CN113388766A - Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof - Google Patents

Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof Download PDF

Info

Publication number
CN113388766A
CN113388766A CN202110661600.2A CN202110661600A CN113388766A CN 113388766 A CN113388766 A CN 113388766A CN 202110661600 A CN202110661600 A CN 202110661600A CN 113388766 A CN113388766 A CN 113388766A
Authority
CN
China
Prior art keywords
amorphous
alloy
manganese
equal
based nanocrystalline
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
CN202110661600.2A
Other languages
Chinese (zh)
Other versions
CN113388766B (en
Inventor
罗厅
杨元政
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.)
Guangdong University of Technology
Original Assignee
Guangdong 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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202110661600.2A priority Critical patent/CN113388766B/en
Publication of CN113388766A publication Critical patent/CN113388766A/en
Application granted granted Critical
Publication of CN113388766B publication Critical patent/CN113388766B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Continuous Casting (AREA)

Abstract

The application belongs to the technical field of composite structure alloy, and particularly relates to a manganese-based nanocrystalline/amorphous composite structure alloy and a preparation method thereof. The manganese-based nanocrystalline/amorphous composite structural alloy has a general formula as follows: mnbalSiaBbMcRdTe(ii) a bal is more than or equal to 55; a is more than or equal to 10 and less than 30; b is more than 5 and less than or equal to 12; m is selected from one or more of Fe, Co, Ni and Cr, and c is more than or equal to 0 and less than or equal to 25; r is selected from one or more of Ag, Mg and Cu, and d is more than or equal to 0 and less than or equal to 5; t is selected from one or more of Zr, Ti, V, Nb, Hf and Ta, and e is more than or equal to 0 and less than or equal to 8. The present application providesThe manganese-based nanocrystalline/amorphous composite structure alloy has excellent magnetic transformation characteristics and abundant magnetic structures, provides the possibility of a wide-temperature-range zero-magnetic-field-stability Sgeminmun magnetic structure material, and has academic research value and potential practical application value in the field of spintronics.

Description

Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof
Technical Field
The application belongs to the technical field of composite structure alloy, and particularly relates to a manganese-based nanocrystalline/amorphous composite structure alloy and a preparation method thereof.
Background
In the alloy or the composite material, one of the components is subjected to one-dimensional, two-dimensional or three-dimensional nano-crystallization, and the alloy or the composite material often shows more excellent structure and performance. The preparation of nanocrystalline/amorphous dual-phase composite structure materials of Fe-base, Co-base, Mg-base, Al-base and other alloys shows particularly outstanding performance. Mn is a metal element having an odd structure and magnetism among transition group metal elements. However, the existing manganese-based amorphous alloy documents report that the magnetron sputtering method and the mechanical ball milling method are mainly used for preparing the manganese-based amorphous alloy thin film or powder of binary systems (such as Mn-Si, Mn-Ge, Mn-C, Mn-B, Mn-Zr, Mn-Y and the like), and the spin glass transition behavior is found in the manganese-based amorphous samples, but the research of manganese-based amorphous/nanocrystalline material particles is not involved.
The magnetic skynerger is a vortex-like magnetic structure with topological protection characteristics. The magnetic structure has non-trivial topological protection property, local particle characteristic (the size can reach 3nm at the minimum), flexible dynamic characteristic (can be regulated and controlled by a magnetic field, an electric field, current and the like), and the like, so that the magnetic structure is expected to be used as a new generation of magnetic storage basic unit to realize high-density, low-energy consumption and nonvolatile information storage. Besides magnetic storage, logical operation, transistor-like structures, nano-oscillators and the like can be realized by utilizing the abundant and novel physical characteristics of Sgeminzem, and a microelectronic device with more efficient functions can be designed by utilizing the dual attributes of electronic charge and spin in the field of electronics.
However, in the currently discovered magnetic sigmin materials, the sigmin topological magnetic structure in most materials can be stabilized only under the dual actions of low temperature and external magnetic field, and only a few materials reach above room temperature, but a certain external magnetic field is needed for stabilization, so that the materials of the sigmin which can be stabilized by zero magnetic field at room temperature are rare. Therefore, the search for a sigramite magnetic structure material with wide temperature range and zero magnetic field stability is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the present application provides a manganese-based nanocrystalline/amorphous composite structural alloy and a preparation method thereof, the composite structural alloy has excellent magnetic transformation characteristics and abundant magnetic structures, provides a possibility of a wide-temperature-range zero-magnetic-field-stable sigramite magnetic structural material, and has academic research values and potential practical application values in the field of spintronics.
The application provides a manganese-based nanocrystalline/amorphous composite structure alloy, which has the following general formula:
MnbalSiaBbMcRdTe；
in the general formula, MnbalThe alloy system takes Mn as a main component, and the atomic mole number bal of the alloy system is more than or equal to 55; the mole number a of the Si element satisfies that a is more than or equal to 10 and less than 30; the mole number B of the B element satisfies that B is more than 5 and less than or equal to 12; m is selected from one or more of Fe, Co, Ni or Cr elements, and the atomic mole number c is more than or equal to 0 and less than or equal to 25; r is selected from one or more of Ag, Mg and Cu elements, and the atomic mole number d is more than or equal to 0 and less than or equal to 5; t is selected from one or more of Zr, Ti, V, Nb, Hf and Ta, and the atomic number e is more than or equal to 0 and less than or equal to 8; the atomic molar number of the sum of bal + a + b + c + d + e is 100.
In another embodiment, the M element and the T element are present simultaneously; the M element and the T element are not simultaneously present; the R element and the T element exist simultaneously.
In another embodiment, the M is selected from Fe.
In another embodiment, the R is selected from Ag or Cu.
In another embodiment, the T is selected from one of Nb, Zr, or V.
Specifically, the M element and the T element exist simultaneously, and the synergistic effect of the M element and the T element can effectively promote the nucleation and precipitation of manganese or manganese-silicon, so that the single-stage crystallization of the amorphous alloy is changed into the double-stage crystallization.
In another embodiment, the manganese-based nanocrystalline/amorphous composite structural alloy has the chemical formula: mn68Si25B7、Mn64Si25B7Ag1Nb3、Mn64Si25B7Cu1Nb3Or Mn55Fe15Si20B7EM3(ii) a WhereinAnd EM is one or more of Nb, Zr and V.
Specifically, the Mn55Fe15Si20B7EM3EM is one or more of Nb, Zr and V, including Mn55Fe15Si20B7Nb3、Mn55Fe15Si20B7Zr3Or Mn55Fe15Si20B7V3、Mn55Fe15Si20B7Nb1Zr1V1、Mn55Fe15Si20B7Nb2Zr1、Mn55Fe15Si20B7Nb1Zr2、Mn55Fe15Si20B7Zr2V1、Mn55Fe15Si20B7Zr1V2、Mn55Fe15Si20B7Nb2V1、Mn55Fe15Si20B7Nb1V2。
The second aspect of the application provides a preparation method of a manganese-based nanocrystalline/amorphous composite structure alloy, which comprises the following steps:
step 1, mixing the raw materials of the manganese-based nanocrystalline/amorphous composite structural alloy according to the proportion of the manganese-based nanocrystalline/amorphous composite structural alloy, and then performing melt rapid quenching to obtain an amorphous alloy strip;
and 2, carrying out annealing heat treatment on the amorphous alloy strip according to the thermal characteristic temperature value of the amorphous alloy strip to prepare the manganese-based nanocrystalline/amorphous composite structure alloy.
In another embodiment, in step 1, the process is an arc melting process or a magnetron sputtering process.
Specifically, the arc melting process includes: calculating and converting the atomic weight percentage of each element of the manganese-based nanocrystalline/amorphous composite structure alloy into the atomic weight percentage, and multiplying the atomic weight percentage by 10g to obtain the weight required by each simple substance elementThe raw materials given in table 1 were used for compounding. After each raw material is proportioned according to the atomic percentage, arc melting is carried out by using a WK-IIA type non-consumable vacuum arc melting furnace. In order to ensure the quality of the amorphous alloy strip master alloy, the furnace body is vacuumized before smelting, so that the vacuum degree reaches 3.0 multiplied by 10-4Below Pa, then high purity argon (purity 99.99%) is fed, where the argon, in addition to its protection, also acts as an arc starting and heat source. When each batch of samples are smelted, a smelting pot is reserved for containing a titanium ingot, the titanium ingot is smelted firstly during smelting so as to absorb residual oxygen in the smelting furnace, then the samples are smelted by utilizing electric arcs, and each sample is overturned and repeatedly smelted for 3-4 times so as to ensure the uniformity of alloy components, reduce the component segregation of alloy elements and obtain a high-quality amorphous alloy strip.
Specifically, the melt rapid quenching is the conventional copper roller rapid quenching method.
TABLE 1
Figure BDA0003115285530000031
Figure BDA0003115285530000041
In another embodiment, the thickness of the amorphous alloy strip is 22-25 mm; the width of the amorphous alloy strip is 1.2-1.5 mm.
Specifically, in the step 1 of the method, the melt rapid quenching is a copper roller rapid quenching method, and an NMS-II type induction type solution rapid quenching melt strip throwing machine is used for preparing the amorphous alloy strip by the copper roller rapid quenching method. Before the strip throwing, the copper roller is rotated at a linear speed of less than 15m/s, an oxide layer on the surface of the copper roller is slightly ground by using sand paper with a size of more than 2000 meshes, and the surface of the copper roller is cleaned by using gauze dipped with acetone. The mother alloy is smashed into small blocks with the diameter of about 5-8 mm, the small blocks are placed into a quartz tube, and then the quartz tube is fixed in a heating induction coil above a copper roller. The diameter of the nozzle of the round quartz tube is 0.35-0.45 mm, and the height of the nozzle from the copper roller is 0.25 ∞0.30mm, the linear velocity of the copper roller is 45-60 m/s, the pressure difference of the spraying belt is 0.03-0.08 MPa and other process parameters. Closing the furnace door, vacuumizing the furnace body to less than 6 x 10-3Pa, at the moment, closing the vacuumizing valve, filling high-purity argon into the furnace chamber to serve as protective gas, simultaneously filling gas into a gas pressure cavity connected with the test tube, paying attention to the fact that the gas pressure of the gas pressure cavity is adjusted to be larger than that of the furnace chamber, heating the master alloy by utilizing high-frequency induction heating, after the alloy is melted, paying attention to the fact that the color of the solution is suddenly changed from orange to yellow, pressing a switch for switching on the pressure cavity, spraying high-temperature melt onto a copper roller which rapidly rotates by utilizing pressure difference, and obtaining an amorphous alloy strip sample with the thickness of 22-25 mm and the width of 1.2-1.5 mm.
In another embodiment, in step 2, the thermal characteristic temperature value of the amorphous alloy strip is determined by X-ray diffraction analysis (XRD) and Differential Scanning Calorimetry (DSC) of the amorphous alloy strip.
In particular, the thermal characteristic temperature values include an initial crystallization temperature (Tx) and a crystallization peak temperature (Tp).
Specifically, X-ray diffraction analysis (XRD) and Differential Scanning Calorimetry (DSC) analysis include: and (3) inspecting whether the amorphous alloy strip sample is a complete amorphous structure or not by adopting X-ray diffraction analysis (XRD). The XRD related test conditions and parameters were: wavelength of X-rays
Figure BDA0003115285530000051
And filtering by a graphite monochromator, wherein the tube voltage is 40kV, the tube current is 30mA, the test range is 20-100 degrees, the step length is 0.02 degree, and the scanning speed is 10 degrees/min. If the XRD diffraction spectrum of the amorphous alloy strip has only one wide diffraction peak (namely a 'steamed bread peak'), the thin alloy strip can be determined to be in a completely amorphous structure.
And carrying out thermal analysis on crystallization behavior of the amorphous alloy strip sample by using a Differential Scanning Calorimeter (DSC), and inspecting the crystallization characteristic of continuous temperature rise of the alloy strip. During testing, an alloy strip sample is cut into small pieces with the area of less than 1mmx1mm, the small pieces are weighed to be about 5-10 mg and then placed into an alumina crucible, the sample is heated under the protection of N2 atmosphere, the heating rate is 20 ℃/min, and the heating range is 50-900 ℃. And obtaining thermal characteristic temperature values such as the initial crystallization temperature (Tx), the crystallization peak temperature (Tp) and the like of the amorphous alloy strip sample according to the DSC curve.
In another embodiment, in the step 2, the annealing heat treatment time is 3-30 min.
The third aspect of the application discloses application of the manganese-based nanocrystalline/amorphous composite structure alloy or the manganese-based nanocrystalline/amorphous composite structure alloy prepared by the preparation method in preparation of Magnestromon materials.
Specifically, Mn is a metal element having an odd structure and magnetism among transition group metal elements. There are four allotropes in the solid state. According to Hongde's rule, the magnetic moment of Mn atom can be as high as 5 μBAnd various magnetic interaction forms of ferromagnetism, antiferromagnetism or ferrimagnetism can be formed in the alloy according to the distance between adjacent atoms, and abundant and variable physical properties are shown. The manganese-based nanocrystalline/amorphous composite structure material can be used as a wide-temperature-range Skeleton magnetic structure material with stable zero magnetic field.
Specifically, the amorphous alloy strip sample is put into a heat treatment furnace for crystallization annealing heat treatment, the heat treatment equipment is a programmable control single vacuum tube high-temperature sintering furnace produced by Nobady materials science and technology Co., Ltd, and the model of the furnace is NBD-O1200-60 IT. During heat treatment, heating to crystallization annealing temperature Ta at a heating rate of 20 ℃/min, keeping the temperature for 10min, and cooling to room temperature along with the furnace, wherein in order to avoid oxidation, the whole heat treatment is carried out in vacuum.
According to the method, an amorphous alloy strip is prepared through specific treatment according to various specific element proportions, then the amorphous alloy strip is subjected to multistage crystallization during heating crystallization, and further through heat treatment annealing crystallization, manganese nanocrystalline particles are separated out from an amorphous alloy matrix to form a manganese-based nanocrystalline/amorphous composite structure alloy; the manganese-based nanocrystalline/amorphous composite structural alloy of the application needs a certain element proportion or the synergistic effect of a plurality of elements.
The preparation method of the alloy strip comprises the steps of carrying out induction heating on uniformly mixed mother alloy ingots to prepare the amorphous alloy strip by a copper roller rapid quenching method, wherein molten alloy liquid is required to have certain fluidity, the Si content is required to be more than 10 at.% in component design, and manganese nanocrystalline particles are separated out from an amorphous matrix through further crystallization annealing treatment to form the manganese-based nanocrystalline/amorphous composite structure alloy, and the manganese-based nanocrystalline/amorphous composite structure alloy has the following outstanding advantages: the amorphous alloy strip is prepared by utilizing an industrially mature melt rapid quenching method, and has the outstanding advantages of flexibility, high production efficiency and the like. Compared with the amorphous alloy film or powder prepared by a magnetron sputtering method and a mechanical ball milling method, the amorphous alloy strip prepared by a melt rapid quenching method has the advantages of simple process, high production efficiency, greenness and no pollution.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows Mn provided in examples of the present application68Si25B7XRD spectrum of the amorphous alloy strip of (a);
FIG. 2 shows Mn provided in examples of the present application68Si25B7DSC curve of the amorphous alloy strip of (a);
FIG. 3 shows Mn provided in examples of the present application68Si25B7XRD spectrum of the amorphous alloy strip after annealing treatment;
FIG. 4 shows Mn provided in examples of the present application68Si25B7Fast quenched (amorphous structure) and annealed (Mn) amorphous alloy strip5Si3Nanocrystalline/amorphous composite structure) temperature versus magnetization;
FIG. 5 shows Mn at rapid quenching according to an example of the present application64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3XRD spectrum of the amorphous alloy strip sample;
FIG. 6 shows Mn at rapid quenching according to an example of the present application64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3DSC curves of amorphous alloy strip samples;
FIG. 7 shows Mn in an annealed state according to examples of the present application64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3An XRD spectrum of an annealing sample with a nanocrystalline/amorphous composite structure;
FIG. 8 shows Mn at rapid quenching according to an example of the present application55Fe15Si20B7EM3(EM is one of Nb, Zr or V) XRD spectrum of amorphous alloy strip sample;
FIG. 9 shows Mn at rapid quenching according to an example of the present application55Fe15Si20B7EM3(EM is one of Nb, Zr or V) DSC curve of amorphous alloy strip;
FIG. 10 shows Mn in an annealed state according to an example of the present application55Fe15Si20B7EM3XRD spectrum of (EM ═ Nb, Zr) nanocrystalline/amorphous composite structure;
FIG. 11 is an XRD spectrum of a rapid quenched alloy strip sample having a mole percent Si less than 10 at.% as provided by a comparative example of the present application;
fig. 12 is an XRD spectrum of a sample of a rapid-quenched alloy strip having a mole percent Si of 30 at.% or more as provided in a comparative example of the present application.
Detailed Description
The application provides a manganese-based nanocrystalline/amorphous composite structure alloy and a preparation method thereof, and provides the possibility of a wide-temperature-range zero-magnetic-field stable sigramine magnetic structure material.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The reagents or raw materials used in the following examples are commercially available or self-made.
Example 1
The embodiment of the application provides Mn68Si25B7The nanocrystalline/amorphous composite tissue structure comprises the following specific steps:
1. adding Mn68Si25B7The atomic mol percentage of each element of the components is calculated and converted into the atomic weight percentage, and the raw materials required by 10g of master alloy ingot are prepared: the Mn content was 8.2767g, Si content was 1.5556g, and B content was 0.1676 g.
2. The raw materials are put into a vacuum arc melting furnace for arc melting, the melting current is preferably 80A, and the alloy ingot is repeatedly turned over for 4 times of melting so as to ensure that the components of the master alloy ingot are uniform.
3. Crushing the mother alloy into small alloy blocks with the diameter of about 5-8 mm, putting the small alloy blocks into a quartz tube, and preparing Mn by utilizing an induction type melt rapid quenching and strip throwing machine68Si25B7Amorphous alloy ribbon. The process for preparing the amorphous alloy strip comprises the following steps: the height of the quartz nozzle from the copper roller is 0.30mm, the linear speed of the copper roller rotation is 50m/s, and the pressure difference of the spraying belt is 0.04 MPa. When in melt spinning, a supersonic high-frequency induction heating power supply with the frequency of 20kHz is used for carrying out induction heating on a mother alloy block arranged in a quartz tube, the heating current is 20A, the heating holding time is about 60s, the alloy block is completely melted into liquid with good flow, at the moment, a strip spraying button is pressed down, the alloy liquid is pressed out of a nozzle of the quartz tube by utilizing the pressure difference between the quartz tube and a furnace body and is sprayed onto a copper roller which rotates rapidly, and the amorphous alloy strip is solidified into the amorphous alloy strip by utilizing the rapid cooling of the copper roller.
4. The amorphous alloy strip prepared in the step 3 is subjected to XRD characterization, as shown in fig. 1, the XRD pattern of the amorphous alloy strip only shows a wide diffraction peak at a diffraction angle 2 theta which is 45 degrees, namely a 'steamed bread peak', and the sample is an amorphous alloy strip sample with an amorphous structure under rapid quenching.
5. DSC thermal analysis is performed on the amorphous alloy strip prepared in the step 3, as shown in figure 2, the DSC curve of the sample has two obvious exothermic peaks, which illustrate the amorphous alloy of the embodimentThe crystallization characteristic of the strip is double-stage crystallization behavior, and the phase separated out corresponding to the first-stage crystallization peak is Mn by combining XRD phase analysis5Si3The phase precipitated corresponding to the second-stage crystallization peak is Mn2B。
6. Based on the crystallization characteristic temperature obtained by the thermal analysis in the step 5, the formulation of a thermal treatment annealing process can be guided, and the amorphous alloy strip in the step 3 is annealed in a vacuum tube furnace for 10min at 540 ℃ and 550 ℃ respectively to prepare Mn68Si25B7。
The XRD spectrum of the amorphous alloy strip in the step 3 after the annealing treatment is shown in figure 3, and only Mn is detected on the XRD spectrum5Si3The diffraction peak of (2) shows that only single Mn is precipitated on the matrix of the amorphous phase (amorphous phase: referring to the matrix parent phase in which Mn, Si and B are disordered and uniformly distributed) after the sample is annealed5Si3The nano-crystalline particles successfully realize the manganese-based nano-crystalline/amorphous composite structure alloy-Mn5Si3A nano-crystalline/amorphous dual-phase composite structure (namely Mn)68Si25B7)。
FIG. 4 shows the amorphous alloy strip of the examples of the present application in the fast-quenched (amorphous structure) and annealed (Mn) states5Si3Nanocrystalline/amorphous composite structure) temperature versus magnetization. Analysis of the magnetization curve reveals that the amorphous alloy strip of step 3 is in a fast quenching state (amorphous structure) and an annealing state (Mn)5Si3Nanocrystalline/amorphous composite structure), the corresponding spin glass transition temperatures (Tf) are 23K and 15K, respectively. In contrast, the amorphous structure of the sample enters the paramagnetic state after the spin-glass transition, while Mn5Si3Nanocrystalline/amorphous composite structure sample (Mn)68Si25B7) After the spin glass transition, the ferromagnetic state (temperature range of 15K to 100K) is first entered, and then the paramagnetic state is entered, and thus, the Mn is shown5Si3Nanocrystalline/amorphous dual-phase composite structure (Mn)68Si25B7) Has more obvious spin glass transition characteristic and richer magnetic transition behavior.
Example 2
The embodiment of the application provides Mn64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3The nanocrystalline/amorphous composite tissue structure comprises the following specific steps:
1. respectively adding Mn64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3The mol percentage of each element atom in the components is calculated and converted into the weight percentage of the atom, and 10g of Mn is prepared64Si25B7Ag1Nb3Raw materials required by the master alloy ingot: 7.6237g of Mn, 1.4328g of Si, 0.1544g of B, 0.2201g of Ag and 0.5687g of Nb. Preparation of 10g of Mn64Si25B7Cu1Nb3Raw materials required by the master alloy ingot: mn is 7.6933g, Si is 1.4459g, B is 0.1558g, Cu is 0.1308g, and Nb is 0.5687 g.
2. The raw materials are put into a vacuum arc melting furnace for arc melting, the melting current is preferably 80A, and the alloy ingot is repeatedly turned over for 4 times of melting so as to ensure that the components of the master alloy ingot are uniform.
3. Crushing the mother alloy into small alloy blocks with the diameter of about 5-8 mm, putting the small alloy blocks into a quartz tube, and preparing Mn by utilizing an induction type melt rapid quenching and strip throwing machine64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3Amorphous alloy ribbon. The process for preparing the amorphous alloy strip comprises the following steps: the height of the quartz nozzle from the copper roller is 0.25mm, the linear speed of the copper roller is 55m/s, and the pressure difference of the spraying belt is 0.06 MPa. When in melt spinning, a supersonic high-frequency induction heating power supply with the frequency of 20kHz is used for carrying out induction heating on the mother alloy block in the quartz tube, the heating current is 30A, the heating holding time is about 100s, the alloy block is completely melted into liquid with good flow, the spray belt button is pressed, the alloy liquid is pressed out of a nozzle of the quartz tube by using the pressure difference between the quartz tube and the furnace body and is sprayed onto a copper roller which rotates rapidly, and the alloy liquid is solidified into the alloy liquid by using the rapid cooling of the copper rollerTwo amorphous alloy ribbons.
4. And (3) carrying out XRD characterization on the two amorphous alloy strip samples prepared in the step (3) under the rapid quenching, wherein as shown in figure 5, the XRD spectrums of the two amorphous alloy strip samples only have a wide diffraction peak at a diffraction angle 2 theta which is 45 degrees, namely a 'steamed bread peak', which indicates that the two amorphous alloy strip samples are in an amorphous structure under the rapid quenching.
5. Respectively carrying out DSC thermal analysis on two amorphous alloy strip samples, as shown in figure 6, three exothermic peaks are arranged on DSC curves of the two amorphous alloy strip samples under rapid quenching, which shows that the crystallization characteristics of the two amorphous alloy strip samples are multistage crystallization behaviors, and the phase correspondingly separated by the first and second crystallization peaks which are overlapped closely and partially is Mn is known by combining XRD phase analysis3Si and Mn5Si3The phase precipitated corresponding to the third-stage crystallization peak is Mn2B。
6. Based on the crystallization characteristic temperatures of the two amorphous alloy strip samples respectively obtained by the thermal analysis in the step 5, the two amorphous alloy strip samples are respectively placed in a vacuum tube furnace to be annealed and preserved for 10min at 580 ℃, and Mn is prepared64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3A nanocrystalline/amorphous composite structure.
FIG. 7 shows Mn in the annealed state64Si25B7Ag1Nb3And Mn64Si25B7Cu1Nb3XRD spectrum of nano crystal/amorphous composite structure, phase analysis of the spectrum to determine Mn3Si and Mn5Si3It is shown that after annealing crystallization treatment, two samples separated out two manganese-silicon compounds, namely Mn, on the amorphous phase (amorphous phase: refers to matrix parent phase with disordered and uniformly distributed Mn, Si, B, Ag and Nb) matrix3Si and Mn5Si3Nanocrystalline particles, successfully realizing Mn3Si and Mn5Si3Preparing a manganese-based nanocrystalline/amorphous multiphase composite organization structure with a two-phase nanocrystalline/amorphous composite structure type.
Example 3
The embodiment of the application provides Mn55Fe15Si20B7Nb3、Mn55Fe15Si20B7Zr3Or Mn55Fe15Si20B7V3The nanocrystalline/amorphous composite tissue structure comprises the following specific steps:
1. the formula component is Mn55Fe15Si20B7EM3(EM ═ Nb, Zr, V). Adding Mn55Fe15Si20B7Nb3The atomic mol percentage of each element of the components is calculated and converted into the atomic weight percentage, and the raw materials required by 10g of master alloy ingot are prepared: 6.3274g of Mn, 1.7542g of Fe, 0.1584g of B and 0.5836g of Nb; and similarly, calculating the raw material dosage for the nanocrystalline/amorphous composite tissue structure sample of EM (the equivalent of Zr) and V according to the corresponding atomic percentage.
2. The raw materials are put into a vacuum arc melting furnace for arc melting, the melting current is preferably 100A, and the alloy ingot is repeatedly turned over for 4 times of melting so as to ensure that the components of the master alloy ingot are uniform.
3. Respectively crushing the master alloy into small alloy blocks with the diameter of about 5-8 mm, putting the small alloy blocks into a quartz tube, and preparing Mn by utilizing an induction type melt rapid quenching and strip throwing machine55Fe15Si20B7EM3(EM ═ Nb, Zr, V) amorphous alloy ribbon. The process for preparing the strip comprises the following steps: the height of the quartz nozzle from the copper roller is 0.25mm, the linear speed of the copper roller is 55m/s, and the pressure difference of the spraying belt is 0.06 MPa. When in melt spinning, a supersonic high-frequency induction heating power supply is used, the frequency is 20kHz, the mother alloy block in the quartz tube is subjected to induction heating, the heating current is 30A, the heating holding time is about 100s, the alloy block is completely melted into liquid with good flow, the ribbon spraying button is pressed, the alloy liquid is pressed out of a nozzle of the quartz tube by using the pressure difference between the quartz tube and the furnace body and is sprayed onto a copper roller which rotates rapidly, and the amorphous alloy ribbon sample is formed by rapid cooling and solidification of the copper roller.
4. Mn is added into the rapidly quenched steel prepared in the step 355Fe15Si20B7EM3The (EM ═ Nb, Zr and V) amorphous alloy strip samples are subjected to XRD characterization, as shown in figure 8, the XRD patterns of the (EM ═ Nb, Zr and V) amorphous alloy strip samples only show one broad diffraction peak at the diffraction angle 2 theta ═ 45 degrees, namely, a 'steamed bread peak', which indicates that the samples are amorphous alloy strip samples with an amorphous structure under rapid quenching.
5. Mn of step 3 respectively55Fe15Si20B7EM3DSC thermal analysis is carried out on (EM ═ Nb, Zr and V) amorphous alloy strip samples, the curve is shown in figure 9, the DSC curves of all the samples have two obvious exothermic peaks, which shows that the crystallization characteristic of the amorphous samples is secondary crystallization behavior, and the phase separated out corresponding to the first-stage crystallization peak is alpha-Mn and Mn combined with XRD phase analysis6Si, the phase precipitated corresponding to the second-stage crystallization peak is Mn2B。
6. Crystallization characteristic temperature obtained based on thermal analysis of step 5 for Mn55Fe15Si20B7Zr3Annealing treatment of the amorphous alloy strip sample at 600 ℃ for 10min to obtain Mn55Fe15Si20B7Nb3Annealing treatment of the amorphous alloy strip sample at the temperature of 620 ℃ for 10min to prepare Mn55Fe15Si20B7Zr3And Mn55Fe15Si20B7Nb3A nanocrystalline/amorphous composite structure.
FIG. 10 shows Mn in the annealed state as described above in an example of the present application55Fe15Si20B7Zr3And Mn55Fe15Si20B7Nb3The XRD spectrum of the nanocrystalline/amorphous composite structure shows that the analysis of the spectrogram shows that after the amorphous alloy strip sample is annealed, two manganese-silicon compounds, namely alpha-Mn and Mn, are separated out on an amorphous phase (amorphous phase: refers to a matrix parent phase in which Mn, Fe, Si, B and Nb are disordered and uniformly distributed) matrix6Si nanocrystalline particles, successfully prepared alpha-Mn and Mn6A manganese-based nanocrystalline/amorphous composite structure alloy of a Si two-phase nanocrystalline/amorphous composite structure type.
Comparative example 1
The application provides manganese-based alloys with different Si contents, and the specific method comprises the following steps:
with reference to the process of example 1, this comparative example differs in that the atomic mole number of Si is less than 10 and the mole number of Si is greater than or equal to 30, i.e. in terms of Mn83Si4B13、Mn82Si6B12、Mn82Si8B10、Mn45Si45B10、Mn63Si30B7The manganese-based alloy strips with different Si contents are prepared by the method of the step 2 and the step 3 in the embodiment 1, namely Mn is obtained83Si4B13Alloy strip, Mn82Si6B12Alloy strip, Mn82Si8B10Alloy strip, Mn45Si45B10Alloy strip, Mn63Si30B7The alloy strip is not subjected to annealing heat treatment, and only subjected to melt rapid quenching treatment.
XRD spectrum analysis was performed on the alloy strip in the rapidly quenched state, and the results are shown in FIGS. 11 to 12. Fig. 11 is an XRD spectrum of a sample of the rapidly quenched alloy strip with a mole percentage of Si less than 10 at.%, which shows that the alloy strip in the rapidly quenched state has a severe crystallization peak, and it is difficult to prepare an amorphous alloy strip with an amorphous structure under the existing conditions; fig. 2 is an XRD spectrum of a sample of a rapidly quenched alloy strip with a mole percentage of Si of 30 at.% or more, which is also severely crystallized in the rapidly quenched sample. Therefore, the amorphous strip with the amorphous structure cannot be obtained by the copper roller rapid quenching method.
In summary, in the embodiments of the present application, one or two kinds of α -Mn and Mn are precipitated on the amorphous alloy substrate by annealing and crystallization of the amorphous alloy precursor5Si3、Mn3Si、Mn6The simple substance of Si or manganese-silicon compound nano-particles form a manganese-based nanocrystalline/amorphous composite structure material. The important point is that the amorphous alloy has multi-stage crystallization during crystallization thermal analysis through the component design of the manganese-based nanocrystalline/amorphous composite structure alloy, and the manganese simple substance or manganese silicon is correspondingly separated out in the first stage of crystallizationThe compound of (2) can control and separate out nanocrystalline particles through heat treatment, and controllable preparation of the manganese-based nanocrystalline/amorphous composite structure alloy is realized. For the Mn-Si-B ternary amorphous alloy, the mole percentage content of Si atoms is 10-20 at.%, and Mn-Si-B is single-stage crystallization (only one exothermic peak is on a DSC curve). The amorphous sample can have multi-stage crystallization behavior only by properly adjusting the Si/B and Si/Mn ratios, for example, the sample Si in example 1 is 25 at.%, DSC has two exothermic peaks, and Mn is correspondingly precipitated5Si3And Mn2And (B) phase. In addition, the nucleation of Mn or manganese compound is promoted by introducing elements such as Cu and Ag which are not in solid solution with Mn, and the Mn is promoted by adding large atoms such as Nb2The separation of the phase B enlarges the temperature interval of crystallization peaks, and is more beneficial to the heat treatment to separate out the manganese-silicon nano particles (example 2). And a proper amount of Fe, Co and Ni can be introduced to make the core center and the synergistic effect of Zr, Nb and other macro atoms, so that the control of the crystallization behavior precipitated phase of the amorphous alloy is realized. The amorphous alloy shows a double-stage crystallization behavior under the synergistic effect of Fe and Zr, Nb or V in the formula of the component in the example 3. The multi-stage crystallization behavior of the amorphous alloy realizes the controllability preparation of the manganese-based nanocrystalline/amorphous composite structure material.
In addition, the manganese-based nanocrystalline/amorphous composite structure alloy prepared by the embodiment of the application endows the material with more excellent characteristics and more abundant magnetic transformation phenomena. In the material of example 1, fig. 4 discloses the magnetic behavior of the manganese-based nanocrystalline/amorphous composite structural alloy sample and the amorphous sample of the present example, and it is apparent that the manganese-based nanocrystalline/amorphous composite structural alloy sample of the present example has an extraordinary amorphous alloy magnetic transformation characteristic and a richer magnetic transformation behavior. The manganese-based nanocrystalline/amorphous composite structure alloy provides possibility for developing a skyrmion magnetic structure material with wide temperature range and zero magnetic field stability, and has academic research value and potential practical application value in the field of spintronics.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims (10)

1. The manganese-based nanocrystalline/amorphous composite structural alloy is characterized by having the following general formula:
MnbalSiaBbMcRdTe；
in the general formula, MnbalThe alloy system takes Mn as a main component, and the atomic mole number bal of the alloy system is more than or equal to 55; the mole number a of the Si element satisfies that a is more than or equal to 10 and less than 30; the mole number B of the B element satisfies that B is more than 5 and less than or equal to 12; m is selected from one or more of Fe, Co, Ni or Cr elements, and the atomic mole number c satisfies 0-25; r is selected from one or more of Ag, Mg and Cu elements, and the atomic mole number d of the R is more than or equal to 0 and less than or equal to 5; t is selected from one or more of Zr, Ti, V, Nb, Hf and Ta, and the atomic number e is more than or equal to 0 and less than or equal to 8; the atomic molar number of the sum of bal + a + b + c + d + e is 100.
2. The manganese-based nanocrystalline/amorphous composite structural alloy according to claim 1, wherein in the general formula, M is selected from Fe.
3. The manganese-based nanocrystalline/amorphous composite structural alloy according to claim 1, wherein in the general formula, R is selected from Ag or Cu.
4. The manganese-based nanocrystalline/amorphous composite structural alloy according to claim 1, wherein in the general formula, T is selected from one of Nb, Zr, or V.
5. The manganese-based nanocrystalline/amorphous composite structural alloy according to claim 1, wherein the manganese-based nanocrystalline/amorphous composite structural alloy has a chemical formula of: mn68Si25B7、Mn64Si25B7Ag1Nb3、Mn64Si25B7Cu1Nb3Or Mn55Fe15Si20B7EM3(ii) a Wherein E isM is one or more of Nb, Zr and V.
6. A preparation method of a manganese-based nanocrystalline/amorphous composite structure alloy is characterized by comprising the following steps:
step 1, mixing the raw materials of the manganese-based nanocrystalline/amorphous composite structural alloy according to the proportion of the manganese-based nanocrystalline/amorphous composite structural alloy in any one of claims 1 to 5, and then performing melt rapid quenching to obtain an amorphous alloy strip;
and 2, carrying out annealing heat treatment on the amorphous alloy strip according to the thermal characteristic temperature value of the amorphous alloy strip to prepare the manganese-based nanocrystalline/amorphous composite structure alloy.
7. The production method according to claim 6, wherein in step 1, the treatment is an arc melting treatment or a magnetron sputtering treatment.
8. The method according to claim 6, wherein the amorphous alloy strip has a thickness of 22 to 25 mm; the width of the amorphous alloy strip is 1.2-1.5 mm.
9. The method according to claim 6, wherein in step 2, the thermal characteristic temperature value of the amorphous alloy strip is determined by X-ray diffraction analysis and differential scanning calorimetry analysis of the amorphous alloy strip.
10. The method according to claim 6, wherein in the step 2, the annealing heat treatment time is 3 to 30 min.
CN202110661600.2A 2021-06-15 2021-06-15 Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof Active CN113388766B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110661600.2A CN113388766B (en) 2021-06-15 2021-06-15 Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110661600.2A CN113388766B (en) 2021-06-15 2021-06-15 Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113388766A true CN113388766A (en) 2021-09-14
CN113388766B CN113388766B (en) 2022-09-13

Family

ID=77621523

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110661600.2A Active CN113388766B (en) 2021-06-15 2021-06-15 Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113388766B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115125428A (en) * 2022-08-09 2022-09-30 杭州电子科技大学 Wide-temperature-zone trans-room-temperature Magnetitum material and preparation method and application thereof
CN117840422A (en) * 2024-03-08 2024-04-09 朗峰新材料启东有限公司 Manganese-based amorphous nanocrystalline composite powder and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101255536A (en) * 2008-03-13 2008-09-03 江苏波瑞电气有限公司 Production of high-squareness-ratio amorphous nanocrystalline strip and iron core
CN102181808A (en) * 2011-04-08 2011-09-14 郭莉 Method for producing high-permeability amorphous nanocrystalline alloy
CN106756644A (en) * 2016-12-28 2017-05-31 广东工业大学 A kind of iron-based amorphous and nanocrystalline soft magnetic alloy based on element silicon and preparation method thereof
CN110670000A (en) * 2019-09-24 2020-01-10 全球能源互联网研究院有限公司 Nanocrystalline magnetically soft alloy, amorphous magnetically soft alloy and preparation method thereof
US20200335246A1 (en) * 2019-04-19 2020-10-22 Baolong Shen Fe-Co BASED AMORPHOUS SOFT MAGNETIC ALLOY AND PREPARATION METHOD THEREOF
CN112899586A (en) * 2021-01-15 2021-06-04 广东工业大学 Manganese-based amorphous alloy and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101255536A (en) * 2008-03-13 2008-09-03 江苏波瑞电气有限公司 Production of high-squareness-ratio amorphous nanocrystalline strip and iron core
CN102181808A (en) * 2011-04-08 2011-09-14 郭莉 Method for producing high-permeability amorphous nanocrystalline alloy
CN106756644A (en) * 2016-12-28 2017-05-31 广东工业大学 A kind of iron-based amorphous and nanocrystalline soft magnetic alloy based on element silicon and preparation method thereof
US20200335246A1 (en) * 2019-04-19 2020-10-22 Baolong Shen Fe-Co BASED AMORPHOUS SOFT MAGNETIC ALLOY AND PREPARATION METHOD THEREOF
CN110670000A (en) * 2019-09-24 2020-01-10 全球能源互联网研究院有限公司 Nanocrystalline magnetically soft alloy, amorphous magnetically soft alloy and preparation method thereof
CN112899586A (en) * 2021-01-15 2021-06-04 广东工业大学 Manganese-based amorphous alloy and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115125428A (en) * 2022-08-09 2022-09-30 杭州电子科技大学 Wide-temperature-zone trans-room-temperature Magnetitum material and preparation method and application thereof
CN115125428B (en) * 2022-08-09 2023-03-10 杭州电子科技大学 Wide-temperature-zone trans-room-temperature Magnetitum material and preparation method and application thereof
CN117840422A (en) * 2024-03-08 2024-04-09 朗峰新材料启东有限公司 Manganese-based amorphous nanocrystalline composite powder and preparation method thereof

Also Published As

Publication number Publication date
CN113388766B (en) 2022-09-13

Similar Documents

Publication Publication Date Title
CN104934179B (en) Fe-based nanocrystalline magnetically soft alloy of strong amorphous formation ability and preparation method thereof
CN101834046B (en) High saturation magnetization intensity Fe-based nanocrystalline magnetically soft alloy material and preparation method thereof
CN113388766B (en) Manganese-based nanocrystalline/amorphous composite structure alloy and preparation method thereof
CA1181262A (en) Amorphous alloys for electromagnetic devices
JP7387008B2 (en) Iron-based amorphous alloy containing sub-nanoscale ordered clusters, method for preparing the same, and nanocrystalline alloy derivatives using the same
JP6561117B2 (en) Rare earth permanent magnet and manufacturing method thereof
TW200533767A (en) Ternary and multi-nary iron-based bulk glassy alloys and nanocrystalline alloys
JP6673536B1 (en) Powder for magnetic core, magnetic core and coil parts using the same
JPS6356297B2 (en)
CN105671460B (en) The preparation method of inexpensive FeNbB ternarys non-crystaline amorphous metal soft magnetic materials
JP2001226753A (en) Iron-base alloy soft magnetic material and manufacturing method
Larimian et al. Spark plasma sintering of Fe–Si–B–Cu–Nb/Finemet based alloys
CN112899586B (en) Manganese-based amorphous alloy and preparation method and application thereof
JP6648856B2 (en) Fe-based alloy, crystalline Fe-based alloy atomized powder, and magnetic core
Liu et al. Preparation, thermal stability, and magnetic properties of Fe Co Zr Mo W B bulk metallic glass
Neamţu et al. Structural and magnetic characteristics of Co-based amorphous powders prepared by wet mechanical alloying
CN109880985B (en) Method for producing soft magnetic material
WO2020024870A1 (en) Alloy composition, fe-based nanocrystalline alloy and manufacturing method therefor, and magnetic component
KR20090069473A (en) Gd-based phase separating metallic amorphous alloy having unique magnetic properties
JP5946922B2 (en) Sputtering target for magnetic recording media
Lei et al. Fabrication of spherical Fe-based magnetic powders via the in situ de-wetting of the liquid–solid interface
Lee et al. Compositional effect on the magnetic and microstructural properties of Fe-based nano-crystalline alloys
Cotai et al. A Comparative Study of Nanocrystalline Fe 38.5 Co 38.5 Nb 7 P 15Cu 1 Alloys Obtained by Mechanical Alloying and Rapid Quenching
WO2021132272A1 (en) Alloy
WO2021149590A1 (en) Alloy and molded body

Legal Events

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