云路先进材料技术股份有限公司 | Nanocrystalline magnetically soft alloy and preparation method and equipment thereof |
| CN113025912A (en) * | 2021-03-01 | 2021-06-25 | 西北工业大学重庆科创中心 | Iron-nickel-based hard magnetic material and preparation method thereof |
| CN113838624A (en) * | 2020-06-08 | 2021-12-24 | 株式会社Bmg | Super-soft magnetic Fe-based amorphous alloy |
| CN116479321A (en) * | 2023-03-08 | 2023-07-25 | 国网智能电网研究院有限公司 | Nanocrystalline magnetically soft alloy strip and preparation method and application thereof |
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| CN111101076A (en) * | 2019-12-27 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Iron-based nanocrystalline magnetically soft alloy |
| CN113838624A (en) * | 2020-06-08 | 2021-12-24 | 株式会社Bmg | Super-soft magnetic Fe-based amorphous alloy |
| CN113035484A (en) * | 2021-03-01 | 2021-06-25 | 青岛云路先进材料技术股份有限公司 | Nanocrystalline magnetically soft alloy and preparation method and equipment thereof |
| CN113025912A (en) * | 2021-03-01 | 2021-06-25 | 西北工业大学重庆科创中心 | Iron-nickel-based hard magnetic material and preparation method thereof |
| CN116479321A (en) * | 2023-03-08 | 2023-07-25 | 国网智能电网研究院有限公司 | Nanocrystalline magnetically soft alloy strip and preparation method and application thereof |
| CN116479321B (en) * | 2023-03-08 | 2024-01-16 | 国网智能电网研究院有限公司 | Nanocrystalline magnetically soft alloy strip and preparation method and application thereof |
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