CN1403615A - Iron-base bulk amorphous soft-magnetic alloy material - Google Patents

Abstract

The invention belongs to the field of production of functional materials. It is more suitable for preparing iron-based bulk amorphous soft magnetic alloy materials with good soft magnetic properties. The iron-based bulk amorphous soft magnetic alloy material is characterized in that the specific chemical composition of the iron-based bulk amorphous soft magnetic alloy material is Fe.75-95%; Sn.0.5-10%; B.0.2-10 %; Al.≤6%; V.≤10%; Nb.≤10%; Mo.≤10%; P.≤15%; C.≤5; Si.≤10; Cr, Mn, W, Ta, Any one or the sum of two or more of Nd and Cu elements ≤ 10%. Compared with the prior art, the iron-based bulk amorphous soft magnetic alloy material of the present invention has a wide ultra-cold liquid phase region and good use effects in various soft magnetic performance technical indicators.

Description

Iron-based bulk amorphous soft magnetic alloy materials

technical field

The invention belongs to the field of production of functional materials. It is more suitable for preparing iron-based bulk amorphous soft magnetic alloy materials with good soft magnetic properties.

Background technique

With the rapid development of the electronics industry, the technical performance indicators of various electronic components used in various fields are also constantly improving. Therefore, the use of amorphous alloys as the necessary materials for soft magnetic materials has long been widely used. use. As we all know, the current preparation method of amorphous alloy materials generally adopts the single-roll method. The working principle of the single-roll method is to directly spray molten steel onto the chilled surface of a high-speed rotating copper roll for rapid solidification. Therefore, the preparation method can be Continuous mass production of amorphous alloy thin strips can be industrially produced in batches. This method has in recent years become one of the most important methods for the continuous production of thin strips of amorphous alloys. In 1988, Akihisa Inoue and others in Japan carried out research and development work on the glass forming ability (GFA) of the multi-element amorphous alloy system, and used methods such as water quenching and die casting, and successively discovered Mg-, Ln-, Zr-, Pd-Cu-, Pd-Fe-, Ti- and several other alloy systems with low critical cooling rate (R _c ) and wide supercooled liquid region. However, none of the above bulk amorphous alloys obtained ferromagnetic properties. The supercooled liquid phase region is an important index to measure the amorphous formation ability of alloys. Generally speaking, the traditional amorphous alloy does not have a supercooled liquid phase region, but the existence of a wide supercooled liquid phase region (ΔT _x > 5OK) indicates that the alloy has a greater potential anti-crystallization ability. As the width of the supercooled liquid phase region (ΔT _x ) increases, the critical cooling rate (R _c ) required for the alloy to form an amorphous state decreases, so the alloy's amorphous formation ability (GFA) increases. Because when the interval between the glass transition temperature (T _g ) and the crystallization temperature (T _x ) is larger, the thermal stability of the molten metal above T _g is higher, the alloy is less likely to crystallize, and the amorphous state is more stable. The easier it is to form bulk amorphous. The size of the supercooled liquid phase region is characterized by the following formula: supercooled liquid phase region width (ΔT _x ) = crystallization temperature (T _x ) - glass transition temperature (T _g ). Unit: K. Generally, a differential scanning calorimeter is used to measure the glass transition temperature T _g and the crystallization temperature T _x .

In the 7 years since 1995, Inoue Akihisa and others have obtained four types of ferromagnetic bulk amorphous alloys, namely (1) Fe-(Al, Ga)-(P, C, B) and Fe-Ga-(P,C,B),

(2) Fe-(Zr, Hf, Nb)-B, (3) Fe-(Cr, Mo)-B-C, (4) Fe-Co-Ln-B. Should

The Fe-like bulk amorphous alloy system has a wide supercooled liquid phase region (ΔT _x ) and a high saturation magnetic induction

strength, and low coercive force and other magnetic properties. See Table 1.

Table 1 Properties of Akihisa Inoue’s partial Fe-based bulk amorphous soft magnetic alloy in the prior art Alloy ΔT _x (K) B _s (T) B _r /B _s H _c (A/m) μ _o (1kHz) Fe ₇₂ Al ₅ Ga ₂ P ₁₀ C ₆ B ₄ Si ₁ 63 1.10 0.38-0.45 0.5-12.7 7000-12000 Fe ₇₂ Al ₅ Ga ₂ P ₁₁ C ₆ B ₄ 61 1.07 about 0.40 5.1 9000 Fe ₇₄ Al ₄ Ga ₂ P ₁₂ Si ₄ B ₄ 49 1.14 0.35 6.4 19000 Fe ₆₂ Nb ₈ B ₃₀ 71 0.68 - 2.6 19300 Fe ₅₆ Co ₇ Ni ₇ Zr ₁₀ B ₂₀ 68 0.96 0.60 2.41 17700 Co ₄₀ Fe ₂₂ Nb ₈ B ₃₀ 81 0.41 - 2.0 29300 Fe ₆₂ Co _9.5 Gd _3.5 B ₂₅ 63 1.41 - 1.9 11000

However, the main disadvantages of this Fe-based bulk amorphous alloy are that the material itself has the characteristics of high loss, low square ratio and magnetic permeability μ _m , and expensive metal Ga, which still has a certain distance from practicality.

The purpose and content of the invention

The purpose of the invention is to propose an iron-based bulk amorphous soft magnetic alloy material with a wide ultra-cooled liquid phase region and good technical indicators of soft magnetic properties.

The iron-based bulk amorphous soft magnetic alloy material proposed by the present invention is mainly suitable for soft magnetic amorphous alloy materials. We consider that in order to make the material have ideal soft magnetic properties and a wider ultra-cooled liquid phase region, so A soft magnetic alloy material based on FeSnB is proposed. The purpose of the present invention is to improve the material properties and various magnetic properties of the alloy of the present invention by rationally adjusting the alloy composition and adding some other trace metal elements. According to the above-mentioned requirements and design considerations, the iron-based bulk amorphous soft magnetic alloy material proposed by the present invention is characterized in that the specific chemical composition of the soft magnetic alloy material is (% by weight): Fe.75-95%; Sn .0.5-10%; B.0.2-10%; Al.≤6%; V.≤10%; Nb.≤10%; Mo.≤10%; P.≤15%; C.≤5; Si. ≤10; the sum of any one or two or more of Cr, Mn, W, Ta, Nd, Cu elements ≤10%. For the iron-tin-boron-based bulk amorphous soft magnetic alloy material proposed by the present invention, it is necessary to consider that the material has a wide supercooled liquid phase region, and at the same time, the material should obtain excellent soft magnetic properties. Therefore, in the composition of the material of the present invention, iron is still adopted as the main constituent element of the soft magnetic material of the present invention, and boron is added as an important element that is conducive to the formation of amorphous, and the addition of tin element is to help expand the supercooling liquid. At the same time, tin can also improve the process characteristics of alloy materials during casting, and has the advantage of being cheap. In the iron-based bulk amorphous soft magnetic alloy material of the present invention, in order to further increase the width of the supercooled liquid phase region of the amorphous alloy and improve the soft magnetic properties of the alloy material, some other elements, such as adding P, Elements such as C and Si are metalloid elements that are conducive to the formation of amorphous materials. The addition of V, Al, Nb, Mo and other elements is considered for widening the ultra-cooled liquid phase region and forming amorphous bulk materials. Therefore, Fe is added as the main ferromagnetic element in the composition of the amorphous bulk material of the present invention, and Sn is an alloying element. In addition to being cheap, it is mainly used to reduce the melting point of the alloy, which can obviously improve the performance of the amorphous alloy material. The process at the time of casting. B is a metalloid element. In addition to reducing the critical cooling rate for forming amorphous alloys, its main function is to form amorphous alloys and improve the magnetic properties of amorphous alloys, such as square ratio. Al is an alloying element, which can be added together with Sn to further expand the width of the supercooled liquid phase region. P and Si are metalloid elements that can reduce the critical cooling rate for forming amorphous alloys, and are mainly conducive to the formation of amorphous alloys. C It is a metalloid element, which can increase the saturation magnetic induction of amorphous alloys and is beneficial to the formation of amorphous alloys. V, Mo, and Nb are alloying elements. In addition to further expanding the width of the supercooled liquid phase region, they can also increase the alloy's Heat treatment stability. The material of the iron-tin-boron-based amorphous alloy of the present invention can be prepared by a single-roll method or a copper mold casting method. The single-roll method is to take a set amount of master alloy rods and put them into the nozzle bag of the single-roll spraying machine. The main process parameters are adjusted as follows: the nozzle gap width at the lower end of the nozzle package is 0.2-0.6mm, the nitrogen or argon injection pressure can be set at 0.01-0.5MPa, the distance between the nozzle and the copper cooling roller is 0.05-0.30mm, and the copper cooling roller is adjusted The speed of the wheel rim is 15-40m/s. The prepared amorphous strips have a width of 2-10 mm and a thickness of 20-50 μm. The equipment used is a single-roller belt spraying machine. The bulk amorphous sample of the present invention is prepared by adopting the "copper mold suction casting method". The principle is to use gas pressure to push the metal liquid, connect the copper mold to the vacuum, and introduce argon positive pressure into the furnace cavity, and use the arc After the alloy is melted, the vacuum valve is opened to suck the alloy into the copper mold (by using the gas pressure of the furnace cavity) into the copper mold. The bulk amorphous sample in the present invention is prepared by the "copper mold suction casting method". (In order to reduce the influence of the oxygen content in the furnace cavity, an electric arc will be used to melt a titanium block to absorb the oxygen in the furnace cavity before melting the alloy, and then melt the sample.) Adopt the ultra-cold liquid phase region of the present invention For rods with a diameter of 1mm and 2mm made of iron-tin-boron alloy, in order to obtain a circular amorphous iron core sample, the groove of the copper mold can be directly designed as a circular groove, and the sample taken out after casting is a circular groove. Block core.

Adopt the prepared sample of the iron-tin-boron-based amorphous alloy with wide ultra-cold liquid phase region of the present invention, through different detection methods: 1. differential scanning calorimetry analysis; adopt differential scanning calorimeter to measure amorphous Glass transition temperature T _g and crystallization temperature T _x of the sample. Put the sample of the amorphous strip to be tested into the sample pan, and take about 10 mg of the strip each time. The temperature range of the analysis is 373 to 853K, the heating rate is controlled at 10-40K/min, and helium is used as the protective atmosphere, and the flow rate is 20-50cc/min. 2. X-ray diffraction analysis: use X-ray diffraction analyzer to identify the structure of the alloy, scan continuously in the θ-2θ wide-angle incident mode, the scanning speed is 2 degrees per minute, from 20 degrees to 110 degrees, the operating voltage is 30kV, the current It is 20mA, and the incident light source is a Co target. 3. Scanning electron microscope: scan the XY grid on the cross section of the sample with the electron beam, and scan in the same XY mode on the cathode ray tube. The position of each group of electron beams on the sample and each point on the cathode ray tube are determined. Point-by-point correspondence, the image of the sample is formed. 4. Iron core winding; the prepared amorphous strip is wound into an iron core with an inner diameter of 23 mm and an outer diameter of 25-31 mm. 5. Heat treatment of the iron core: put the iron core of the amorphous sample to be tested into a vacuum heat treatment furnace, and heat it for 5-300 minutes at a temperature of 320°C-565°C according to the measurement requirements. 6. Static magnetic measurement: measure the static magnetic properties of the heat-treated amorphous sample iron core by impact method, and use the impact galvanometer as an integrator to test the change of magnetic flux in the sample. 7. Dynamic magnetic measurement: measure the corresponding B _m value of the heat-treated amorphous sample iron core under different AC magnetic field H _m , and the B _m -H _m curve made at this time is the dynamic magnetization under the AC magnetic field curve. The dynamic magnetization curves were measured by voltammetry. Use a voltmeter to measure the voltage U corresponding to B, and use an ammeter to measure the current I corresponding to H, so as to determine the B _m (H _m ) magnetization curve. The magnetization field is: H _m =1.414 IN ₁ /l; in the formula, N ₁ is the total number of turns of the magnetization coil, I is the effective value of the magnetization current measured by the ammeter, and l is the average magnetic circuit length of the sample. Use a rectifier voltmeter to measure the average value U _av of the induced electromotive force of the measuring coil N ₂ , then it can be calculated: B _m = U _av /(4fN ₂ A _s ); in the formula, f is the frequency of the magnetizing current, and A _s is The cross-sectional area of the sample.

Compared with the prior art by using the iron-based bulk amorphous soft magnetic alloy material of the present invention, the iron-based bulk amorphous soft magnetic alloy material has a wide ultra-cooled liquid phase region and various soft magnetic performance technical indicators are good. Effect. According to the above-mentioned measurement of the amorphous sample of the present invention and the results of Table 3 in the embodiments of the present invention, it can be seen that in the iron-tin-boron-based bulk amorphous soft magnetic alloy of the present invention, most of the bulk amorphous alloy soft magnetic It can be obviously superior to existing metal materials, and its characteristics have the following points:

(1) The iron-based bulk amorphous soft magnetic alloy material of the present invention has a wide ultra-cooled liquid phase region, such as No. 1, 2, 3, 9, and 10 alloys;

(2) The iron-based bulk amorphous soft magnetic alloy material of the present invention has a high B ₁₀ , such as No. 1, 4, 5, and 6 alloys;

(3) The iron-based bulk amorphous soft magnetic alloy material of the present invention has a high square ratio, such as No. 3 alloy;

(4) The iron-based bulk amorphous soft magnetic alloy material of the present invention has a high _μm , such as No. 1, 5, 7, 8, and 10 alloys;

(5) The iron-based bulk amorphous soft magnetic alloy material of the present invention has a high effective magnetic permeability μ _e , such as No. 7 and No. 8 alloys;

(6) The iron-based bulk amorphous soft magnetic alloy material of the present invention has low H _c , such as No. 3, 5, 6, 7, 8, and 10 alloys;

(7) The iron-based bulk amorphous soft magnetic alloy material of the present invention has low loss P, such as No. 3, 5, 7, and 8 alloys.

Description of drawings

In the accompanying drawings of the iron-based bulk amorphous soft magnetic alloy material of the present invention, Fig. 1 is a bulk amorphous alloy round rod with a diameter of 1 mm and 2 mm for alloy numbers 3, 5, and 10 prepared by the "suction casting method" Figure 2 is the X-ray diffraction pattern of the cross-section of alloy No. 5 and 10 block alloy rods with a diameter of 2mm. It can be seen from the diffraction pattern that the alloy rod is amorphous, and Fig. 3 is an alloy with a diameter of 2mm Scanning electron microscope photographs of the cross-sections of the bulk amorphous alloy rods No. 5 and No. 10. It can be seen from the photos that there are no grains and defects in the cross-section of the amorphous alloy round rods. Figure 4 is the alloy No. 10 amorphous strip The differential scanning calorimetry curve of this curve shows that the glass transition temperature and crystallization temperature of the amorphous alloy are 696.14K and 745.95K respectively, so the width of the supercooled liquid phase region of the amorphous alloy is 49.81K, and Fig. 5 is Alloy 5 and 10 annular amorphous alloy iron cores (5×8×1mm) prepared by “suction casting method”. Figure 6 shows alloy 6 and 10 annular amorphous alloy iron cores prepared by “suction casting method” ( 6×10×1mm).

Example

Adopt within the composition scope of iron-based bulk amorphous soft magnetic alloy material of the present invention, we have done 10 groups of experiments altogether (seeing table 2), wherein serial number 1,2,4,7,8,9 are that thickness is in 25- 50μm amorphous ribbon samples, No. 3 and 10 are amorphous rod samples with a diameter of φ1mm. Serial numbers 5 and 10 are amorphous rod samples with a diameter of φ2mm, serial numbers 5 and 10 are amorphous ring samples with an inner diameter of 5×outer diameter 8×height 1mm, and serial numbers 6 and 10 are amorphous samples with an inner diameter of 6×outer diameter 10×height 1mm For ring samples, the equipment used is a single-roller belt spraying machine. The preparation process is to take 50 grams of master alloy rods with serial numbers 1, 2, 4, 7, 8, and 9 and put them into the nozzle bag of the single-roller belt spraying machine. . The main process parameters are adjusted as follows: the nozzle gap width at the lower end of the nozzle package is 0.5mm, the nitrogen or argon injection pressure can be set at 0.2MPa, the distance between the nozzle and the copper cooling roller is 0.20mm, and the copper cooling roller rim speed is adjusted to 30m/ s. The prepared amorphous strip has a width of 8 mm and a thickness of 35 μm. Using the "suction casting method" to prepare serial numbers 5, 6, and 10, they were respectively prepared into amorphous annular samples with an inner diameter of 5×outer diameter 8×height 1mm and an inner diameter of 6×outer diameter 10×height of 1mm. A positive pressure of argon gas with a pressure of 0.2Mpa is introduced into the cavity. After the alloy is melted by an electric arc, the vacuum valve is opened to connect the cavity of the copper mold with a vacuum (<1.0×10 ^-2 Pa), and the metal liquid is pushed by argon gas. , the alloy is inhaled (squeezed in by the gas pressure of the furnace chamber) into the copper mold, and the samples taken out after casting are ring-shaped block iron cores of different set sizes. Following table 2 is the composition table (weight %) of the embodiment of the present invention; Table 3 is the performance table of the embodiment of the present invention; Table 4 is the annular iron core (φ5 × φ8 × 1mm of sequence number 6, 10 in the embodiment) ) soft magnetic properties. Table 2 Composition table (weight %) of the embodiment of the present invention serial number sn Al P Si B C Mo V Nb Cr mn W Ta Nd Cu Fe 1 2.55 - - - 5.11 - - - - - - - - - - Remain 2 0.83 - 6.92 2.09 0.81 - - - - - - - - - - Remain 3 4.74 2.16 7.43 2.24 0.86 - - - - - - - - - - Remain 4 4.98 2.27 1.95 1.77 2.27 2.65 - - - - - - - - - Remain 5 3.80 2.18 3.78 3.79 1.46 1.24 - - - - - - - - - Remain 6 4.90 2.23 2.56 2.32 2.68 - - - - - - - - 3.17 - Remain 7 4.62 2.10 6.03 2.19 0.84 - 3.74 - - 1.56 - - - - - Remain 8 3.48 1.22 5.79 1.83 1.03 - - 1.96 - - 2.45 2.33 - - 1.41 Remain 9 3.68 4.35 5.65 1.95 0.92 - - - 4.03 - - - 1.02 - 0.74 Remain 10 4.58 2.05 4.87 2.35 1.14 0.47 2.42 - - - - - - - - Remain

The performance table of the embodiment of the present invention of table 3 Alloy serial number ΔT _x (K) B _r (T) B ₁₀ (T) B _r /B _{10 μm} μ _e (1kHz) H _c (A/m) P _50Hz (W/kg) 1 65 0.437 1.465 0.30 9.6×10 ⁴ - 6.2 - 2 46.5 0.446 1.114 0.40 4.8×10 ⁴ - 7.687 0.249(0.9T) 3 50.3 0.616 1.182 0.52 1.8×10 ⁵ - 3.449 0.161(1.1T) 4 37.2 1.382 1.454 0.95 9000 - 81.09 3.574(1.3T) 5 31.7 0.761 1.305 0.56 1.9×10 ⁵ - 3.635 0.225(1.3T) 6 21.0 1.123 1.357 0.83 - - 4.526 - 7 34.6 0.725 1.112 0.65 5.3×10 ⁵ 7.0×10 ⁴ 0.725 0.096(1.1T) 8 40.9 0.736 1.227 0.60 1.6×10 ⁵ 6.6×10 ⁴ 1.870 0.153(1.2T) 9 51.4 0.294 0.881 0.33 - - 7.820 - 10 49.8 0.74 1.175 0.63 2.3×10 ⁵ - 1.52 - Table 4 The soft magnetic properties of the toroidal iron core (5×8×1mm) with serial number 10 in the embodiment Soft Magnetic Properties B ₁₀ (T) B ₂₀ (T) B ₃₀ (T) B _r (T) H _c (A/m) quenched state 0.658 0.896 1.005 - - annealing 1.072 1.206 - 0.012 4.82

Claims (2)

1. iron-base bulk amorphous soft-magnetic alloy material, the concrete Chemical Composition that it is characterized in that forming this iron-base bulk amorphous soft-magnetic alloy material is (weight %): Fe.75-95%; Sn.0.5-10%; B.0.2-10%; Al.≤6%; V.≤10%; Nb.≤10%; Mo.≤10%; P.≤15%; C.≤5; Si.≤10; In Cr, Mn, W, Ta, Nd, the Cu element any one≤10%.

2. according to the described alloy material of claim 1, it is characterized in that any two kinds and two or more sum≤10% in Cr, Mn, W, Ta, Nd, the Cu element in this composition.

Images