CN110216249B - Preparation method of iron-based amorphous alloy thin strip with high thermal stability - Google Patents
Preparation method of iron-based amorphous alloy thin strip with high thermal stability Download PDFInfo
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Abstract
The invention discloses a preparation method of an iron-based amorphous alloy thin strip with high thermal stability, which comprises the step of carrying out Fe treatment on Fe76PCSi8B14The alloy melt is subjected to overheating treatment, then is cooled to the set casting temperature, and then Fe is added76PCSi8B14The alloy melt is continuously poured onto a rapidly rotating cooling copper roller through a nozzle and is rapidly solidified into Fe at a set solidification temperature76PCSi8B14An amorphous alloy thin strip; wherein the casting temperature is 1250-1450 ℃, and the solidification temperature is 320-480 ℃. The invention regulates and controls Fe76PCSi8B14Further increase of Fe by casting temperature of alloy melt76PCSi8B14Solidification temperature, and further increase Fe76PCSi8B14Thermal stability of amorphous alloy, obtaining high quality Fe76PCSi8B14Amorphous alloy ribbon.
Description
Technical Field
The invention belongs to the technical field of preparation of metal functional materials, and particularly relates to a preparation method of an iron-based amorphous alloy thin strip with high thermal stability.
Background
The iron-based amorphous alloy is obtained by directly solidifying an alloy melt by adopting a non-equilibrium state preparation method, so that the structural characteristics of the melt are retained by the iron-based amorphous alloy. The nonequilibrium structural characteristics of the iron-based amorphous alloy are closely related to the initial structure and the preparation process of the alloy melt, and any changes of the preparation process and the solidification process can cause obvious changes of the local structure of the iron-based amorphous alloy. The thermal stability of the iron-based amorphous alloy material is very important for the iron-based amorphous alloy material, because when the iron-based amorphous alloy is used for preparing an iron core or a device, the iron-based amorphous alloy material needs to be annealed, and if the annealing temperature is close to or higher than the melt solidification temperature during the preparation of the iron-based amorphous alloy, the obvious change of the amorphous alloy structure is inevitably caused, and the performance of the iron core is seriously influenced. The solidification temperature is increased, so that the annealing temperature is far lower than the solidification temperature of the melt, the influence of annealing treatment on the performance of the iron-based amorphous alloy device is reduced, and the process window for preparing the iron-based amorphous alloy device is widened.
The direct solidification of alloy melt into amorphous alloy is a supercooling solidification process of melt, in the process, the viscosity of the melt is increased along with the reduction of the temperature of the alloy melt, so that the melt gradually loses fluidity and is transformed into solid with melt structure characteristics. Supercooling solidification of an alloy melt is therefore a process in which the viscosity of the melt changes with the temperature of the melt. In fact, the necessary condition for achieving the supercooled solidification of the alloy melt is that the degree of supercooling of the alloy melt is larger than the temperature difference between the natural solidification temperature of the alloy melt and the amorphous transition temperature Tg, i.e., the state of the alloy melt must be maintained to a temperature lower than the amorphous transition temperature Tg. However, when the melt is naturally cooled, the supercooling degree of the iron-based alloy melt is usually very small, and the supercooling degree required by the supercooling solidification of the alloy melt cannot be achieved, so that the supercooling degree of the iron-based alloy melt must be artificially increased. In essence, the supercooling degree of the alloy melt is represented by the relation between the melt viscosity and the melt temperature, and since the melt viscosity is derived from the movement resistance between fluid layers in the melt, and the movement resistance between the fluid layers is related to the melt structure, the change of the melt viscosity reflects the change of the melt structure. Unlike the anionic and cationic structures of organic solutions, the basic unit of the alloy melt structure is an atomic cluster. The resistance of the clusters of atoms with different sizes to the movement between fluid layers is different, and generally, the resistance of the movement between fluid layers in the melt is in direct proportion to the size of the clusters of atoms, that is, the resistance of the clusters of atoms with small sizes to the movement between fluid layers is small. The change of the melt structure is caused by the change of the melt temperature, the change of the melt temperature depends on the heat absorbed or released by the melt in unit time, the change of the melt structure depends on the diffusion speed of atoms in the melt, therefore, the influence degree of the change of the melt structure by the change of the melt temperature depends on the difference of the change of the diffusion speed of the atoms in the melt and the change speed of the melt temperature, if the change of the diffusion speed of the atoms in the melt is synchronous with the change speed of the melt temperature, the change of the melt structure is synchronous with the change of the melt temperature, otherwise, if the change speed of the melt temperature is faster than the change of the diffusion speed of the atoms in the melt, the change of the melt structure. Therefore, the dependence of the melt structure on the melt temperature can be regulated and controlled by artificially controlling the variation speed of the alloy melt temperature, namely, the reduction speed of the alloy melt temperature is artificially increased, so that the reduction speed of the melt temperature is higher than the variation speed of the melt structure, and the melt has an atomic cluster structure higher than the actual temperature. When the temperature of the melt rises faster than the rate of change of the melt structure, this also results in a melt having a lower atomic cluster structure than its actual temperature. Therefore, the supercooling degree of the alloy melt can be regulated and controlled by artificially changing the cooling speed of the melt based on the characteristic that the structural change of the alloy melt lags behind the temperature change of the melt. When the alloy melt is cooled at a high speed, the cooling degree of the produced alloy melt is in direct proportion to the cooling speed, the higher the cooling speed is, the higher the cooling degree of the obtained alloy melt is, the supercooling degree required by supercooling solidification of the alloy melt can be completely met, and a process technology for preparing an amorphous alloy material by using a high-speed cooling method is formed.
The non-equilibrium state structure of the amorphous alloy enables the amorphous alloy local structure to have multiple states. Since the local structure and the electronic energy band structure of the amorphous alloy are closely related to the temperature and the viscosity of the alloy melt during casting, the adjustment and control of the melt viscosity and the casting temperature have important influence on the improvement of the performance of the amorphous alloy. Chinese patent application 201610555453.X discloses a process method for improving amorphous forming ability of an alloy melt, and relates to the improvement of amorphous structure forming ability of the alloy melt by the characteristic that structural change of a FeSiB alloy melt subjected to thermal cycle treatment lags behind temperature change of the alloy melt. The method has the main defects that: the alloy melt needs to be treated at 1900 ℃ high temperature, which is easy to cause the oxidation of metal in the melt.
Chinese patent application 201610879582.4 discloses a method for preparing an amorphous solid alloy thin strip for reducing the casting temperature of an alloy melt, which relates to the reduction of the casting temperature of the alloy melt by utilizing the characteristic that the structural change of a FeSiB alloy melt subjected to thermal cycle treatment lags behind the temperature change of the alloy melt. The method has the following main defects: the alloy melt needs to be treated at a high temperature of 1700 ℃, and metal in the melt is easily oxidized.
In summary, although the adjustment and control of the solidification temperature of the iron-based alloy melt plays an important role in improving the thermal stability of the iron-based amorphous alloy strip, a technical method for effectively adjusting and controlling the solidification temperature of the iron-based alloy melt is still lacking at present, and the method is one of the key problems which cannot be solved in the field of iron-based amorphous alloy materials at present. Therefore, the establishment of the process method for regulating and controlling the solidification temperature of the iron-based alloy melt is a key technology for meeting important iron-based amorphous alloy strip research and engineering production, and is also an important technology urgently needed for developing novel high-thermal-stability iron-based amorphous alloy materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing an iron-based amorphous alloy thin strip with high thermal stability, which can improve Fe76PCSi8B14Further regulating and controlling Fe by pouring temperature of alloy melt76PCSi8B14The solidification temperature of the alloy melt is effectively improved, and Fe is effectively improved76PCSi8B14Thermal stability of amorphous alloy ribbon.
The invention provides a preparation method of an iron-based amorphous alloy thin strip with high thermal stability, which comprises the following steps: firstly to Fe76PCSi8B14Alloy melt feedingCarrying out overheating treatment, then reducing the temperature to the set casting temperature, and then adding Fe76PCSi8B14The alloy melt is continuously poured onto a rapidly rotating cooling copper roller through a nozzle and is rapidly solidified into Fe at a set solidification temperature76PCSi8B14An amorphous alloy thin strip; wherein the casting temperature is 1250-1450 ℃, and the solidification temperature is 320-480 ℃.
Further, in the method for preparing the iron-based amorphous alloy ribbon with high thermal stability provided by the invention, the establishment of the correlation between the pouring temperature and the solidification temperature comprises the following steps: (1) first, Fe is set76PCSi8B14The casting temperature of the alloy melt is 1250-1450 ℃; respectively adding Fe at 1250-1450 deg.C in 50 deg.C76PCSi8B14Preparation of alloy melt into Fe76PCSi8B14Thin ribbon of amorphous alloy and determination of Fe76PCSi8B14No crystal phase appears in the amorphous alloy; production of Fe at different casting temperatures76PCSi8B14When the amorphous alloy thin strip is used, the laser infrared thermometer is used for in-situ measurement of Fe on the rapidly rotating cooling roller76PCSi8B14The solidification temperature of the amorphous alloy melt is obtained to obtain the melt solidification temperature corresponding to the casting temperature of different melts; wherein the solidification temperature range of the melt is 320-480 ℃; (2) according to measured Fe76PCSi8B14Establishing a mutual relation between the solidification temperature of the melt and the casting temperature; resetting the required Fe76PCSi8B14And selecting the corresponding casting temperature of the alloy melt according to the established relation between the solidification temperature of the alloy melt and the casting temperature.
Further, in the preparation method of the iron-based amorphous alloy ribbon with high thermal stability provided by the invention, the casting temperature is 1250-.
Further, in the method for preparing the iron-based amorphous alloy ribbon with high thermal stability, the temperature of the overheating treatment is higher than the set casting temperature by 100 ℃.
Further, in the preparation method of the iron-based amorphous alloy ribbon with high thermal stability provided by the invention, the surface linear velocity of the rapidly rotating cooling copper roller is 18-25 m/s.
Furthermore, in the preparation method of the iron-based amorphous alloy ribbon with high thermal stability provided by the invention, the Fe76PCSi8B14The thickness of the amorphous alloy thin strip is 27-30 microns.
Further, Fe according to the present invention76PCSi8B14The thermal stability measurement of the amorphous alloy thin strip comprises the following steps: (1) using a mold to mix Fe76PCSi8B14Cutting the amorphous alloy thin strip into a wafer with the diameter of 3 mm, mechanically grinding and polishing the wafer, cooling the polished sample to-40 ℃ by using a liquid nitrogen-cooled sample stage sample, and performing ion bombardment thinning to finally obtain a film-shaped sample which can be penetrated by an electron beam; (2) prepared Fe76PCSi8B14And the amorphous alloy transmission electron microscope sample is arranged on a transmission electron microscope sample table with a heating function, is heated, and simultaneously observes the change of the microstructure of the iron-based amorphous alloy in situ and records the temperature of the crystallized structure.
The principle and the beneficial effects of the preparation method of the iron-based amorphous alloy thin strip with high thermal stability provided by the invention are as follows:
the technical principle is as follows: the casting temperature and the solidification temperature of the alloy melt are two very important factors for determining the microstructure of the iron-based amorphous alloy, wherein the casting temperature determines the initial structure of the melt to enter a high-speed cooling process, and the solidification temperature determines the atomic cluster structure of the iron-based amorphous alloy. Therefore, the regulation of the solidification temperature of the melt is one of important ways for regulating the microstructure of the iron-based amorphous alloy. Because the temperature of the supercooled solidification of the iron-based alloy melt must be lower than the amorphous transformation temperature Tg, the difference between the actual solidification temperature of the iron-based alloy melt and the amorphous transformation temperature Tg is the controllable range of the solidification temperature of the melt, and the larger the difference between the actual solidification temperature of the melt and the amorphous transformation temperature Tg is, the larger the controllable range of the solidification temperature is. The solidification temperature of the cast iron-based alloy melt is directly related to the supercooling degree generated in the high-speed cooling process, the supercooling degree is related to the cooling capacity of high-speed cooling equipment, the amplitude of temperature reduction of the iron-based alloy melt in the high-speed cooling process is not greatly changed under the condition of not changing the cooling capacity of the high-speed cooling equipment, namely, the actual solidification temperature of the iron-based alloy melt is directly related to the casting temperature, the solidification temperature of the melt is correspondingly changed when the casting temperature of the iron-based alloy melt is changed, when the casting temperature of the iron-based alloy melt is increased, the difference between the actual solidification temperature of the melt and the amorphous transformation temperature Tg is reduced, and when the casting temperature of the iron-based alloy melt is reduced, the difference between the actual solidification temperature of the melt and the amorphous transformation temperature Tg is increased. The direct proportion relation between the solidification temperature of the iron-based alloy melt and the casting temperature of the iron-based alloy melt enables the purpose of regulating the solidification temperature of the iron-based alloy melt to be achieved by changing the casting temperature of the iron-based alloy melt.
When the iron-based amorphous alloy is obtained by supercooling and solidifying the iron-based alloy melt, the structure of the iron-based amorphous alloy is still the structure of the melt, but the higher the solidification temperature of the melt is, the higher the overheating temperature of the melt structure corresponding to the iron-based amorphous alloy structure is, if the solidification temperature is 300 ℃, the obtained iron-based amorphous alloy structure corresponds to the melt structure at 1100 ℃, and if the solidification temperature is increased to 400 ℃, the melt structure corresponding to the iron-based amorphous alloy structure may be 1200 ℃ or higher. The thermal activation energy KT (K is Boltzmann constant and T is absolute temperature) of the melt structure at 1200 ℃ is greater than that of 1100 ℃, so that the thermal stability of the melt structure at 1200 ℃ is higher than that of the melt structure at 1100 ℃, and therefore, the improvement of the solidification temperature is beneficial to improving the thermal stability of the amorphous alloy.
The Fe with high thermal stability provided by the invention76PCSi8B14In the preparation method of the amorphous alloy thin strip, because Fe is in the high-speed cooling process76PCSi8B14Alloy melt solidification temperature and Fe76PCSi8B14The casting temperature of the alloy melt has a direct proportion relation, and the influence of the casting temperature of the alloy melt on the solidification temperature is utilized to regulate and control Fe76PCSi8B14The casting temperature of the alloy melt is used for regulating and controlling the solidification temperature of the alloy melt, so that the purpose of improving the thermal stability of the iron-based amorphous alloy is achieved. In the invention, Fe76PCSi8B14The casting temperature of the alloy melt is regulated to 1250-1450 ℃, the solidification temperature is regulated to 320-480 ℃, and Fe with high thermal stability is obtained76PCSi8B14Amorphous alloy thin strip. The invention has the characteristics of simple and convenient implementation, high efficiency, low cost, strong controllability and repeatability and the like.
Drawings
FIG. 1 shows examples 1 of the present invention for Fe76PCSi8B14And the corresponding relation between the solidification temperature of the melt and the casting temperature measured by the iron-based alloy melt is shown.
FIG. 2 shows example 1 of the present invention, in which Fe with a solidification temperature of 480 ℃ is photographed by a transmission electron microscope76PCSi8B14Schematic diagram of high-resolution image of iron-based amorphous alloy thin band heating crystallization.
FIG. 3 shows example 2 of the present invention, in which Fe with a solidification temperature of 320 ℃ is photographed by a transmission electron microscope76PCSi8B14Schematic diagram of high-resolution image of iron-based amorphous alloy thin band heating crystallization.
FIG. 4 shows that in example 3 of the present invention, Fe with a solidification temperature of 390 ℃ is photographed by a transmission electron microscope76PCSi8B14Schematic diagram of high resolution image of amorphous alloy thin band heating crystallization.
Detailed Description
The following detailed description of embodiments of the present invention will be made with reference to the accompanying drawings and examples.
The invention provides a preparation method of an iron-based amorphous alloy thin strip with high thermal stability, which comprises the following steps: firstly to Fe76PCSi8B14The alloy melt is subjected to overheating treatment, then is cooled to the set casting temperature, and then Fe is added76PCSi8B14The alloy melt is continuously poured onto a rapidly rotating cooling copper roller through a nozzle and is rapidly solidified into Fe at a set solidification temperature76PCSi8B14An amorphous alloy thin strip; wherein the casting temperature is 1250-1450 ℃, and the solidification temperature is 320-480 ℃.
The specific embodiment of the preparation method of the iron-based amorphous alloy thin strip with high thermal stability provided by the invention is as follows:
example 1
To use Fe76PCSi8B14The amorphous alloy thin strip is taken as an example, the number in the chemical formula is at%, and the amorphous alloy thin strip is prepared by adopting a high-speed plane flow continuous casting method commonly used in the field. The method for preparing the iron-based amorphous alloy thin strip with high thermal stability provided by the invention comprises the following specific operation steps:
step 1, establishing Fe76PCSi8B14The corresponding relation between the casting temperature and the solidification temperature of the alloy melt is as follows: first, Fe is set76PCSi8B14Interval of alloy melt casting temperature: 1250 ℃ -1450 ℃; respectively adding Fe at 1250-1450 deg.C in 50 deg.C76PCSi8B14Preparation of alloy melt into Fe76PCSi8B14Thin ribbon of amorphous alloy and determination of Fe76PCSi8B14No crystal phase appears in the amorphous alloy; production of Fe at different casting temperatures76PCSi8B14When the amorphous alloy thin strip is used, the laser infrared thermometer (model: Marathon MM) is used for in-situ measurement of Fe on the rapidly rotating cooling roller76PCSi8B14The solidification temperature of the amorphous alloy melt, which obtains melt solidification temperatures corresponding to different melt casting temperatures, as shown in fig. 1;
step 2, selecting the solidification temperature of the melt within the measured solidification temperature interval of the iron-based alloy melt: fe measured according to the aforementioned step 176PCSi8B14The corresponding relation between the solidification temperature and the casting temperature of the alloy melt is established, and the solidification temperature and the casting temperature of the alloy melt are establishedCorrelation of temperature; setting the desired Fe76PCSi8B14The solidification temperature of the alloy melt is 480 ℃, and corresponding Fe is selected according to the established relation between the solidification temperature of the melt and the casting temperature76PCSi8B14The casting temperature of the alloy melt is 1450 ℃;
step 3, adding Fe at the set casting temperature76PCSi8B14Alloy melt is rapidly solidified into Fe76PCSi8B14Amorphous alloy thin strip: at a temperature 100 ℃ above the set casting temperature, i.e. 1550 ℃ for Fe76PCSi8B14Carrying out overheating treatment on the alloy melt, and then reducing the temperature to 1450 ℃ which is set as a casting temperature; mixing Fe76PCSi8B14 alloy melt is continuously poured onto a rapidly rotating cooling copper roller with the surface linear speed of 18-25 m/s through a nozzle, and is rapidly solidified into Fe at a set solidification temperature76PCSi8B14Amorphous alloy thin strip.
Testing of Fe76PCSi8B14Thermal stability of amorphous alloy ribbon: (1) using a mold to mix Fe76PCSi8B14Cutting the amorphous alloy thin strip into a wafer with the diameter of 3 mm, mechanically grinding and polishing the wafer, cooling the polished sample to-40 ℃ by using a liquid nitrogen-cooled sample stage sample, and performing ion bombardment thinning to finally obtain a film-shaped sample which can be penetrated by an electron beam; (2) prepared Fe76PCSi8B14The amorphous alloy transmission electron microscope sample is arranged on a transmission electron microscope sample table with a heating function, heating is carried out, meanwhile, the change of the microstructure of the iron-based amorphous alloy is observed in situ, and the temperature of the iron-based amorphous alloy with the crystallized structure is recorded as 580 ℃.
Fe obtained by the above procedure76PCSi8B14A schematic diagram of a high resolution image of the presence of crystallized structures in the thin amorphous alloy band is shown in fig. 2.
Example 2
To use Fe76PCSi8B14For example, the amorphous alloy thin strip is represented by the chemical formula in which the number is at%, and the amorphous alloy thin strip is represented by the chemical formula in which the number is at%The bulk alloy thin strip is prepared by a high-speed planar flow continuous casting method commonly used in the field. The method for preparing the iron-based amorphous alloy thin strip with high thermal stability provided by the invention comprises the following specific operation steps:
step 1, establishing Fe76PCSi8B14The corresponding relation between the casting temperature and the solidification temperature of the alloy melt is as follows: first, Fe is set76PCSi8B14Interval of alloy melt casting temperature: 1250 ℃ -1450 ℃; respectively adding Fe at 1250-1450 deg.C in 50 deg.C76PCSi8B14Preparation of alloy melt into Fe76PCSi8B14Thin ribbon of amorphous alloy and determination of Fe76PCSi8B14No crystal phase appears in the amorphous alloy; production of Fe at different casting temperatures76PCSi8B14When the amorphous alloy thin strip is used, the laser infrared thermometer (model: Marathon MM) is used for in-situ measurement of Fe on the rapidly rotating cooling roller76PCSi8B14The solidification temperature of the amorphous alloy melt is obtained to obtain the melt solidification temperature corresponding to the casting temperature of different melts;
step 2, selecting the solidification temperature of the melt within the measured solidification temperature interval of the iron-based alloy melt: fe measured according to the aforementioned step 176PCSi8B14Establishing the correlation between the solidification temperature of the melt and the casting temperature; setting the desired Fe76PCSi8B14The solidification temperature of the alloy melt is 320 ℃, and corresponding Fe is selected according to the established relation between the solidification temperature of the melt and the casting temperature76PCSi8B14The casting temperature of the alloy melt is 1250 ℃;
step 3, adding Fe at the set casting temperature76PCSi8B14Alloy melt is rapidly solidified into Fe76PCSi8B14Amorphous alloy thin strip: at a temperature 100 ℃ above the set casting temperature, i.e. 1350 ℃ for Fe76PCSi8B14The alloy melt is subjected to overheating treatment and then is reduced toThe fixed casting temperature is 1250 ℃; mixing Fe76PCSi8B14Continuously pouring the alloy melt onto a rapidly rotating cooling copper roller with the surface linear velocity of 18-25 m/s through a nozzle, and rapidly solidifying the alloy melt into Fe at a set solidification temperature76PCSi8B14Amorphous alloy thin strip.
Testing of Fe76PCSi8B14Thermal stability of amorphous alloy ribbon: (1) using a mold to mix Fe76PCSi8B14Cutting the amorphous alloy thin strip into a wafer with the diameter of 3 mm, mechanically grinding and polishing the wafer, cooling the polished sample to-40 ℃ by using a liquid nitrogen-cooled sample stage sample, and performing ion bombardment thinning to finally obtain a film-shaped sample which can be penetrated by an electron beam; (2) prepared Fe76PCSi8B14The amorphous alloy transmission electron microscope sample is arranged on a transmission electron microscope sample table with a heating function, heating is carried out, meanwhile, the change of the microstructure of the iron-based amorphous alloy is observed in situ, and the temperature of the iron-based amorphous alloy with the crystallized structure is recorded to be 520 ℃.
Fe obtained by the above procedure76PCSi8B14A schematic diagram of a high resolution image of the presence of crystallized structures in the amorphous alloy ribbon is shown in fig. 3.
Example 3
To use Fe76PCSi8B14The amorphous alloy thin strip is taken as an example, the number in the chemical formula is at%, and the amorphous alloy thin strip is prepared by adopting a high-speed plane flow continuous casting method commonly used in the field. The method for preparing the iron-based amorphous alloy thin strip with high thermal stability provided by the invention comprises the following specific operation steps:
step 1, establishing Fe76PCSi8B14The corresponding relation between the casting temperature and the solidification temperature of the alloy melt is as follows: first, Fe is set76PCSi8B14Interval of alloy melt casting temperature: 1250 ℃ -1450 ℃; respectively adding Fe at 1250-1450 deg.C in 50 deg.C76PCSi8B14Preparation of alloy melt into Fe76PCSi8B14Thin ribbon of amorphous alloy and determination of Fe76PCSi8B14No crystal phase appears in the amorphous alloy; production of Fe at different casting temperatures76PCSi8B14When the amorphous alloy thin strip is used, the laser infrared thermometer (model: Marathon MM) is used for in-situ measurement of Fe on the rapidly rotating cooling roller76PCSi8B14The solidification temperature of the amorphous alloy melt is obtained to obtain the melt solidification temperature corresponding to the casting temperature of different melts;
step 2, selecting the solidification temperature of the melt within the measured solidification temperature interval of the iron-based alloy melt: fe measured according to the aforementioned step 176PCSi8B14Establishing the correlation between the solidification temperature of the melt and the casting temperature; setting the desired Fe76PCSi8B14The solidification temperature of the alloy melt is 390 ℃, and corresponding Fe is selected according to the established relation between the solidification temperature of the melt and the casting temperature76PCSi8B14The casting temperature of the alloy melt is 1370 ℃;
step 3, adding Fe at the set casting temperature76PCSi8B14Alloy melt is rapidly solidified into Fe76PCSi8B14Amorphous alloy thin strip: at a temperature 100 ℃ higher than the set casting temperature, i.e. 1470 ℃ for Fe76PCSi8B14Carrying out overheating treatment on the alloy melt, and then reducing the temperature to 1370 ℃ of a set casting temperature; mixing Fe76PCSi8B14Continuously pouring the alloy melt onto a rapidly rotating cooling copper roller with the surface linear velocity of 18-25 m/s through a nozzle, and rapidly solidifying the alloy melt into Fe at a set solidification temperature76PCSi8B14Amorphous alloy thin strip.
Testing of Fe76PCSi8B14Thermal stability of amorphous alloy ribbon: (1) using a mold to mix Fe76PCSi8B14Cutting the amorphous alloy thin strip into a wafer with the diameter of 3 mm, mechanically grinding and polishing the wafer, cooling the polished sample to-40 ℃ by using a sample table sample cooled by liquid nitrogen,ion bombardment thinning is carried out, and finally a film-shaped sample which can be penetrated by an electron beam is obtained; (2) prepared Fe76PCSi8B14The amorphous alloy transmission electron microscope sample is arranged on a transmission electron microscope sample table with a heating function, heating is carried out, meanwhile, the change of the microstructure of the iron-based amorphous alloy is observed in situ, and the temperature of the iron-based amorphous alloy with the crystallized structure is recorded as 550 ℃.
Fe obtained by the above procedure76PCSi8B14A schematic diagram of a high resolution image of the presence of crystallized structures in the amorphous alloy ribbon is shown in fig. 4.
In summary, the preparation method of the iron-based amorphous alloy ribbon with high thermal stability provided by the invention can regulate and control Fe76PCSi8B14Further increase of Fe by casting temperature of alloy melt76PCSi8B14Solidification temperature, and further increase Fe76PCSi8B14Thermal stability of amorphous alloy, obtaining high quality Fe76PCSi8B14Amorphous alloy ribbon.
The invention obtains satisfactory trial effect through repeated test verification.
It should be noted that the above examples are only for clearly illustrating the process proposed by the present invention, and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. A preparation method of an iron-based amorphous alloy thin strip with high thermal stability is characterized by comprising the following steps: firstly to Fe76PCSi8B14The alloy melt is subjected to overheating treatment, then is cooled to the set casting temperature, and then Fe is added76PCSi8B14Alloy melt is continuously poured through a nozzleOnto a rapidly rotating cooled copper roll, is rapidly solidified into Fe at a set solidification temperature76PCSi8B14An amorphous alloy thin strip; wherein the casting temperature is 1250-1450 ℃, and the solidification temperature is 320-480 ℃.
2. The method for preparing the ribbon of the Fe-based amorphous alloy with high thermal stability of claim 1, wherein the correlation between the casting temperature and the solidification temperature is established as follows: (1) first, Fe is set76PCSi8B14The casting temperature of the alloy melt is 1250-1450 ℃; respectively adding Fe at 1250-1450 deg.C in 50 deg.C76PCSi8B14Preparation of alloy melt into Fe76PCSi8B14Thin ribbon of amorphous alloy and determination of Fe76PCSi8B14No crystal phase appears in the amorphous alloy; production of Fe at different casting temperatures76PCSi8B14When the amorphous alloy thin strip is used, the laser infrared thermometer is used for in-situ measurement of Fe on the rapidly rotating cooling roller76PCSi8B14The solidification temperature of the amorphous alloy melt is obtained to obtain the melt solidification temperature corresponding to the casting temperature of different melts; wherein the solidification temperature range of the melt is 320-480 ℃; (2) according to measured Fe76PCSi8B14Establishing a mutual relation between the solidification temperature of the melt and the casting temperature; resetting the required Fe76PCSi8B14And selecting the corresponding casting temperature of the alloy melt according to the established relation between the solidification temperature of the alloy melt and the casting temperature.
3. The method for preparing the ribbon of Fe-based amorphous alloy with high thermal stability as claimed in claim 1, wherein the temperature of the heat treatment is 100 ℃ higher than the set casting temperature.
4. The method for preparing the ribbon of Fe-based amorphous alloy with high thermal stability as claimed in claim 1, wherein the surface linear velocity of the fast rotating cooling copper roller is 18-25 m/s.
5. The method as claimed in claim 1, wherein the Fe is selected from the group consisting of Fe, Cr, Mo76PCSi8B14The thickness of the amorphous alloy thin strip is 27-30 microns.
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