WO2022227425A1

WO2022227425A1 - Amorphous alloy strip and preparation method therefor

Info

Publication number: WO2022227425A1
Application number: PCT/CN2021/124999
Authority: WO
Inventors: 刘国栋; 史杨; 李百松; 李志刚; 陈文智
Original assignee: 安泰非晶科技有限责任公司; 安泰科技股份有限公司
Priority date: 2021-04-25
Filing date: 2021-10-20
Publication date: 2022-11-03
Also published as: CN115247242A

Abstract

The present invention provides an amorphous alloy strip and a preparation method therefor. The width of the amorphous alloy strip is ≥80 mm, the thickness thereof is ≥30 μm, and the toughness value thereof is <4.0. The amorphous alloy strip is obtained by cooling an alloy liquid by means of a cooling roller. The cooling roller comprises a roller sleeve. The thermal conductivity of the roller sleeve, the maximum usable thickness of the roller sleeve, and the thickness of the amorphous alloy strip have the following relationship: a requirement on the cooling capacity of the cooling roller during preparation of a strip is achieved by means of optimized fitting among the thickness of the strip, the thermal conductivity of the roller sleeve, and the maximum usable thickness of the roller sleeve, to thereby prepare a strip having a width of ≥80 mm and a thickness of ≥30 μm.

Description

A kind of amorphous alloy strip and preparation method thereof

technical field

The invention belongs to the technical field of alloy preparation, and particularly relates to an amorphous alloy strip and a preparation method thereof.

Background technique

Amorphous alloys are a class of soft magnetic materials that have developed rapidly in recent years. Compared with traditional electrical steel, ferrite and other soft magnetic materials, they have higher permeability and lower AC loss, and have been widely used in transformers. , inductors, transformers, motor stators and other magnetic components of the iron core.

Amorphous alloy strips are generally manufactured by plane flow technology. The method is: melting a certain proportion of raw materials into an alloy liquid in a smelting furnace; then, pouring the alloy liquid into a nozzle package with a slit nozzle at the bottom; the nozzle package The alloy liquid flows out from the nozzle, spreads on the outer circumferential surface of the high-speed rotating copper alloy cooling roll under the nozzle, and forms a molten pool of a certain size between the cooling roll surface and the bottom surface of the nozzle, and the alloy liquid is quickly drawn out and quickly. Cooling, and at the same time, the alloy liquid in the nozzle slit is continuously replenished into the molten pool, thereby forming a continuous thin strip with an amorphous structure. The thin strip is close to the outer surface of the cooling roll and rotates at a high speed with the cooling roll, and is peeled off by high-pressure gas or mechanical device at an appropriate position on the outer circumferential surface of the cooling roll, and finally the thin strip is wound into a roll by a coiling device.

In the manufacturing process of amorphous strip, rapid solidification of the alloy liquid is a necessary condition for the strip formed by cooling to have an amorphous structure. For the common amorphous strips in the prior art, the cooling rate of the alloy liquid to form solid amorphous strips near the glass transition temperature T _g should reach more than 10 ⁵ ℃/sec. The temperature at the time of peeling (peeling temperature) should be lower than about 200°C. Also, different amorphous materials have different requirements for cooling rates. If the actual cooling rate of the alloy liquid or the strip does not meet the requirements, the strip will undergo structural relaxation or even crystallization due to insufficient cooling, which will seriously embrittle the strip and seriously deteriorate its properties.

In the manufacturing process of the amorphous strip, the rapid solidification of the alloy liquid and the cooling process of the strip are completed on the outer surface of the cooling roll. The cooling roll is generally assembled from two parts, the annular cooling roll sleeve and the cylindrical roll core. An annular channel is formed between the roll sleeve and the roll core, and high-speed cooling water flows into the channel. In the manufacturing process of the amorphous strip, the heat contained in the alloy liquid must pass through the molten pool, the interface between the alloy liquid and the outer surface of the roll sleeve, the roll sleeve with a certain thickness, and the intersection of the inner surface of the roll sleeve and the cooling water. interface, which is eventually passed to the flowing cooling water. Among them, the thermal conductivity of the cooling roll sleeve determines the cooling capacity of the cooling system to a large extent, and thus plays a decisive role in the formation of the amorphous strip. In order to achieve rapid solidification of the alloy liquid, copper alloys with high thermal conductivity are generally used as cooling roll sleeve materials, such as chromium zirconium copper, beryllium bronze, nickel silicon bronze, etc. in the prior art.

Among the amorphous alloy strips, iron-based amorphous strips are the most widely used, and their main advantages are low cost and high saturation magnetic induction, which can be applied to the cores of various transformer components. The existing technology can generally manufacture iron-based amorphous strips with a thickness of about 25 microns and a width of 100-300 mm.

With the technological progress of the transformer industry and the intensification of market competition, there is an urgent need for iron-based amorphous alloy wide and thick strips (thickness above 30μm and width above 80mm). For example, in the manufacture of transformer cores, the use of thick strips will reduce the workload of core processing and improve production efficiency; it can also reduce the debris generated by strip breakage, which is conducive to improving the reliability of components.

However, stable production of wide and thick iron-based amorphous alloy strips has always been a problem. For nickel-based or cobalt-based amorphous alloys, their critical cooling rate is relatively low, making it easier to manufacture thick strips. For example, the prior art can produce nickel-based amorphous alloy brazing foils with a thickness of more than 50 microns. However, since the critical cooling rate of iron-based amorphous alloys is higher than that of nickel-based amorphous alloys, when manufacturing iron-based amorphous alloys with a thickness of more than 30 μm, the heat contained in the thick strips is significantly higher than that of ordinary thin strips. The thermal load on the sleeve increases significantly; and the cooling capacity of the cooling roll sleeve used in the prior art is not enough to ensure that the cooling rate of the alloy liquid and the strip is higher than its critical cooling rate, resulting in the produced strip. It is obviously embrittled and even crystallized, so it is difficult to stably manufacture wide and thick iron-based amorphous alloy strips. No relevant solutions are proposed in the prior art.

For example, Chinese patent CN107442750B, Chinese patent CN204486736U and Japanese patent JP3280778B2 respectively propose a method for manufacturing thick amorphous alloy strips by using multiple nozzles, that is, using multiple nozzles adjacent to each other to flow out alloy liquid at the same time, so that the Alloy liquid or already solidified strips are combined into thick strips. However, the technical key to making thick amorphous alloy strips is not how to form the thick strips, but how to ensure that the equipment has sufficient cooling capacity during the manufacturing process of the thick strips, so that the materials can form an amorphous structure.

US Patent No. 4,537,239 discloses a cooling roll for manufacturing amorphous strips. The material is beryllium copper alloy, the diameter is about 380mm, and the thickness of the roll sleeve is about 6.35mm. Because the diameter of the roll sleeve is too small, the bonding time between the strip and the roll surface is very short, so the thickness of the roll sleeve must be very thin to ensure its cooling capacity, so it is impossible to stably manufacture amorphous alloy broadband with a thickness greater than 26 microns.

Chinese invention patent application CN110976794A discloses the manufacturing method of iron-based amorphous alloy strip. By improving the cooling capacity of the cooling system, iron-based amorphous strips with a thickness of up to 40 microns can be realized. The above method of thinning to 20mm can improve the cooling capacity of the roll sleeve. However, the cooling capacity of the roll sleeve is not only related to its thickness, but also depends on its thermal conductivity, and this application does not mention the thermal conductivity of the used roll sleeve, so it lacks practical guidance for the selection of cooling roll sleeve parameters.

Non-patent literature (Guo Qian, Yan Mi. Numerical simulation of temperature field of cooling roll in flat casting process, Rare Metal Materials and Engineering, 2015, Vol. 44, No. 8, 2048-2052) on the manufacture of amorphous alloy strips The temperature field of the cooling roll in the process was simulated and calculated. Under the condition of using a copper alloy with a thermal conductivity of 180W/m·K as the material of the cooling roll, the cooling effect of the iron-based amorphous strip with a thickness of 30 μm and a width of 220 mm was obtained. The best size of the roller: the thickness of the roller sleeve is 10mm, and the diameter of the roller sleeve is 1200mm. However, this document also does not propose a selection scheme for cooling roll sleeves with a thickness of more than 30 μm in amorphous alloy broadband.

To sum up, the existing technology provides some technical solutions for the manufacture of amorphous alloy thick strips from the aspects of amorphous material composition and thick strip formation process, but the core problem of thick strip manufacturing—alloy liquid and strip cooling rate—has not been Providing any guarantee, even some prior art attempts to improve the cooling capacity do not provide a method for producing a thick strip of amorphous alloy with a width of more than 80 mm and a thickness of more than 30 μm with good toughness.

SUMMARY OF THE INVENTION

In view of the above problems, the present invention provides an amorphous alloy strip and a preparation method thereof. The cooling rate of the cooling roller to the alloy liquid in the strip preparation can be realized by the coordination between the thickness of the strip, the thermal conductivity of the roll sleeve, and the available thickness of the roll sleeve. requirements, so as to prepare a strip with a width of ≧80mm and a thickness of ≧30μm.

In order to achieve the above object, the present invention adopts the following technical solutions:

An amorphous alloy strip, the width of the amorphous alloy strip is ≥80 mm, the thickness is ≥30 μm, and the toughness value is less than 4.0.

Preferably, the amorphous alloy strip comprises the following composition: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn, Any one or more of Al or Sn; any one or more of Si, B, P or C with a total content of 15-30at%; one or more of Co or Ni with a total content of 0-20at% one or two; the remainder is Fe.

Preferably, the amorphous alloy strip is obtained by cooling the alloy liquid through a cooling roll, the cooling roll includes a roll sleeve, and the thermal conductivity of the roll sleeve, the maximum usable thickness of the roll sleeve and the thickness of the amorphous alloy strip have The following relationship:

Among them: λ is the thermal conductivity of the roller sleeve, the unit is W/m·K;

d _max is the maximum available thickness of the roller sleeve, the unit is mm;

δ is the average thickness of the amorphous alloy strip, in μm;

The value range of k is 1-2 mm ³ K/W; the optimal value of k can be combined with the properties of the amorphous alloy strip, the width of the amorphous alloy strip and process parameters, the parameters include the temperature of the alloy liquid, the surface line of the cooling roll Speed, roller nozzle spacing, alloy hydraulic pressure at nozzle, molten pool protection parameters, cooling water flow rate and temperature.

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the method comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, The alloy liquid is then sprayed onto the surface of the cooling roll for cooling.

Preferably, the temperature of the alloy liquid is 1250-1450°C; the linear speed of the surface rotation of the cooling roller is 15-30m/s, and the temperature of the cooling roller surface is 70-150°C; the amorphous alloy strip is peeled off. The temperature of the surface of the cooling roll is 120-200° C.; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 20-60 kPa, and the width of the nozzle slit is 0.4-1.0 mm.

Preferably, the temperature of the alloy liquid is 1300-1400°C.

Preferably, the static pressure for spraying the alloy liquid onto the surface of the cooling roll is 25-50 kPa.

Preferably, the temperature of the surface of the cooling roll is 90-120°C.

Preferably, the temperature when the amorphous alloy strip is peeled off the surface of the cooling roll is 140-180°C.

Preferably, the value of λ is 80-350 W/m·K; the value of d _max is 4-20 mm.

Preferably, the value of d _max is 4-20 mm; the value of λ is 100-300 W/m·K.

In the iron-based amorphous alloy of the present invention, Fe is the most important element providing ferromagnetism to the material. Compared with Co or Ni, Fe has the highest atomic magnetic moment, so it can make the alloy have the highest saturation magnetic induction among all amorphous alloys. In order to obtain some special properties such as increasing the induced magnetic anisotropy, Fe can be partially substituted with Co and/or Ni, but the substitution ratio should not be higher than 20at%, otherwise the saturation magnetic induction intensity of the material will be significantly reduced.

A small amount of any one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn, Al or Sn may be added to the iron-based amorphous alloy of the present invention. Several, whose purposes include improving the thermal stability, corrosion resistance or mechanical properties of the alloy, or giving the alloy the ability to form nanocrystalline structures upon subsequent heat treatment. The total amount of these elements should not be higher than 20 at%, otherwise the saturation magnetic induction of the material will be significantly reduced.

Si, B, P, and C in the iron-based amorphous alloy of the present invention are indispensable elements for forming an amorphous structure during rapid solidification of the alloy, and are also called amorphizing elements or vitrifying elements. In order to obtain better amorphous forming ability, two or more elements should be added at the same time. The total content of these elements is between 15-30 at%, and too high or too low content will reduce the amorphous forming ability of the alloy.

Beneficial effects of the invention: The thickness and width of the strip determine the thermal load on the roll sleeve, and in order to achieve a sufficiently high cooling rate under this condition, the thermal conductivity and thickness of the roll sleeve must be reasonably selected. Therefore, the strip thickness, the thermal conductivity of the roll sleeve, and the maximum available thickness of the roll sleeve are mutually restrained and influenced each other. There is an optimal matching range for these three variables to achieve stable production of iron-based amorphous wide and thick strips. The invention provides a method for manufacturing an iron-based amorphous wide-thick strip with a thickness of 30 microns or more and a width of 80 mm or more. According to the specific requirements of other aspects, the material, thickness and other parameters of the roller sleeve should be reasonably selected, so that the roller sleeve has the required thermal conductivity, good thermal fatigue resistance, good performance consistency of the roller sleeve and lower manufacturing cost of the roller sleeve. and other comprehensive characteristics. The iron-based amorphous wide and thick strips made with this kind of roller sleeve can ensure the electromagnetic properties that meet the requirements, and have both good consistency and low cost.

Other features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure pointed out in the description, claims and drawings.

Description of drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative efforts.

Figure 1 shows the relationship between the thermal conductivity of the roll sleeve, the maximum usable thickness of the sleeve and the thickness of the strip according to the present invention.

Detailed ways

In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments These are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Embodiment 1:

An amorphous alloy strip, the amorphous alloy strip has a width of 171 mm and a thickness of 32 μm; the alloy composition of the amorphous alloy strip is Fe ₇₈ Si ₉ B ₁₃ (wherein 78, 9, 13 and other subscript numbers represents the mole percent of the corresponding element).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 171mm and the thickness is 32μm; the temperature of the alloy liquid is 1370°C; the linear speed of the surface rotation of the cooling roll is 22m/ s, the temperature of the surface of the cooling roll is 70 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 120 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 35kPa; The width is 0.8mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 104W/m·K, the thickness of the roll cover is 5.0mm, the inner diameter of the roll cover is 600mm, and the roll cover material is Cu-Be alloy.

Embodiment 2:

This example has the same process and conditions as Example 1, except that the thickness of the roll sleeve is 3.2 mm, the width of the strip is 213 mm, and the thickness is 32 μm.

Embodiment 3:

An amorphous alloy strip, the amorphous alloy strip has a width of 143 mm and a thickness of 38 μm; the alloy composition of the amorphous alloy strip is Fe ₇₈ Si ₉ B ₁₃ (wherein 78, 9, 13 and other subscript numbers represents the mole percent of the corresponding element).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 143 mm and the thickness is 38 μm; the temperature of the alloy liquid is 1390 ° C; the linear speed of the surface rotation of the cooling roll is 20 m/ s, the temperature of the surface of the cooling roll is 150 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 200 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 45kPa; The width is 0.6mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 346W/m·K, the thickness of the roll cover is 17.0mm, and the inner diameter of the roll cover is 1200mm.

Embodiment 4:

This example has the same process and conditions as Example 3, except that the thickness of the roll sleeve is 11.8 mm, the width of the strip is 142 mm, and the thickness is 38 μm.

Embodiment 5:

An amorphous alloy strip, the amorphous alloy strip has a width of 143 mm and a thickness of 38 μm; the alloy composition of the amorphous alloy strip is Fe ₈₂ Si ₄ B ₁₃ C ₁ (wherein the subscript numbers represent the mole percentage. The same below).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 85mm and the thickness is 48μm; the temperature of the alloy liquid is 1380°C; the linear speed of the surface rotation of the cooling roll is 21m/ s, the temperature of the surface of the cooling roll is 80 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 130 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 55kPa; The width is 0.7mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 82W/m·K, the thickness of the roll cover is 48.0mm, and the inner diameter of the roll cover is 600mm.

Embodiment 6:

An amorphous alloy strip, the width of the amorphous alloy strip is 100mm and the thickness is 41μm; the alloy composition of the amorphous alloy strip is Fe ₈₃ Si ₃ B ₁₁ C ₁ P ₂ (wherein the subscript numbers represent the corresponding mole percent of elements).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 100mm and the thickness is 41μm; the temperature of the alloy liquid is 1365°C; the linear speed of the surface rotation of the cooling roll is 22m/ s, the temperature of the surface of the cooling roll is 90 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 140 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 52kPa; The width is 0.7mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 180W/m·K, the thickness of the roll cover is 7.5mm, and the inner diameter of the roll cover is 600mm.

Embodiment 7:

The process and conditions of this example are the same as those of Example 6, except that the thickness of the roll sleeve is 4.5 mm, the width of the strip is 284 mm, and the thickness is 41 μm.

Embodiment 8:

An amorphous alloy strip, the width of the amorphous alloy strip is 85mm and the thickness is 49μm; the alloy composition of the amorphous alloy strip is Fe ₆₀ Co ₁₈ Ta ₂ Si ₈ B ₁₂ (wherein the subscript numbers represent the corresponding mole percent of elements).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 85mm and the thickness is 49μm; the temperature of the alloy liquid is 1360°C; the linear speed of the surface rotation of the cooling roll is 20m/ s, the temperature of the surface of the cooling roll is 100 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 160 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 55kPa; The width is 0.7mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 200W/m·K, the thickness of the roll cover is 11.2mm, and the inner diameter of the roll cover is 1600mm.

Embodiment 9:

The process and conditions of this example are the same as those of Example 8, except that the thickness of the roll sleeve is 5.7 mm, the width of the strip is 85 mm, and the thickness is 49 μm.

Comparative Example 1:

An amorphous alloy strip, the width of the amorphous alloy strip is 170mm and the thickness is 32μm; the alloy composition of the amorphous alloy strip is Fe ₈₂ Si ₄ B ₁₃ C ₁ (wherein the subscript numbers represent the corresponding element mole percent).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid onto the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 170 mm and the thickness is 32 μm; the temperature of the alloy liquid is 1380 ° C; the linear speed of the surface rotation of the cooling roll is 20 m/m s, the temperature of the surface of the cooling roller is 70°C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roller is 120°C; the static pressure of spraying the alloy liquid on the surface of the cooling roller is 45kPa; The width is 0.6mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 104W/m·K, the thickness of the roll cover is 6.5mm, and the inner diameter of the roll cover is 600mm.

Comparative Example 2:

An amorphous alloy strip, the amorphous alloy strip has a width of 143 mm and a thickness of 31 μm; the alloy composition of the amorphous alloy strip is Fe ₈₂ Si ₄ B ₁₃ C ₁ (wherein the numbers represent mole percentages. The same below) ).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 143 mm and the thickness is 31 μm; the temperature of the alloy liquid is 1380 ° C; the linear speed of the surface rotation of the cooling roll is 21 m/ s, the temperature of the surface of the cooling roller is 70°C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roller is 120°C; the static pressure of spraying the alloy liquid on the surface of the cooling roller is 55kPa; The width is 0.7mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 346W/m·K, the thickness of the roll cover is 22.8mm, and the inner diameter of the roll cover is 1200mm.

Comparative Example 3:

An amorphous alloy strip, the width of the amorphous alloy strip is 100mm and the thickness is 41μm; the alloy composition of the amorphous alloy strip is Fe ₈₃ Si ₃ B ₁₁ C ₁ P ₂ (wherein the numbers represent mole percentages. The same below).

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 100mm and the thickness is 41μm; the temperature of the alloy liquid is 1365°C; the linear speed of the surface rotation of the cooling roll is 22m/ s, the temperature of the surface of the cooling roll is 70 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 120 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 52kPa; The width is 0.7mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 180W/m·K, the thickness of the roll cover is 11mm, and the inner diameter of the roll cover is 800mm.

Comparative Example 4:

An amorphous alloy strip has a width of 85 mm and a thickness of 49 μm; the alloy composition of the amorphous alloy strip is Fe ₈₃ Si ₃ B ₁₁ C ₁ P ₂ .

A method for preparing an amorphous alloy strip, the method adopts a plane flow rapid solidification process to prepare the amorphous alloy strip, and the process comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, Then spray the alloy liquid on the surface of the cooling roll for cooling. The width of the amorphous alloy strip is 85mm and the thickness is 49μm; the temperature of the alloy liquid is 1365°C; the linear speed of the surface rotation of the cooling roll is 21m/ s, the temperature of the surface of the cooling roll is 70 °C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 120 °C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 46kPa; The width is 0.6mm; the cooling roll includes a roll cover, the thermal conductivity of the roll cover is 220W/m·K, the thickness of the roll cover is 13.6mm, and the inner diameter of the roll cover is 1600mm.

In order to verify the technical effect of the present invention, cooling roll sleeves with key parameter combinations such as different thermal conductivity, different thicknesses, and different inner diameters are designed. As a comparison, the parameters of the roll sleeves which are not within the scope of the present invention were also tested as comparative examples. The process parameters of Examples 1 to 9 and Comparative Examples 1-4 are shown in Table 1. The parameters of the cooling roll sleeve, the average thickness of the strip, the toughness value and the lamination coefficient and The magnetic properties measurement data are shown in Table 2, in which the width, thickness, lamination factor and magnetic properties of the strip are measured by the method of the national standard GB/T19345.1-2017; the method of the International Electrotechnical Commission Standard IEC 60404-8-11 is used to measure The toughness value of the strip.

Table 1 Process parameters used in the manufacture of strips

Table 2 Cooling roll sleeve parameters, strip performance measurement data

It can be seen that when the technical solution provided by the present invention is adopted (that is, the thermal conductivity of the roll sleeve and the thickness of the roll sleeve are within the shaded area in FIG. 1 ), the produced iron-based amorphous alloy wide and thick strip has good The toughness value of , the lamination coefficient ≥ 0.86, the saturation magnetic induction intensity B _s ≥ 1.50T, the coercive force H _c ≤ 2.0A/m, the specific total loss P _c (50Hz, 1.3T) ≤ 0.15W/kg, can reach this The purpose of the invention; when the technical solution of the present invention is not adopted (that is, the thermal conductivity of the roll sleeve and the thickness of the roll sleeve are above the shaded area in FIG. 1), the toughness of the iron-based amorphous wide and thick strip is obviously deteriorated.

When manufacturing iron-based amorphous wide and thick strips with a thickness of more than 30 μm and a width of more than 80 mm, the maximum available thickness of the cooling roll sleeve is closely related to the thermal conductivity of the roll sleeve. When the roller sleeve is made of high thermal conductivity material, the maximum thickness of the roller sleeve can be appropriately increased; when the roller sleeve is made of low thermal conductivity material, the maximum thickness of the roller sleeve must be reduced, otherwise the strip will be brittle or even crystallized due to insufficient cooling. change. According to the present invention, when the thermal conductivity of the used roller sleeve material is increased from 80 W/m·K to 350 W/m·K, the maximum usable thickness of the roller sleeve can be increased from 5 mm to 18 mm.

When manufacturing iron-based amorphous wide and thick strips with a thickness of more than 30 μm and a width of more than 80 mm, the relationship between the maximum usable thickness of the roll sleeve and the thermal conductivity of the roll sleeve can be intuitively shown as straight line AB in Figure 1. The straight section AB has two meanings: First, if the thermal conductivity of the roll sleeve is determined in advance, the maximum available thickness of the roll sleeve must be below the maximum available thickness of the roll sleeve corresponding to the thermal conductivity on the straight section AB, otherwise it cannot be. Second, if the maximum thickness of the roller sleeve is determined in advance, the thermal conductivity of the roller sleeve material must be higher than the thermal conductivity value of the roller sleeve corresponding to the maximum thickness on the straight section AB, otherwise the cooling capacity cannot be guaranteed. . That is to say, the straight line AB actually gives the upper limit of the maximum usable thickness of the roll cover when the thermal conductivity of the roll cover is constant and the lower limit of the thermal conductivity of the roll cover when the maximum thickness of the roll cover is constant.

The maximum usable thickness of the sleeve is also related to the thickness of the strip being produced, given the thermal conductivity of the sleeve. If the strip to be produced is thicker, the thermal load on the sleeve is greater, and the maximum thickness of the sleeve must be further reduced. In the same way, the thermal conductivity of the sleeve material must be further increased when making thicker strips while maintaining the maximum thickness of the sleeve. Thus, under the condition of different strip thickness, the preferred range of "roll cover thermal conductivity - roll cover maximum usable thickness" will be located below the straight line AB in FIG. 1 .

Therefore, when manufacturing iron-based amorphous wide and thick strips with a thickness of more than 30 μm and a width of more than 80 mm, the optimal range of thermal conductivity of the roller sleeve and its actual thickness range are located in the shaded part of Figure 1. The polygon ABCD range , where the coordinates of each point are A(80,4), B(350,20), C(80,2), D(350,2).

The diameter of the cooling roll sleeve is mainly selected according to the process equipment conditions. Although the diameter of the cooling roll also has a certain influence on the cooling capacity of the cooling roll system, its influence is less than the thermal conductivity and thickness of the roll sleeve. According to the present invention, a suitable range of the inner diameter of the roll sleeve is 400-1600 mm. More preferably, the optimum range of the inner diameter of the roll sleeve is 500-1200 mm.

Since the roller sleeve is a consumable material, it needs to be turned to remove the surface thermal fatigue layer after each belt production. Therefore, the actual thickness of the roller sleeve gradually decreases during the entire service life of the roller sleeve. When the thickness of the roller sleeve is reduced to a certain extent, a new roller sleeve must be replaced. In order to reduce production costs, it is always desirable that the initial thickness of the new roll sleeve be as large as possible. However, according to the present invention, the determination of the maximum thickness of the roll sleeve must also take into account the guarantee of the cooling capacity. Therefore, in actual production, there are two ways to determine the initial thickness of the roll sleeve: one is to directly limit the initial thickness of the new roll sleeve within the maximum available thickness, so that the new roll sleeve can be directly used to manufacture iron-based non-ferrous materials. Crystal wide and thick strip. The second is to intentionally make the initial thickness of the new roll sleeve exceed the maximum usable thickness when manufacturing iron-based amorphous wide and thick strips. When the actual thickness of the roll sleeve is greater than the maximum usable thickness, it is only used to manufacture thinner, or to reduce the cooling rate. Amorphous strips with lower requirements; when the thickness of the roll sleeve is consumed below the maximum available thickness when manufacturing iron-based amorphous wide and thick strips, the production of iron-based amorphous wide and thick strips begins. That is to say, when purchasing or manufacturing a new roll cover, the initial thickness of the roll cover can be limited below the maximum usable thickness, or the initial thickness of the new roll cover can be made larger than the maximum usable thickness.

Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements to some of the technical features; and these Modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

An amorphous alloy strip, characterized in that the amorphous alloy strip has a width of ≥80 mm, a thickness of ≥30 μm, and a toughness value of <4.0.
The amorphous alloy strip according to claim 1, wherein the amorphous alloy strip comprises the following composition: Ti, Zr, Hf, V, Nb, Ta, Cr, Any one or more of Mo, W, Mn, Cu, Ag, Au, Zn, Al or Sn; any one or more of Si, B, P or C with a total content of 15-30 at%; One or both of Co or Ni with a total content of 0-20 at%; the balance is Fe.
The amorphous alloy strip according to claim 1 or 2, wherein the amorphous alloy strip is obtained by cooling the alloy liquid through a cooling roll, the cooling roll comprises a roll sleeve, and the thermal conductivity of the roll sleeve is , the maximum available thickness of the roll sleeve and the thickness of the amorphous alloy strip have the following relationship:

Among them: λ is the thermal conductivity of the roller sleeve, the unit is W/m·K;

d max is the maximum available thickness of the roller sleeve, the unit is mm;

δ is the average thickness of the amorphous alloy strip, in μm;

The value range of k is 1-2mm 3 K/W.
A method for preparing an amorphous alloy strip according to claim 3, wherein the method comprises heating and melting the raw material of the amorphous alloy strip into an alloy liquid, and then spraying the alloy liquid into an alloy liquid. The surface of the cooling roll is cooled.
The method for preparing an amorphous alloy strip according to claim 4, wherein the temperature of the alloy liquid is 1250-1450°C; the linear speed of the surface rotation of the cooling roll is 15-30m/s, and the cooling roll The temperature of the surface is 70-150°C; the temperature of the amorphous alloy strip when peeling off the surface of the cooling roll is 120-200°C; the static pressure of spraying the alloy liquid on the surface of the cooling roll is 20-60kPa, the nozzle The width of the slit is 0.4-1.0mm.
The method for preparing an amorphous alloy strip according to claim 4, wherein the temperature of the alloy liquid is 1300-1400°C.
The method for preparing an amorphous alloy strip according to claim 4, wherein the static pressure for spraying the alloy liquid onto the surface of the cooling roll is 25-50 kPa.
The method for preparing an amorphous alloy strip according to claim 4, wherein the temperature of the surface of the cooling roll is 90-120°C.
The method for preparing an amorphous alloy strip according to claim 4, wherein the temperature when the amorphous alloy strip is peeled off the surface of the cooling roll is 140-180°C.
The method for preparing an amorphous alloy strip according to claim 4, wherein the value of λ is 80-350 W/m·K; the value of d max is 4-20 mm.
The method for preparing an amorphous alloy strip according to claim 4, wherein the value of the d max is 4-20 mm; the value of the λ is 100-300 W/m·K.