Magnetic fe-p-based amorphous alloy with positive and negative mixing heat elements and synergistic microalloying and preparation method thereof

Abstract

This invention provides a magnetic FeP-based amorphous alloy microalloyed with a combination of positive and negative thermal elements and its preparation method. The chemical formula of the amorphous alloy is Fe. a Al b Cr c Sn d RE e P f B g C h Si i In the formula, RE represents rare earth elements, which are one or more combinations of Y, Er, Gd, Dy, La, and Ce; Al, Cr, Sn, RE, and Si are microalloying elements; the content of each element in the formula is expressed as an atomic percentage (at.%), as follows: b is 0-2, c is 0.5-3, d is 0.5-2, e is 0.2-2, f is 6-11, g is 4-7, h is 5-11, i is 0.5-2, and the remainder is Fe, and a+b+c+d+e+f+g+h+i=100; the amorphous alloy of this invention has the advantages of soft magnetic properties, high strength, high hardness, high thermal properties and resistance to crystallization failure, and excellent corrosion resistance; at the same time, through composition optimization, rod-shaped bulk materials with a maximum critical diameter of not less than 4 mm can also be prepared; this alloy can be applied to the preparation of soft magnetic component materials and corrosion-resistant and wear-resistant coating materials, and has high engineering value and economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloys, specifically relating to a magnetic FeP-based amorphous alloy microalloyed by synergistic microalloying of positive and negative mixed thermal elements and its preparation method. Background Technology

[0002] FeP-based amorphous alloys, as typical Fe-based amorphous alloys with disordered atomic arrangement and structural defects such as dislocations in their internal structure, theoretically possess the advantages of combining good soft magnetic properties, mechanical properties, and corrosion resistance. Therefore, FeP-based amorphous alloys can serve as a potential functional, structural, or integrated functional and structural material with high scientific research and engineering application value in fields such as electromagnetics, new energy, and near-shore corrosion and wear resistance protection. However, a major problem with FeP-based amorphous alloys is that current technologies primarily rely on the addition of alloying elements with positive heats of mixing (or enthalpies of mixing) with the matrix element Fe, such as Sn (11 kJ / mol for FeSn) and Cu (13 kJ / mol for FeCu), or with negative heats of mixing, such as Al (-11 kJ / mol for FeAl), Cr (-1 kJ / mol for FeCr), and Mo (-2 kJ / mol for FeMo). This often results in a loss of some of the alloy's superior properties (or amorphous forming ability) while optimizing its amorphous forming ability (or properties), making it difficult to reconcile the excellent properties of FeP-based amorphous alloys with their good amorphous alloying ability. Meanwhile, single-element alloying with elements exhibiting positive or negative heat of mixing with the matrix element Fe often requires higher alloying element content. This characteristic not only leads to lower alloying efficiency but also further reduces some of the superior properties of FeP-based amorphous alloys (e.g., the deterioration of magnetic properties when excessive non-ferromagnetic alloying elements are added). These characteristics severely restrict the development and application of FeP-based amorphous alloys. Therefore, it is necessary to optimize the existing techniques for controlling the glass-forming ability and properties of FeP-based amorphous alloys, thereby achieving a balance between the amorphous forming ability and properties of this type of alloy, and ultimately developing more FeP-based amorphous alloys that possess both excellent properties and high glass-forming ability. Summary of the Invention

[0003] This invention provides a magnetic FeP-based amorphous alloy and its preparation method using microalloying with positive and negative mixed heat elements. This solves the problem in the prior art that the alloying elements with positive or negative mixed heat with the matrix element Fe are mainly added individually, which makes it difficult to coordinate the excellent properties and good amorphous alloy forming ability of such alloys.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows:

[0005] In a first aspect, the present invention provides a magnetic FeP-based amorphous alloy microalloyed with a combination of positive and negative thermal elements, characterized in that the chemical formula of the amorphous alloy is Fe. a Al b Cr c Sn d RE e P f B g C h Si i In the formula, RE represents rare earth elements; Al, Cr, Sn, RE, and Si are microalloying elements; the content of each element in the formula is expressed as an atomic percentage (at.%), specifically as follows: b is 0-2, c is 0.5-3, d is 0.5-2, e is 0.2-2, f is 6-11, g is 4-7, h is 5-11, i is 0.5-2, and the remainder is Fe, and a+b+c+d+e+f+g+h+i=100; the RE is one or more of Y, Er, Gd, Dy, La, and Ce.

[0006] Furthermore, the microalloying elements include at least one positive mixing heat microalloying element that has a positive mixing heat with Fe, and at least one negative mixing heat microalloying element that has a negative mixing heat with Fe.

[0007] Furthermore, the positive mixed thermal microalloying elements include Sn, La, and Ce; the negative mixed thermal microalloying elements include Al, Cr, Si, Y, Er, Gd, and Dy.

[0008] Furthermore, the amorphous alloy is a strip material with a thickness of 20–30 μm.

[0009] Furthermore, the amorphous alloy is a rod-shaped bulk material with a maximum critical diameter of not less than 4 mm.

[0010] Furthermore, the chemical formula of the amorphous alloy is Fe. 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 or Fe 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 or Fe 75 Al 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si 0.5 or Fe 76 Al2Cr2Sn 1.5 La1P7B4C6Si0.5 .

[0011] Secondly, this invention provides a method for preparing a magnetic FeP-based amorphous alloy by synergistic microalloying of positive and negative mixed thermal elements, characterized by comprising:

[0012] Ingredients: According to Fe a Al b Cr c Sn d RE e P f B g C h Si i Weigh each raw material according to its chemical formula;

[0013] Melting the master alloy ingot: Place the weighed raw materials into a vacuum induction melting furnace and melt them 1 to 5 times to make the raw materials melt evenly. After cooling in the furnace, take out the master alloy ingot.

[0014] Preparation of amorphous alloys: The master alloy ingot is completely melted in an induction furnace using a rapid solidification apparatus to obtain an alloy melt. The alloy melt is then rapidly cooled and solidified using a melt spin quenching method or a copper mold casting method to obtain Fe. a Al b Cr c Sn d RE e P f B g C h Si i Amorphous alloy.

[0015] Furthermore, the alloy melt is rapidly cooled and solidified using the copper mold casting method to obtain a rod-shaped block material, the maximum critical diameter of which is not less than 4 mm; the alloy melt is rapidly cooled and solidified using the melt spin quenching method to obtain a strip material, the thickness of which is 20-30 μm.

[0016] Furthermore, the conditions for smelting the master alloy ingot are: adjusting the vacuum degree inside the furnace to ≤3×10 -2 Pa, melting temperature 1300 ℃~1700 ℃, single-pass melting time 1~4 min;

[0017] The conditions for preparing the ribbon material by the melt spin quenching method are: vacuum degree 1~3×10⁻⁶ -2 Pa, induced current 7~10 A, spraying pressure 0.02~0.05 MPa, copper wheel speed 2500~3500 r / min;

[0018] The conditions for preparing bulk materials using the copper mold casting method are: vacuum degree 1~3×10⁻⁶. -2Pa, induced current 7~10 A, spray casting pressure 0.03~0.06 MPa.

[0019] Thirdly, this invention provides the application of the magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements in the preparation of soft magnetic component materials and corrosion-resistant and wear-resistant coating materials.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. The magnetic FeP-based amorphous alloy microalloyed with a combination of positive and negative mixed thermal elements provided in this embodiment of the invention, when the composition is relatively similar (i.e., the ferromagnetic element is only iron and the content difference does not exceed 1 at.%), and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2 at.%), has a lower initial crystallization temperature (T) than the magnetic FeP-based amorphous alloy microalloyed with only a single thermal element that has a positive or negative mixed relationship with the matrix element Fe. x The initial crystallization temperature is at least 10 °C higher; this feature gives the alloys better resistance to crystallization failure (the initial crystallization temperature is higher or the crystallization time is longer when crystallizing at the same isothermal temperature, or the same crystallization time is required at a higher temperature to crystallize) and service stability.

[0022] 2. The magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements provided in this embodiment of the invention has a saturation magnetic induction intensity (M). s The saturation magnetic induction intensity is not less than 1.2T and can reach up to 1.55T. Under the conditions that the only ferromagnetic element is Fe and the content difference does not exceed 1% and the metalloid elements are the same (i.e. P, C, B and Si) and the total content difference does not exceed 2%, the saturation magnetic induction intensity is higher than that of magnetic FeP-based amorphous alloys that are alloyed with a single thermal element that has a positive or negative mixture with the base element Fe.

[0023] 3. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this embodiment of the invention has a higher saturation magnetic induction intensity than a magnetic FeP-based amorphous alloy that is alloyed with only a single thermal element that has a positive or negative mixed relationship with the matrix element Fe. Under similar conditions (the ferromagnetic element is only Fe and the content difference does not exceed 1%, and the metalloid elements are the same (i.e., P, C, B and Si) and the total content difference does not exceed 2%), fracture strength (difference does not exceed 0.5 GPa), hardness (difference does not exceed 0.5 GPa), and resistance to near-shore and marine corrosion (e.g., no significant weight loss after soaking in 3 wt.% NaCl solution for 7 days). On the other hand, under similar compositional characteristics (where the ferromagnetic element is only Fe with a content difference of no more than 1% and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2%) and magnetic properties (saturation magnetic induction intensity difference of no more than 0.1T), compared with magnetic FeP-based amorphous alloys alloyed solely with a single alloying element that exhibits positive or negative mixing with the base element Fe, the alloy of this invention also possesses excellent resistance to near-shore and marine corrosion (e.g., no significant weight loss after immersion in a 3wt.% NaCl solution for 7 days). Furthermore, under similar compositional characteristics (where the ferromagnetic element is only Fe with a content difference of no more than 1% and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2%) and magnetic properties (saturation magnetic induction intensity difference of no more than 0.1T), the bulk material obtained by optimizing the alloy composition of this invention can also possess a fracture strength (σ) of no less than 3.3 GPa. f Vickers microhardness (H) of 9 GPa v ) and 1% compressive plasticity.

[0024] 4. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this embodiment of the invention has, compared with a magnetic FeP-based amorphous alloy that is alloyed with a single thermal element that is positive or negatively mixed with the matrix element Fe, superior magnetic properties (i.e., higher saturation magnetic induction intensity) and resistance to crystallization failure (higher initial crystallization temperature or longer time required for crystallization at the same isothermal temperature or higher temperature for crystallization at the same crystallization time) when the composition characteristics (the ferromagnetic element is only Fe and the content difference is no more than 1% and the metalloid elements are the same (i.e. P, C, B and Si) and the total content difference is no more than 2%) and the alloy amorphous forming ability (i.e. the critical diameter of rod-shaped bulk materials or the critical thickness of strip-shaped materials) are similar. Meanwhile, compared with magnetic FeP-based amorphous alloys that are alloyed solely with a single thermal element that has a positive or negative mixture with the base element Fe, the alloy of this invention has similar compositional characteristics (the ferromagnetic element is only Fe with a content difference of no more than 1%, and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2%), fracture strength (difference of no more than 0.5 GPa), hardness (difference of no more than 0.5 GPa), and resistance to near-shore and marine corrosion (e.g., no significant weight loss after immersion in 3 wt.% NaCl solution for 7 days), and the same amorphous forming ability (i.e., the critical diameter of rod-shaped bulk materials or the critical thickness of strip-shaped materials). Under the same conditions, the total amount of microalloying elements required for the alloy of this invention is lower or the relative alloying efficiency is higher.

[0025] 5. The magnetic FeP-based amorphous alloy with positive and negative mixed thermal elements synergistic microalloying provided in the embodiments of the present invention can also obtain a rod-shaped bulk material with a maximum critical diameter of not less than 4 mm while having excellent magnetic properties, high mechanical strength and hardness, excellent resistance to near-river and sea corrosion and high resistance to crystallization failure by optimizing the alloy composition.

[0026] Of course, implementing the various technical solutions of this invention does not necessarily require achieving all of the advantages described above at the same time. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other embodiments can be obtained from these drawings without creative effort.

[0028] Figure 1 These are the X-ray diffraction (XRD) patterns of the amorphous alloy as-cast specimens corresponding to Examples 1-4 of the present invention;

[0029] Figure 2These are photographs of the amorphous alloy as-cast specimens corresponding to Examples 1-4 of the present invention. Detailed Implementation

[0030] The present invention will now be described in further detail with reference to specific embodiments and accompanying drawings. Similar elements in different embodiments are referred to by associated similar element reference numerals. In the following embodiments, many details are described to facilitate a better understanding of this application. However, those skilled in the art will readily recognize that some features may be omitted in different situations, or may be replaced by other elements, materials, or methods. In some cases, certain operations related to this application are not shown or described in the specification. This is to avoid obscuring the core parts of this application with excessive description. For those skilled in the art, detailed description of these related operations is not necessary; they can fully understand the related operations based on the description in the specification and general technical knowledge in the art.

[0031] Furthermore, the features, operations, or characteristics described in the specification can be combined in any suitable manner to form various embodiments. At the same time, the steps or actions in the method description can be rearranged or adjusted in a manner obvious to those skilled in the art. Therefore, the various orders in the specification and drawings are only for the clear description of a particular embodiment and do not imply a necessary order, unless otherwise stated that a particular order must be followed.

[0032] This invention designs a magnetic FeP-based amorphous alloy with microalloying characteristics different from existing FeP-based amorphous alloys, superior comprehensive performance, high potential application value, and the ability to be fabricated as a bulk material using a synergistic microalloying of positive and negative mixed thermal elements. The chemical formula of this alloy is Fe. a Al b Cr c Sn d RE e P f B g C h Si i In the formula, RE represents rare earth elements, which are one or more combinations of Y, Er, Gd, Dy, La, and Ce; Al, Cr, Sn, RE, and Si are microalloying elements; the content of each element in the formula is expressed as an atomic percentage (at.%), as follows: b is 0-2, c is 0.5-3, d is 0.5-2, e is 0.2-2, f is 6-11, g is 4-7, h is 5-11, i is 0.5-2, and the remainder is Fe, and a+b+c+d+e+f+g+h+i=100.

[0033] The present invention will be further illustrated below through several typical embodiments:

[0034] Example 1:

[0035] The chemical formula of the magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements provided in this embodiment is Fe. 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 It can be prepared by the following method:

[0036] Step 1, Ingredient preparation: Calculate and weigh the required purity of pure Fe, pure Cr, pure Sn, pure Y, pure C, pure Si, and FeP and FeB alloys, all with a purity greater than 99 wt.% according to the composition.

[0037] Step 2, Melting the master alloy ingot: Place the raw materials weighed in Step 1 into a vacuum induction melting furnace, and adjust the vacuum degree inside the furnace to 2×10⁻⁶. －2 Pa, the melting temperature is 1350℃~1500℃, the melting time is 2 min, and the raw material is melted 3 times to make the raw material melt evenly. After cooling in the furnace, the master alloy ingot is taken out.

[0038] Step 3, Preparation of amorphous alloy: The alloy ingot of Example 1 obtained in Step 2 was placed in a rapid solidification device and completely melted using its electromagnetic induction furnace. Then, alloy strip samples with a thickness of approximately 20–30 μm were obtained by melt spin quenching. The corresponding preparation parameters were: vacuum degree 1–3 × 10⁻⁶. -2 Pa, induced current 7~9 A, spray casting pressure 0.02~0.04MPa.

[0039] See the photograph of the actual strip obtained in Example 1. Figure 2 (a); The as-cast strip alloy sample obtained in Example 1 was subjected to XRD (e.g., Figure 1 As shown), differential scanning calorimetry (DSC) and magnetic property experiments were used for testing and analysis, which revealed that its structure is a single amorphous state (as shown). Figure 1 As shown in the figure, the initial crystallization temperature is 511℃ and the saturation magnetic induction intensity is 1.53T.

[0040] Example 2:

[0041] The chemical formula of the magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements provided in this embodiment is Fe. 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 It can be prepared by the following method:

[0042] Step 1, Ingredients: Calculate and weigh the required purity of pure Fe, pure Al, pure Cr, pure Sn, pure Y, pure C, pure Si, and FeP and FeB alloys, all with a purity greater than 99 wt.% according to the composition.

[0043] Step 2, Melting the master alloy ingot: Place the raw materials weighed in Step 1 into a vacuum induction melting furnace, and adjust the vacuum degree inside the furnace to 1×10⁻⁶. －2 Pa, the melting temperature is 1400℃~1600℃, the melting time is 2 min, and the raw material is melted three times to make the raw material melt evenly. After cooling in the furnace, the master alloy ingot is taken out.

[0044] Step 3, Preparation of amorphous alloy: The alloy ingot of Example 2 obtained in Step 2 is placed in a rapid solidification device and completely melted using its electromagnetic induction furnace. Then, a rod-shaped block sample of the alloy with a critical diameter of not less than 4 mm is obtained by copper mold casting. The corresponding preparation parameters are: vacuum degree 1~3×10 -2 Pa, induced current 9-10 A, spray casting pressure 0.03-0.05 MPa.

[0045] The as-cast rod-shaped alloy sample obtained in Example 2 was subjected to XRD (e.g., Figure 1 As shown), differential scanning calorimetry (DSC), magnetic property tests, axial compression tests, Vickers microhardness tests, and immersion tests were used for testing and analysis, which revealed that its structure is a single amorphous state (as shown). Figure 1 As shown), the initial crystallization temperature is 505℃, the saturation magnetic induction intensity is 1.46T, the compressive fracture strength is 3.43GPa, the compressive plasticity is 1.2%, the Vickers microhardness is 9.8GPa, and there is no significant weight loss after soaking in 3wt.% NaCl solution for one week.

[0046] Example 3:

[0047] The chemical formula of the magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements provided in this embodiment is Fe. 75 Al 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si 0.5 It can be prepared by the following method:

[0048] Step 1, Ingredients: Calculate and weigh the required purity of pure Fe, pure Al, pure Cr, pure Sn, pure Y, pure Er, pure C, pure Si, and FeP and FeB alloys, all with a purity greater than 99 wt.% according to the composition.

[0049] Step 2, Melting the master alloy ingot: Place the raw materials weighed in Step 1 into a vacuum induction melting furnace, and adjust the vacuum degree inside the furnace to 2×10⁻⁶. －2Pa, the melting temperature is 1450℃~1650℃, the melting time is 2 min, and the raw material is melted 3 times to make the raw material melt evenly. After cooling in the furnace, the master alloy ingot is taken out.

[0050] Step 3, Preparation of amorphous alloy: The alloy ingot of Example 3 obtained in Step 2 is placed in a rapid solidification device and completely melted using its electromagnetic induction furnace. Then, a rod-shaped block sample of the alloy with a critical diameter of not less than 3 mm is obtained by copper mold casting. The corresponding preparation parameters are: vacuum degree 1×10 -2 Pa, induced current 9~10 A, spray casting pressure 0.04~0.06MPa.

[0051] The as-cast rod-shaped alloy sample obtained in Example 3 was subjected to XRD (e.g., Figure 1 As shown), differential scanning calorimetry (DSC), magnetic property tests, axial compression tests, Vickers microhardness tests, and immersion tests were used for testing and analysis, which revealed that its structure is a single amorphous state (as shown). Figure 1 As shown), the initial crystallization temperature is 493℃, the saturation magnetic induction intensity is 1.36T, the compressive fracture strength is 3.33GPa, the Vickers microhardness is 9.5GPa, and there is no significant weight loss after soaking in 3wt.% NaCl solution for one week.

[0052] Example 4:

[0053] The chemical formula of the magnetic FeP-based amorphous alloy microalloyed by the synergistic microalloying of positive and negative mixed thermal elements provided in this embodiment is Fe. 76 Al2Cr2Sn 1.5 La1P7B4C6Si 0.5 It can be prepared by the following method:

[0054] Step 1, Ingredients: Calculate and weigh the required purity of pure Fe, pure Al, pure Cr, pure Sn, pure La, pure C, pure Si, and FeP and FeB alloys, all with a purity greater than 99 wt.% according to the composition.

[0055] Step 2, Melting the master alloy ingot: Place the raw materials weighed in Step 1 into a vacuum induction melting furnace, and adjust the vacuum degree inside the furnace to 1×10⁻⁶. －2 Pa, the melting temperature is 1400℃~1600℃, the melting time is 2 min, and the raw material is melted three times to make the raw material melt evenly. After cooling in the furnace, the master alloy ingot is taken out.

[0056] Step 3, Preparation of amorphous alloy: The alloy ingot of Example 4 obtained in Step 2 is placed in a rapid solidification device and completely melted using its electromagnetic induction furnace. Then, a rod-shaped block sample of the alloy with a diameter of not less than 2 mm is obtained by copper mold casting. The corresponding preparation parameters are: vacuum degree 1×10 -2Pa, induced current 9-10 A, spray casting pressure 0.03-0.05 MPa.

[0057] The cast rod-shaped alloy sample obtained in Example 4 was subjected to XRD (e.g., Figure 1 As shown), differential scanning calorimetry (DSC), magnetic property tests, axial compression tests, Vickers microhardness tests, and immersion tests were used for testing and analysis, which revealed that its structure is a single amorphous state (as shown). Figure 1 As shown), the initial crystallization temperature is 491℃, the saturation magnetic induction intensity is 1.32T, the compressive fracture strength is 3.3GPa, the Vickers microhardness is 9.3GPa, and there is no significant weight loss after soaking in 3wt.% NaCl solution for one week.

[0058] Comparison Patent 1:

[0059] Patent application number 201710364081.7, patent title: "A Method for Preparing an Fe-Based Amorphous Alloy with All Raw Materials Being Low-Purity Industrial Alloys," is selected as the comparative patent 1. The typical embodiment involving the Fe amorphous alloy... 79.32 Mn 0.051 Cr 0.021 Al 0.002 P 10.001 C 8.102 B2Si 0.501 S 0.002 This is a comparative example that meets the requirements. According to industry common sense, Mn, Cr, Al, B, and Si elements in the comparative example can be considered as microalloying elements (alloying elements with a content not exceeding 3 at.%). The heat of mixing between FeMn is 0 kJ / mol, between FeCr is -1 kJ / mol, between FeAl is -11 kJ / mol, between FeB is -26 kJ / mol, and between FeSi is -35 kJ / mol. There are no positive heat-mixing alloying elements. This comparative example has a typical compositional characteristic of being primarily alloyed by a single element with a negative heat of mixing. Note that although according to industry common sense, S element in the comparative example can also be considered a microalloying element, since there is currently no publicly available data on the heat of mixing between FeS, the role of S is not considered in this comparative description. Furthermore, in the typical embodiment 1 of this invention (Fe... 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 () is the amorphous alloy corresponding to the comparative example in this invention.

[0060] Comparative example of amorphous alloy (Fe) in patent 1 79.32 Mn 0.051 Cr 0.021 Al 0.002 P10.001 C 8.102 B2Si 0.501 S 0.002 ) and the typical embodiment 1 of the present invention (Fe 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 The main performance parameters are listed in Table 1. As can be seen from the table, the amorphous alloy in the comparative example is quite similar in its main composition to that of Typical Example 1 of this invention, i.e., the ferromagnetic element is only iron with a content difference of no more than 1 at.%, and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2 at.%. The initial crystallization temperature of the comparative example is 465℃, and the saturation magnetic induction intensity is 1.33T. Both performance parameter values ​​are 46℃ and 0.20T lower than the corresponding performance parameter values ​​of Example 1 of this invention, respectively. This result sufficiently illustrates that "the magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this invention, when the composition is relatively similar (i.e., the ferromagnetic element is only iron with a content difference of no more than 1 at.%, and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2 at.%), has a lower initial crystallization temperature (T) than the magnetic FeP-based amorphous alloy alloyed only with a single thermal element that has a positive or negative mixed relationship with the matrix element Fe." x The saturation magnetic induction intensity is higher than that of magnetic FeP-based amorphous alloys alloyed with a single thermal element that exhibits positive or negative mixed thermal elements with Fe as the matrix element. This invention provides a magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements, exhibiting superior magnetic properties and resistance to crystallization failure under similar conditions. It has significant potential application value as a high-performance magnetic component material in the power and new energy fields. The ferromagnetic element is Fe with a content difference of no more than 1%, and the total content of the same metalloid elements (P, C, B, and Si) differs by no more than 2%.

[0061] Table 1 compares the main performance parameters of the comparative amorphous alloy in Patent 1 with those of Typical Embodiment 1 of this invention.

[0062]

[0063] Comparison Patent 2:

[0064] Meanwhile, patent application number 200910089314.2, patent title: Fe-Al-PCM bulk amorphous alloy with soft magnetic properties and its preparation method, is selected as the comparative patent 2 of this invention, wherein the Fe involved... 79 Al1P9B2C8Si1, Fe 78 Al2P9B2C8Si1, Fe77 Al3P9B2C8Si1, Fe 76 Al4P9B2C8Si1, Fe 75 Al5P9B2C8Si1, Fe 77 Al3P9B2C7Si2, Fe 77 Al3P9B2C6Si3, Fe 77 Al3P9B2C5Si4, Fe 77 Al3P7B6C5Si2, Fe 77 Al3P 11 B4C4Si1 amorphous alloy is used as a comparative example. Specifically, the comparative example Fe in Comparative Patent 2... 79 Al1P9B2C8Si1 and typical embodiment 1 of the present invention (Fe 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 Correspondingly; compared to the comparative example Fe in patent 2 78 Al2P9B2C8Si1, Fe 77 Al3P9B2C8Si1, Fe 76 Al4P9B2C8Si1, Fe 77 Al3P9B2C7Si2, Fe 77 Al3P9B2C6Si3, Fe 77 Al3P9B2C5Si4, Fe 77 Al3P7B6C5Si2, Fe 77 Al3P 11 B4C4Si1 and typical embodiment 2 of the present invention (Fe 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 Correspondingly; compared to the comparative example Fe in patent 2 76 Al4P9B2C8Si1 and Fe 75 Al5P9B2C8Si1 and typical embodiment 3 of the present invention (Fe75Al) 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si 0.5 Corresponding to ).

[0065] Table 2 shows the examples of Example 1 (Fe) in this invention. 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 ) and the corresponding comparative example in patent 2 (Fe 79The main performance parameters of Al1P9B2C8Si1 are shown in the table. It can be seen from the table that the two amorphous alloys have similar main compositional characteristics, namely, the only ferromagnetic element is iron with a content difference of no more than 1 at.%, and the same metalloid elements (i.e., P, C, B, and Si) with a total content difference of no more than 2 at.%. Therefore, Example 1 of this invention can be compared with the comparative example in Patent 2. According to industry common sense, Al, B, and Si elements in the comparative example can be considered as microalloying elements, with the heat of mixing between FeAl being -11 kJ / mol, between FeB being -26 kJ / mol, and between FeSi being -35 kJ / mol. Therefore, this comparative example is a typical example of a single alloying element with a negative heat of mixing. Table 2 shows that the initial crystallization temperature of the comparative example is 469℃ (or 742K), and the saturation magnetic induction intensity is 1.40T. Both performance parameter values ​​are 42℃ and 0.13T lower than the corresponding performance parameter values ​​of Example 1 of this invention, respectively. This result sufficiently demonstrates that "the magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this invention, when the composition is relatively similar (i.e., the ferromagnetic element is only iron and the content difference does not exceed 1 at.%), and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2 at.%), has a higher initial crystallization temperature (T) than the magnetic FeP-based amorphous alloy microalloyed with only a single thermal element that has a positive or negative mixed relationship with the matrix element Fe." x The saturation magnetic induction intensity is at least 10 °C higher than that of magnetic FeP-based amorphous alloys alloyed with a single thermal element that exhibits a positive or negative mixture with Fe as the matrix element. This characteristic further illustrates that the magnetic FeP-based amorphous alloy microalloyed with a positive or negative mixture of thermal elements possesses superior magnetic properties and resistance to crystallization failure under similar conditions, making it a high-performance magnetic component material with greater potential application value in the power and new energy fields. Furthermore, under the conditions that the only ferromagnetic element is Fe with a content difference of no more than 1% and the same metalloid elements (i.e., P, C, B, and Si) with a total content difference of no more than 2%, the saturation magnetic induction intensity is higher than that of magnetic FeP-based amorphous alloys alloyed with a single thermal element that exhibits a positive or negative mixture with Fe as the matrix element.

[0066] Table 2 compares the main performance parameters of the comparative amorphous alloy in Patent 2 with those of Typical Embodiment 1 of this invention.

[0067]

[0068] Table 3 shows Example 2 (Fe) of the present invention. 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 ) and the corresponding comparative example in patent 2 (Fe 78 Al2P9B2C8Si1, Fe 77 Al3P9B2C8Si1, Fe 76Al4P9B2C8Si1, Fe 77 Al3P9B2C7Si2, Fe 77 Al3P9B2C6Si3, Fe 77 Al3P9B2C5Si4, Fe 77 Al3P7B6C5Si2, Fe 77 Al3P 11 The main performance parameters of B4C4Si1 are shown in the table. As can be seen from the table, the main compositional characteristics of Example 2 in this invention and the comparative examples in Patent 2 are quite similar, namely, the only ferromagnetic element is iron, and the content difference does not exceed 1 at.%, and the same metalloid elements (i.e., P, C, B, and Si) are present, with a total content difference not exceeding 2 at.%. Therefore, Example 2 in this invention can be compared with the comparative examples in Patent 2. According to industry common sense, Al, B, and Si can be considered the main microalloying elements in the comparative examples, with the mixing heat between FeAl being -11 kJ / mol, between FeB being -26 kJ / mol, and between FeSi being -35 kJ / mol. Therefore, this comparative example is a typical example of compositional characteristics mainly based on single alloying with elements having negative mixing heat. Table 3 also shows that the highest initial crystallization temperature in the comparative examples is 492℃ (765K), which is 13℃ lower than the corresponding value in Example 2 of this invention. Meanwhile, the highest saturation magnetic induction intensity in the comparative example was 1.44T, which is lower than the corresponding value (1.46T) in Example 2 of this invention. This result sufficiently illustrates that "the magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this invention, when the composition is relatively similar (i.e., the ferromagnetic element is only iron and the content difference does not exceed 1 at.%, and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2 at.%), has a lower initial crystallization temperature (T) than the magnetic FeP-based amorphous alloy microalloyed with only a single thermal element that has a positive or negative mixed relationship with the matrix element Fe." x The saturation magnetic induction intensity is at least 10 °C higher than that of magnetic FeP-based amorphous alloys alloyed with a single alloy of Fe as the base element, where the ferromagnetic element is only Fe and the content difference does not exceed 1 at.% and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2%. This characteristic further illustrates that the magnetic FeP-based amorphous alloy microalloyed with positive or negative mixed thermal elements of this invention exhibits superior magnetic properties and resistance to crystallization failure under similar conditions, making it a high-performance magnetic component material with greater potential application value in the power and new energy fields.

[0069] Table 3 compares the main performance parameters of the comparative amorphous alloy in Patent 2 with those of Typical Embodiment 2 of the present invention.

[0070]

[0071] Furthermore, as can be seen from Table 3, the critical diameter of all comparative examples is smaller than that of Example 2 in this invention (Fe). 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 The results show that, under similar compositional characteristics (where the ferromagnetic element is only Fe with a content difference of no more than 1% and the metalloid elements are the same (i.e., P, C, B, and Si) with a total content difference of no more than 2%) and magnetic properties (saturation magnetic induction intensity difference of no more than 0.1T), compared with magnetic FeP-based amorphous alloys alloyed with a single alloy of positive or negative mixed thermal elements among the Fe matrix element, the alloy composition of this invention can achieve a larger critical diameter by optimizing the alloy composition. This characteristic is beneficial for obtaining larger-sized alloys and their components without changing existing preparation process conditions, thereby effectively expanding the application fields of this type of alloy.

[0072] Table 4 shows Example 3 (Fe) of the present invention. 75 Al 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si 0.5 ) and the corresponding comparative example in patent 2 (Fe 76 Al4P9B2C8Si1 and Fe 75The main performance parameters of Al5P9B2C8Si1 are shown in the table. It can be seen from the table that the main compositional characteristics of these amorphous alloys in Example 3 of this invention are quite similar to those in Comparative Patent 2, namely, the only ferromagnetic element is iron, and the content difference does not exceed 1 at.%, and the same metalloid elements (i.e., P, C, B, and Si) have a total content difference of no more than 2 at.%. Therefore, Example 2 of this invention can be compared with these comparative examples in Comparative Patent 2. According to industry common sense, B and Si can be considered as the main microalloying elements in the comparative examples, with the heat of mixing between FeB being -26 kJ / mol and the heat of mixing between FeSi being -35 kJ / mol. Therefore, this comparative example is a typical example of a single alloying element with a negative heat of mixing. Table 4 also shows that the highest initial crystallization temperature in the comparative examples is 481℃ (754K), which is 12℃ lower than the corresponding value in Example 3 of this invention. At the same time, the highest saturation magnetic induction intensity in the comparative examples is 1.31T, which is lower than the corresponding value (1.36T) in Example 3 of this invention. This result also sufficiently demonstrates that "the magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements provided in this invention, under similar compositional characteristics (where the ferromagnetic element is only Fe and the content difference does not exceed 1%, and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2%), has a lower initial crystallization temperature (T) than the magnetic FeP-based amorphous alloy microalloyed with only a single thermal element that exhibits positive or negative mixed thermal interaction with the matrix element Fe." x The saturation magnetic induction intensity is at least 10 °C higher than that of magnetic FeP-based amorphous alloys alloyed with a single alloy of Fe as the base element, where the ferromagnetic element is only Fe and the content difference does not exceed 1 at.% and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2%. This characteristic further illustrates that the magnetic FeP-based amorphous alloy microalloyed with positive or negative mixed thermal elements of this invention exhibits superior magnetic properties and resistance to crystallization failure under similar conditions, making it a high-performance magnetic component material with greater potential application value in the power and new energy fields.

[0073] Table 4 compares the main performance parameters of the comparative amorphous alloy in Patent 2 with those of Typical Embodiment 3 of the present invention.

[0074]

[0075] Furthermore, as can be seen from Table 4, although the comparative example (Fe) 76 The critical diameter of Al4P9B2C8Si1 is similar to that of Example 3 of this invention (Fe 75 Al 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si0.5 The critical diameter of all alloys is 3.0 mm, but their saturation magnetic induction intensity is lower than the corresponding value in Example 3 of this invention. This result sufficiently demonstrates that "compared with magnetic FeP-based amorphous alloys that are alloyed solely with a single thermal element that exhibits positive or negative mixing with the base element Fe, the alloy of this invention has superior magnetic properties (i.e., higher saturation magnetic induction intensity) when the compositional characteristics (the ferromagnetic element is only Fe and the content difference does not exceed 1%, and the metalloid elements are the same (i.e., P, C, B, and Si) and the total content difference does not exceed 2%) and the alloy amorphous forming ability (i.e., the critical diameter of rod-shaped bulk materials or the critical thickness of strip-shaped materials) are the same." This characteristic further indicates that the magnetic FeP-based amorphous alloy of this invention, which is micro-alloyed with positive and negative mixed thermal elements, has superior performance characteristics and greater potential application value than magnetic FeP-based amorphous alloys that are alloyed solely with a single thermal element that exhibits positive or negative mixing with the base element Fe.

[0076] The above examples illustrate the present invention only to aid in understanding it and are not intended to limit the scope of the invention. Those skilled in the art can make various simple deductions, modifications, or substitutions based on the principles of this invention.

Claims

1. A magnetic FeP-based amorphous alloy microalloyed with a combination of positive and negative thermal elements, characterized in that, The chemical formula of the amorphous alloy is Fe. a Al b Cr c Sn d RE e P f B g C h Si i In the formula, RE represents rare earth elements; Al, Cr, Sn, RE, and Si are microalloying elements; the content of each element in the formula is expressed as an atomic percentage (at.%), specifically as follows: b is 0-2, c is 0.5-3, d is 0.5-2, e is 0.2-2, f is 6-11, g is 4-7, h is 5-11, i is 0.5-2, and the remainder is Fe, and a+b+c+d+e+f+g+h+i=100; the RE is one or more of Y, Er, Gd, Dy, La, and Ce.

2. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements according to claim 1, characterized in that, The microalloying elements include at least one positive mixing heat microalloying element that has a positive mixing heat with Fe, and at least one negative mixing heat microalloying element that has a negative mixing heat with Fe.

3. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements according to claim 1, characterized in that, The positive mixed thermal microalloying elements include Sn, La, and Ce; the negative mixed thermal microalloying elements include Al, Cr, Si, Y, Er, Gd, and Dy.

4. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements according to claim 1, characterized in that, The amorphous alloy is a strip material with a thickness of 20-30 μm.

5. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements according to claim 1, characterized in that, The amorphous alloy is a rod-shaped bulk material with a maximum critical diameter of not less than 4 mm.

6. The magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements according to claim 1, characterized in that, The chemical formula of the amorphous alloy is Fe. 80 Cr 0.5 Sn 0.5 Y 0.5 P7B6C5Si 0.5 or Fe 77 Al1Cr1Sn1Y 0.5 P7B6C6Si 0.5 or Fe 75 Al 1.5 Cr1Sn1Y 0.5 Er 0.5 P7B7C6Si 0.5 or Fe 76 Al2Cr2Sn 1.5 La1P7B4C6Si 0.5 .

7. The method for preparing magnetic FeP-based amorphous alloys microalloyed by synergistic microalloying of positive and negative mixed thermal elements according to claim 1, characterized in that, include: Ingredients: According to Fe a Al b Cr c Sn d RE e P f B g C h Si i Weigh each raw material according to its chemical formula; Melting the master alloy ingot: Place the weighed raw materials into a vacuum induction melting furnace and melt them 1 to 5 times to make the raw materials melt evenly. After cooling in the furnace, take out the master alloy ingot. Preparation of amorphous alloys: The master alloy ingot is completely melted in an induction furnace using a rapid solidification apparatus to obtain an alloy melt. The alloy melt is then rapidly cooled and solidified using a melt spin quenching method or a copper mold casting method to obtain Fe. a Al b Cr c Sn d RE e P f B g C h Si i Amorphous alloy.

8. The preparation method according to claim 7, characterized in that, The alloy melt is rapidly cooled and solidified by the copper mold casting method to obtain a rod-shaped block material, the maximum critical diameter of the rod-shaped block material being not less than 4 mm; the alloy melt is rapidly cooled and solidified by the melt spin quenching method to obtain a strip material, the thickness of the strip material being 20-30 μm.

9. The preparation method according to claim 7, characterized in that, The conditions for smelting the master alloy ingot are: adjusting the vacuum degree inside the furnace to ≤3×10 -2 Pa, melting temperature 1300 ℃~1700 ℃, single-pass melting time 1~4 min; The conditions for preparing the ribbon material by the melt spin quenching method are: vacuum degree 1~3×10⁻⁶ -2 Pa, induced current 7~10 A, spraying pressure 0.02~0.05 MPa, copper wheel speed 2500~3500 r / min; The conditions for preparing bulk materials using the copper mold casting method are: vacuum degree 1~3×10⁻⁶. -2 Pa, induced current 7~10 A, spray casting pressure 0.03~0.06 MPa.

10. The application of the magnetic FeP-based amorphous alloy microalloyed with positive and negative mixed thermal elements as described in any one of claims 1-6 in the preparation of soft magnetic component materials and corrosion-resistant and wear-resistant coating materials.

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