CN111014599B - Process method for preparing low residual thermal stress amorphous alloy - Google Patents
Process method for preparing low residual thermal stress amorphous alloy Download PDFInfo
- Publication number
- CN111014599B CN111014599B CN201911349539.7A CN201911349539A CN111014599B CN 111014599 B CN111014599 B CN 111014599B CN 201911349539 A CN201911349539 A CN 201911349539A CN 111014599 B CN111014599 B CN 111014599B
- Authority
- CN
- China
- Prior art keywords
- alloy
- temperature
- amorphous alloy
- melt
- thermal stress
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0637—Accessories therefor
- B22D11/068—Accessories therefor for cooling the cast product during its passage through the mould surfaces
- B22D11/0682—Accessories therefor for cooling the cast product during its passage through the mould surfaces by cooling the casting wheel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
- B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
Abstract
The invention provides a process method for preparing low residual thermal stress amorphous alloy, which comprises the following steps: step S1, selecting a reference alloy, forming a series of alloys with different components in a mode that a non-metal element forming a low-melting-point alloy with a metal element partially replaces a non-metal element forming a high-melting-point alloy with the metal element, measuring the viscosity of the series of alloys at different casting temperatures, and establishing a relation between the viscosity and the casting temperature and the components; step S2, measuring the solidification temperature of the series of alloy melts under different cooling conditions at different casting temperatures, and establishing a relation of cooling conditions-solidification temperature-casting temperature-components; step S3, firstly, selecting low-viscosity alloy components according to the relation obtained in step S1 and setting the casting temperature according to the viscosity standard; then, according to the selected alloy composition, the set casting temperature and the relation obtained in the step S2, selecting a cooling condition corresponding to the supercooling solidification temperature increase; finally, the amorphous alloy is prepared.
Description
Technical Field
The invention belongs to the technical field of metal functional material preparation, and particularly relates to a process method for preparing low-residual-thermal-stress amorphous alloy.
Background
The process of preparing the alloy melt into the amorphous alloy is essentially a supercooling solidification process of the alloy melt, in the process, the alloy melt firstly becomes supercooled liquid, and the viscosity of the melt is rapidly increased along with the increase of the supercooling degree of the melt, so that the melt loses the flowing ability and is finally solidified into hard solid. When the alloy melt temperature is below its natural solidification temperature, it is referred to as a supercooled liquid. To make the melt a supercooled liquid, the change in viscosity of the melt must be delayed from the change in temperature of the melt, so that the melt can maintain its fluidity at temperatures below the natural solidification temperature of the melt. In order to convert the alloy melt into the amorphous alloy, the supercooling degree of the alloy melt must reach a critical supercooling degree, namely the supercooling degree must be larger than the difference between the natural cooling solidification temperature and the amorphous transformation temperature of the alloy melt.
Taking an iron-based amorphous alloy as an example, the natural cooling solidification temperature and the amorphous transformation temperature Tg of an iron-based alloy melt are usually different by several hundred degrees, so that the iron-based alloy melt must have a supercooling degree of several hundred degrees to be prepared into the amorphous alloy. However, the supercooling degree of the iron-based alloy melt is very small, only about 20 ℃, so the supercooling degree of the iron-based alloy melt must be artificially improved to prepare the iron-based amorphous alloy. To increase the supercooling degree of the iron-based alloy melt, it is necessary to increase the difference between the rate of change in the melt temperature and the rate of change in the melt viscosity. Since the rate of change of the melt temperature is dependent on the rate of heat exchange between the melt and the surrounding environment, the rate of change of the melt temperature is controlled by the manner of cooling. The speed of change of the melt viscosity depends on the speed of change of the melt structure, namely the speed of atomic diffusion, so that the influence of the cooling mode on the speed of change of the melt viscosity is very limited. Therefore, the supercooling degree of the melt can be regulated and controlled by utilizing a cooling mode. The heat of the melt can be rapidly transferred to the cooling medium through a rapid cooling mode, so that the temperature of the melt is rapidly reduced, and the difference between the temperature of the melt and the viscosity increasing speed of the melt is increased. The viscosity of the melt casting temperature determines the initial state of the melt from which the amorphous alloy is formed, and the melt solidification temperature determines the final solidification state of the amorphous alloy formed. Because the change of the melt structure lags behind the change of the melt temperature in the supercooling solidification process, the structure change lag phenomenon enables the structure of the amorphous alloy to be in a non-equilibrium state, and meanwhile, the structure lag effect is kept in the amorphous alloy in a residual thermal stress mode to influence the macroscopic performance of the amorphous alloy. Since the rapid change in the melt temperature during the supercooling solidification is the cause of the generation of the residual thermal stress, the faster the change in the melt temperature, the larger the residual thermal stress generated. Also, the phenomenon that the difference between the melt temperature change rate and the melt structure change rate is reflected in the supercooling solidification process is that the difference between the melt casting temperature and the solidification temperature is larger the faster the melt temperature change rate is. Therefore, reducing the difference between the melt casting temperature and the solidification temperature can be an important way to prepare low residual thermal stress amorphous alloys. However, those skilled in the art mainly aim to increase the iron content of the fe-based amorphous alloy to improve saturation induction, and the idea of reducing the residual thermal stress in the amorphous alloy product has not been realized for the time being. Chinese patent application 201610879582.4 discloses a method for preparing an amorphous solid alloy ribbon for reducing the casting temperature of an alloy melt, which relates to the reduction of the casting temperature of the alloy melt by treating FeSiB alloy melt by using a thermal cycle. The method reduces the casting temperature of the alloy melt, but does not reduce the difference between the casting temperature and the solidification temperature of the melt, so that the method does not contribute to reducing the residual thermal stress of the amorphous alloy.
In conclusion, exploring the process method for preparing the amorphous alloy with low residual thermal stress is an important technology urgently needed by the high-performance amorphous alloy material. Based on the above findings, the present application provides a process for preparing an amorphous alloy with low residual thermal stress, which achieves the goal of effectively reducing the residual thermal stress in the amorphous alloy structure by reducing the difference between the melt casting temperature and the solidification temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process method for preparing the amorphous alloy with low residual thermal stress, which can effectively reduce the residual thermal stress in the amorphous alloy structure and obviously improve the quality and the macroscopic physical property of the amorphous solid alloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process method for preparing low residual thermal stress amorphous alloy comprises the following steps:
step S1, selecting a reference alloy, forming a series of alloys with different components by partially replacing a non-metal element forming a low-melting-point alloy with a metal element to form a high-melting-point alloy with the metal element on the basis of the components of the reference alloy, measuring the viscosity of the series of alloy melts at different casting temperatures, and establishing the relationship between the viscosity of the series of alloy melts and the casting temperature-components;
step S2, aiming at the series of alloy melts, measuring the supercooling solidification temperature under different cooling conditions at different casting temperatures, and establishing the relation of the cooling conditions, the supercooling solidification temperature, the casting temperature and the components of the series of alloy melts;
step S3, firstly, selecting low-viscosity alloy components according to the relation obtained in the step S1, and setting the casting temperature according to the viscosity standard; then, according to the selected alloy composition, the set casting temperature and the relation obtained in the step S2, selecting a cooling condition corresponding to the supercooling solidification temperature increase; finally, the low residual thermal stress amorphous alloy is prepared.
In the above process for preparing the amorphous alloy with low residual thermal stress, as a preferred embodiment, the alloy melt is subjected to the overheating treatment in the processes of preparing the amorphous alloy in the steps S1, S2 and S3, and the overheating treatment is performed in the same manner.
As a preferred embodiment, the step S1 includes the following sub-steps:
s11, measuring the viscosity of the selected reference alloy melt at the normal casting temperature, and using the measured viscosity as a viscosity standard for selecting the casting temperature of the alloy melt with different components;
s12, under the condition of not changing the content of metal elements, preparing a series of low-viscosity alloys by increasing the content of non-metal elements forming low-melting-point alloys with the metal elements and simultaneously reducing the proportion of the content of non-metal elements forming high-melting-point alloys with the metal elements;
s13, heating and melting the master alloy of the series of alloys, measuring the change of the viscosity of the series of alloy melts along with the temperature in the cooling process, and establishing the relationship of the viscosity of the alloy melts, the casting temperature and the components;
as a preferred embodiment, the step S2 includes the following sub-steps:
s21, increasing the temperature of the cooling water and/or increasing the thickness of the cooling copper sleeve to reduce the cooling capacity of the cooling roller and increase the solidification temperature of the alloy melt;
s22, melting the amorphous alloy with the selected components, then carrying out overheating treatment, and then reducing the temperature to the set casting temperature;
s23, continuously pouring the alloy melt onto the surface of a cooling roller copper sleeve rotating at a high speed through a nozzle under the conditions of a plurality of set different cooling water temperatures and cooling copper sleeve thicknesses to obtain an amorphous alloy thin strip, and measuring the solidification temperature of the alloy melt on the cooling roller copper sleeve in situ; with the reduction of the cooling capacity, the solidification temperature of the alloy melt rises, and when a crystal phase begins to appear in the amorphous alloy thin strip, the solidification temperature of the previous amorphous alloy which can obtain complete amorphous alloy is the highest solidification temperature; the relation of the cooling condition-supercooling solidification temperature-casting temperature-composition of the series of alloy melts is obtained.
In the above-mentioned process method for preparing the amorphous alloy with low residual thermal stress, as a preferred embodiment, in the step S3, the cooling condition corresponding to the highest solidification temperature is selected according to the relationship obtained in the step S2.
As a preferred embodiment, the material of the amorphous alloy is Fe-based, FeNi-based or FeCo-based in an amorphous alloy system; preferably the FeSiB series; further, the material of the amorphous alloy is Fe80PxSi15-xB5The alloy, wherein x is the atom percentage content, and x is 5-10.
In the above process for preparing an amorphous alloy with low residual thermal stress, as a preferred embodiment, in the sub-step S22 of the step S2, the temperature of the overheating process is 80-120 ℃ higher than the set casting temperature, and the time of the overheating process is 50-90 min.
As a preferred embodiment, the casting temperature of the alloy melt is reduced by 0-120 ℃.
As a preferred embodiment, the supercooling solidification temperature of the alloy melt is increased by 0-145 ℃.
As a preferred embodiment, the amorphous alloy is in the shape of a thin strip.
As a preferred embodiment, the process for preparing the amorphous alloy with low residual thermal stress is characterized in that the amorphous alloy is prepared by a high-speed planar flow continuous casting method; the linear speed of the copper sleeve surface of the cooling roller is 18-30 m/s.
The realization principle of the invention is as follows:
since the residual thermal stress in the amorphous alloy is derived from the difference between the casting temperature and the solidification temperature of the alloy melt, reducing the difference between the casting temperature and the solidification temperature of the melt is the key to reducing the residual thermal stress in the amorphous alloy. Since melt viscosity is inversely proportional to temperature, as temperature decreases, melt viscosity increases. The viscosity of the melt at the casting temperature must be less than a critical value without the cooling capacity being changed, i.e. the viscosity of the melt at the casting temperature must be sufficiently low to ensure that the melt solidifies below its amorphous structure transition temperature Tg and is transformed into an amorphous alloy. Since melt viscosity is related to the melting point of the alloy, the lower the melt viscosity at the same temperature. Because the melting point of the alloy depends on the alloy components, the melting point of the melt can be reduced by increasing the non-metallic elements which can form low-melting-point alloy with the metallic elements in the alloy and simultaneously reducing the corresponding amount of non-metallic elements which can form high-melting-point alloy with the metallic elements, thereby achieving the purpose of reducing the viscosity of the melt. When the alloy components are changed to reduce the melt viscosity, the melt temperature corresponding to the critical melt viscosity required by casting is reduced, and the purpose of reducing the melt casting temperature can be achieved.
Under the condition of not changing the cooling capacity of the high-speed cooling equipment, the supercooling degree of the alloy melt with the same composition generated in the high-speed cooling process is basically fixed, the solidification temperature of the melt is correspondingly reduced by reducing the casting temperature of the melt, and the difference between the casting temperature and the solidification temperature is not reduced. Therefore, the difference between the casting temperature and the solidification temperature of the melt can be reduced by increasing the solidification temperature of the melt while reducing the casting temperature of the melt. Increasing the solidification temperature of the melt needs to be accomplished by reducing the cooling capacity of the cooling device. In the high-speed cooling process, the alloy melt firstly transfers heat to the copper sleeve of the cooling rod, and then the cooling water in the cooling rod takes away the heat transferred to the copper sleeve, so that the temperature of the copper sleeve is kept stable. Since the cooling capacity of the cooling device depends on the heat transfer rate of the cooling roller copper jacket and the temperature of the cooling water in the cooling roller, the cooling capacity of the cooling device can be controlled by reducing the heat exchange between the cast melt and the cooling roller copper jacket and the heat exchange between the copper jacket and the cooling water in the cooling roller, respectively. The amount of heat exchanged between the melt and the copper sleeve is proportional to the temperature difference between the melt and the copper sleeve, and the larger the temperature difference is, the more heat is exchanged, and the less heat is vice versa. The temperature rise of the surface of the copper sleeve is inversely proportional to the heat conduction speed of the copper sleeve in the process of exchanging heat between the copper sleeve and the melt, and the heat conduction speed of the copper sleeve is inversely proportional to the thickness of the copper sleeve, so that the heat conduction speed of the copper sleeve can be reduced by increasing the thickness of the cooling copper sleeve. After the thickness of the copper sleeve is increased, the same heat transferred from the melt in unit time can enable the surface temperature of the copper sleeve with large thickness to rise by a larger range than that of the copper sleeve with small thickness, and the surface temperature of the copper sleeve determines the solidification temperature of the melt. Therefore, the cooling capacity of the cooling roller can be reduced and the solidification temperature of the melt can be increased by increasing the thickness of the copper sleeve. Similarly, the amount of heat exchanged between the copper jacket and the cooling water in the cooling rod is also proportional to the temperature difference between the copper jacket and the cooling water, and the higher the temperature of the cooling water is, the less heat is exchanged between the copper jacket and the cooling water. The less heat is exchanged between the copper sleeve and the cooling water, the higher the surface temperature of the copper sleeve and the higher the corresponding solidification temperature of the melt. Thus, increasing the temperature of the cooling water also increases the solidification temperature of the melt. The method for increasing the thickness of the copper sleeve and the temperature of the cooling water can reduce the cooling capacity of the cooling roller and increase the solidification temperature of the melt, so that the copper sleeve and the cooling water can be used independently or jointly in the preparation of the amorphous alloy film.
In other words, the design principle of the process method for preparing the amorphous alloy with low residual thermal stress provided by the invention is as follows: the non-metal element which forms low-melting point alloy with metal element is used for partially replacing the non-metal element which forms high-melting point alloy with metal element to reduce the viscosity of alloy melt, thereby reducing the casting temperature of the melt, eliminating the ineffective superheat degree of the cast melt, increasing the thickness of a cooling rod copper sleeve and increasing the temperature of cooling water to improve the supercooling solidification temperature of the melt, reducing the ineffective supercooling degree of the alloy melt, and reducing the temperature difference between the casting temperature and the solidification temperature of the melt, thereby achieving the purpose of preparing the low residual thermal stress amorphous alloy.
Compared with the prior art, the invention has the following beneficial effects:
the process method for preparing the amorphous alloy with low residual thermal stress provided by the invention creates a new concept and a new scheme for preparing high-quality amorphous alloy in the field.
The invention is suitable for all amorphous alloy materials, and particularly can reduce the residual thermal stress in the amorphous alloy under the condition that the alloy melt components have larger fluctuation.
The invention is suitable for all amorphous alloy materials, and particularly can reduce the casting temperature of the amorphous alloy melt under the condition that the components of the alloy melt have large fluctuation.
The invention is suitable for all amorphous alloy materials, and particularly can improve the solidification temperature of the amorphous alloy melt under the condition that the components of the alloy melt have larger fluctuation.
The invention is suitable for all amorphous alloy materials, and particularly can improve the thermal stability of the amorphous alloy under the condition that the components of the alloy melt have larger fluctuation.
Sixthly, the method has the characteristics of convenience in implementation, high efficiency, low cost, strong controllability and repeatability, high technical reliability and the like, and is suitable for wide application in the technical field of metal functional material preparation.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing a low residual thermal stress amorphous alloy according to the present invention.
FIG. 2 shows Fe pairs of examples 1 of the present invention80PxSi15-xB5Viscosity-temperature dependence of the alloy (x-5-10) melt after a heat treatment at 1450 ℃ and a subsequent measurement of the viscosity during the temperature drop.
FIG. 3 shows Fe in example 1 of the present invention80P10Si5B5And (3) measuring the relation graph of the solidification temperature and the cooling parameter of the alloy melt at the casting temperature 1180 ℃.
FIG. 4 shows example 1 of the present invention, in which Fe with a casting temperature of 1180 ℃ and a solidification temperature of 455 ℃ is photographed by a transmission electron microscope80P10Si5B5High resolution schematic of amorphous alloy; only amorphous structures are shown in the figure, and no crystalline character appears.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention; after reading the present disclosure, various changes or modifications may be made by those skilled in the art, and equivalents may fall within the scope of the invention as defined by the appended claims.
With reference to fig. 1, the present application provides a process for preparing an amorphous alloy with low residual thermal stress, which has a core concept that a nonmetal element forming a low melting point alloy with a metal element is used to partially replace a nonmetal element forming a high melting point alloy with a metal element to reduce the viscosity of an alloy melt, thereby reducing the casting temperature of the alloy melt and eliminating the invalid superheat degree of the alloy melt; the supercooling solidification temperature of the alloy melt is increased by increasing the thickness of the copper sleeve of the cooling rod and/or increasing the temperature of cooling water, the ineffective supercooling degree of the alloy melt is reduced, and the temperature difference between the casting temperature and the solidification temperature of the melt is reduced, so that the low residual thermal stress of the prepared amorphous alloy is reduced.
Specifically, the process method for preparing the low residual thermal stress amorphous alloy comprises the following steps:
step S1, selecting a reference alloy, forming a series of alloys with different components by partially replacing a non-metal element forming a low-melting-point alloy with a metal element to form a high-melting-point alloy with the metal element based on the components of the reference alloy, measuring the viscosity of the series of alloy melts at different casting temperatures, and establishing the relationship between the viscosity of the series of alloy melts and the casting temperature-components, which is shown in FIG. 2; the relationship can guide the reduction of the invalid superheat degree of the alloy melt, such as the selection of proper amorphous alloy components, the selection of proper viscosity value and casting temperature;
step S2, aiming at the series of alloy melts, measuring the supercooling solidification temperature under different cooling conditions at different casting temperatures, and establishing the relation of the cooling conditions, the supercooling solidification temperature, the casting temperature and the components of the series of alloy melts; the relationship can guide the reduction of the ineffective supercooling degree of the alloy melt; the cooling conditions comprise the thickness of a copper sleeve of the cooling rod and the temperature of cooling water;
step S3, firstly, selecting low-viscosity alloy components according to the relation obtained in the step S1, and setting the casting temperature according to the viscosity standard so as to reduce the invalid superheat degree of the alloy melt; then, according to the relation obtained in the step S2, selecting a cooling condition, reducing the ineffective supercooling degree of the alloy melt, and reducing the temperature difference between the casting temperature and the solidification temperature of the alloy melt; finally, the low residual thermal stress amorphous alloy is prepared. The viscosity standard is the viscosity of the reference alloy melt at a certain casting temperature, such as the viscosity of the reference alloy melt at a normal casting temperature; and determining the casting temperature of the selected low-viscosity alloy component melt by taking the viscosity as a reference, wherein the casting temperature is lower than the casting temperature of the reference alloy melt at the viscosity, in other words, by selecting an alloy with more proper components, the melting point of the alloy can be reduced, the melt viscosity can be reduced, the casting temperature can be further reduced on the premise of meeting the critical superheat degree, and finally the invalid superheat degree of the alloy melt can be reduced.
In the above process for preparing the amorphous alloy with low residual thermal stress, as a preferred embodiment, the alloy melt is subjected to the overheating treatment in the processes of preparing the amorphous alloy in the steps S1, S2 and S3, and the overheating treatment is performed in the same manner.
As a preferred embodiment, the step S1 includes the following sub-steps:
s11, measuring the viscosity of the selected alloy melt at the normal casting temperature, and using the measured viscosity as a viscosity standard for selecting the casting temperature of the alloy melt with different components;
s12, under the condition of not changing the content of metal elements, preparing a series of low-viscosity alloys by increasing the content of non-metal elements forming low-melting-point alloys with the metal elements and simultaneously reducing the proportion of the content of non-metal elements forming high-melting-point alloys with the metal elements; s13, heating and melting the master alloy of the series of alloys, then carrying out heat treatment, measuring the change of the viscosity of the series of alloy melts along with the temperature in the process of cooling, and establishing the relationship of the viscosity of the alloy melts, the casting temperature and the alloy components; as shown in fig. 2.
The relation of the viscosity of the alloy melt, the casting temperature and the alloy components is used for guiding the reduction of the ineffective superheat degree of the alloy melt in the subsequent step S3, specifically, the alloy components are selected according to the relation obtained in the step S13, and the casting temperature of the selected low-viscosity alloy melt is determined according to the measured viscosity value (namely the viscosity standard of S11) required when the melt is cast; and may assist in selecting cooling conditions after reducing cooling capacity in subsequent steps.
As a preferred embodiment, the step S2 includes the following sub-steps:
s21, increasing the temperature of the cooling water and/or increasing the thickness of the cooling copper sleeve to reduce the cooling capacity of the cooling roller and increase the solidification temperature of the alloy melt;
s22, melting the amorphous alloy with the selected components, then carrying out overheating treatment, and then reducing the temperature to the set casting temperature;
s23, continuously pouring the alloy melt onto the surface of a cooling roller copper sleeve rotating at a high speed through a nozzle under the conditions of a plurality of set different cooling water temperatures and cooling copper sleeve thicknesses to obtain an amorphous alloy thin strip, and measuring the solidification temperature of the alloy melt on the cooling roller copper sleeve in situ; with the reduction of the cooling capacity, the solidification temperature of the alloy melt rises, and when the solidification temperature is higher than the amorphous structure transformation temperature of the alloy melt, a crystal phase begins to appear in the prepared amorphous alloy thin strip, so that the highest solidification temperature of the melt capable of obtaining the complete amorphous alloy is the limit for increasing the solidification temperature; the relation of the cooling condition-supercooling solidification temperature-casting temperature-composition of the series of alloy melts is obtained.
The solidification temperature is related to both the cooling parameter and the casting temperature, and the casting temperature is related to the alloy composition, so that a solidification temperature-cooling parameter relation graph (such as fig. 3) can be obtained under the condition that the alloy composition and the casting temperature are fixed, a specific solidification temperature-cooling parameter relation graph can change along with the casting temperature and the alloy composition, and a plurality of different solidification temperature-cooling parameter relation graphs (namely a plurality of graphs similar to fig. 3) are obtained in step S3 and are selected for use along with the change of the casting temperature and the alloy composition in step S2.
In the above-mentioned process for preparing the amorphous alloy with low residual thermal stress, as a preferred embodiment, in step S3, the cooling condition corresponding to the highest solidification temperature is selected according to the relationship obtained in step S2.
As a preferred embodiment, the material of the amorphous alloy is Fe-based, FeNi-based or FeCo-based in an amorphous alloy system; preferably the FeSiB series; further, the amorphous alloyThe material is Fe80PxSi15-xB5The alloy, wherein x is the atom percentage content, and x is 5-10.
In the above process for preparing an amorphous alloy with low residual thermal stress, as a preferred embodiment, in the sub-step S22 of the step S2, the temperature of the overheating process is 80-120 ℃ (such as 90 ℃, 100 ℃, 110 ℃) higher than the set casting temperature, and the time of the overheating process is 50-90min (such as 60min, 70min, 80 min).
In the above process for preparing amorphous alloy with low residual thermal stress, the casting temperature of the alloy melt is reduced by 0-120 deg.C (such as 20 deg.C, 40 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 110 deg.C).
In the above-mentioned process for preparing amorphous alloy with low residual thermal stress, as a preferred embodiment, the supercooled solidification temperature of the alloy melt is increased by 0-145 ℃ (such as 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃).
As a preferred embodiment, the amorphous alloy is in the shape of a thin strip.
As a preferred embodiment, the process for preparing the amorphous alloy with low residual thermal stress is characterized in that the amorphous alloy is prepared by a high-speed planar flow continuous casting method; the linear speed of the copper jacket surface of the cooling roll is 18-30m/s (such as 20m/s, 22m/s, 25m/s and 28 m/s).
The process for regulating the casting temperature of the amorphous alloy melt proposed by the present application is further illustrated by a specific example. The amorphous alloy thin strip in the embodiment is prepared by adopting a high-speed plane flow continuous casting method commonly used in the field, and the technological parameters of the high-speed plane flow continuous casting method which are not mentioned in the embodiment, including but not limited to a heat treatment system, the thickness of the prepared amorphous strip, the size of a nozzle gap, the distance between the nozzle gap and a roller sleeve and the like, are kept consistent.
Example 1
To produce Fe80PXSi15-XB5Thin amorphous alloy strip as an example (subscript in chemical formula)The figure is atomic percent content at%), the specific operation steps of the process method for reducing the thermal stress of the amorphous alloy thin strip provided by the invention are as follows:
step 1, reducing the viscosity of the amorphous alloy melt:
(1) firstly, preparing Fe according to actual conditions80Si15B5The casting temperature of the alloy melt is determined to be 1300 ℃ according to the requirement on the casting temperature of the alloy melt during amorphous alloy. Mixing Fe80Si15B5Heating the alloy melt to 1450 ℃, keeping the temperature for 1 hour, then cooling to 1300 ℃, keeping the temperature for 1 hour, then measuring the viscosity of the alloy melt by adopting a high-temperature viscosity measuring instrument (product of GBX company, model: Viscodrop 2000), obtaining that the viscosity value of the alloy melt at the casting temperature is 13.5mPas, and then using the viscosity standard as the casting temperature of the alloy melt with different components;
(2) under the condition of not changing the content of the metal element, a series of low-viscosity Fe is prepared by increasing the partial substitution of the non-metal element P forming a low melting point temperature with the metal element for the non-metal element Si forming a high melting point temperature with the metal element80PXSi15-XB5An alloy melt, wherein X ranges from 5 to 10;
(3) heating the series of alloy melts with different components to 1450 ℃, preserving heat for 1 hour, then measuring the change of the viscosity of the series of alloy melts with the temperature reduction, specifically, setting a measuring point every 50 ℃ from 1450 ℃, measuring the viscosity value of the melt after preserving heat for 1 hour when the temperature is reduced to the temperature of one measuring point, and thus establishing the relationship between the melt viscosity reduction and the amorphous alloy components, as shown in figure 2;
(4) the component of the selected amorphous alloy is Fe80P10Si5B5And determining the selected low-viscosity Fe according to the measured viscosity value 13.5mPas required by the melt casting, namely the viscosity standard selected in the step (1) and the relation obtained in the step (3)80P10Si5B5The casting temperature of the alloy melt was 1180 ℃ (i.e., the set casting temperature), as shown in fig. 2;
step 2, increasing the solidification temperature of the alloy melt:
(1) the cooling capacity of the cooling roller is reduced by singly adopting a method for increasing the temperature of cooling water or singly adopting a method for increasing the thickness of a cooling copper sleeve, or the cooling capacity of the cooling roller is reduced by jointly using the two methods, so that the solidification temperature of the alloy melt is increased;
(2) selected component of Fe80P10Si5B5After the amorphous alloy is melted, carrying out overheating treatment on the alloy melt for 1 hour at 1450 ℃, and then reducing the temperature to 1180 ℃ of the set casting temperature;
(3) forming different cooling parameters by combining a cooling water temperature of 20-35 ℃ and a cooling copper sleeve with the thickness of 22-32 MM, continuously pouring an alloy melt onto the surface of the cooling roller copper sleeve rotating at a high speed through a nozzle under different cooling parameters (cooling conditions), wherein the linear speed of the surface of the copper sleeve is 25m/s, preparing an amorphous alloy thin strip, measuring the solidification temperature of the amorphous alloy melt on the cooling roller copper sleeve rotating at the high speed in situ by using a laser infrared thermometer (model: Marathon MM), establishing the relation between the solidification temperature and the cooling parameters, wherein the obtained melt solidification temperature is 310 ℃ under the cooling conditions that the cooling water temperature is 20 ℃ and the cooling copper sleeve thickness is 22 MM, the cooling capacity of the cooling roller is reduced and the solidification temperature of the melt is increased, when the solidification temperature of the melt is higher than 455 ℃, alpha-Fe crystal phase begins to appear in the amorphous alloy thin strip, so the highest solidification temperature of the melt of the completely amorphous alloy is 455 ℃;
step 3, preparing the amorphous alloy thin strip with reduced thermal stress:
first, according to the relationship obtained in step 1, Fe, which is an alloy component having a low viscosity, is selected80P10Si5B5Setting a casting temperature 1180 ℃ according to a viscosity standard; then, according to the relation obtained in the step 2, the solidification temperature is selected to be 455 ℃, and the cooling conditions are determined to be that the cooling water temperature is 35 ℃ and the thickness of the cooling copper bush is 30 mm; finally, the high-speed plane flow continuous casting method is adopted to prepare the amorphous alloy with low residual thermal stress under the conditions, namely Fe80P10Si5B5After the master alloy is melted, carrying out overheating treatment on the alloy melt for 1 hour at the temperature of 1450 ℃, then reducing the temperature to 1180 ℃ of set casting temperature, continuously casting the alloy melt to the surface of a cooling roller copper sleeve which is provided with a cooling water temperature of 35 ℃ and a cooling copper sleeve thickness of 30 mm and rotates at a high speed through a nozzle, wherein the linear speed of the surface of the copper sleeve is 25m/s, and obtaining a target product Fe80P10Si5B5Amorphous alloy thin strip.
The specific method for detecting the microstructure of the amorphous alloy comprises the following steps: (1) firstly, the target product Fe prepared in the step 3 is80P10Si5B5Cutting an amorphous alloy thin strip prepared at the casting temperature of 1180 ℃ and the solidification temperature of 455 ℃ 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, and performing ion bombardment thinning to finally obtain a film-shaped sample which can be penetrated by an electron beam; (2) and (3) mounting the prepared amorphous alloy transmission electron microscope sample on a transmission electron microscope sample table with a heating function, and shooting a clear two-dimensional transmission electron microscope image of the sample by using a transmission electron microscope under high magnification. The target product Fe is obtained by the detection method80P10Si5B5Fig. 4 shows a schematic diagram of a high-resolution image of a microstructure of an amorphous alloy thin strip, in which the displayed structural features are amorphous disordered structures, and no crystalline structural feature appears, which indicates that the difference between the alloy melt casting temperature and the supercooling solidification temperature can be reduced in this embodiment, and the control of the residual thermal stress in the amorphous alloy thin strip is realized.
The specific method for detecting the residual thermal stress of the amorphous alloy is as follows: each cut out a 2 cm wide and 4 cm long section of Fe with melt solidification temperatures of 310 ℃ and 455 ℃ respectively80P10Si5B5The amorphous alloy thin strip is folded in half along the length direction, and the pressure when the amorphous alloy thin strip is folded in half is measured and kept by a pressure gauge. And (3) measuring: the pressure measured when the amorphous alloy thin strip with the solidification temperature of 455 ℃ is folded in half is 2.2 newtons, and the pressure measured when the amorphous alloy thin strip with the solidification temperature of 310 ℃ is folded in half is 3.2 newtons, which shows the residue of the amorphous alloy thin stripThe thermal stress is lower, and the amorphous alloy with lower residual thermal stress can be prepared by the process method provided by the application.
In conclusion, the process method for reducing the difference between the casting temperature and the solidification temperature of the amorphous alloy melt can obtain the high-quality amorphous alloy thin strip with low residual thermal stress, and is suitable for different amorphous alloy material systems.
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 (15)
1. A process method for preparing low residual thermal stress amorphous alloy is characterized by comprising the following steps:
step S1, selecting a reference alloy, forming a series of alloys with different components by partially replacing a non-metal element forming a low-melting-point alloy with a metal element to form a high-melting-point alloy with the metal element on the basis of the components of the reference alloy, measuring the viscosity of the series of alloy melts at different casting temperatures, and establishing the relationship between the viscosity of the series of alloy melts and the casting temperature-components;
step S2, aiming at the series of alloy melts, measuring the supercooling solidification temperature under different cooling conditions at different casting temperatures, and establishing the relation of the cooling conditions, the supercooling solidification temperature, the casting temperature and the components of the series of alloy melts;
step S3, firstly, selecting low-viscosity alloy components according to the relation obtained in the step S1, and setting the casting temperature according to the viscosity standard; then, according to the selected alloy composition, the set casting temperature and the relation obtained in the step S2, selecting a cooling condition corresponding to the supercooling solidification temperature increase; finally, the low residual thermal stress amorphous alloy is prepared.
2. The process for preparing low residual thermal stress amorphous alloy according to claim 1,
in the processes of preparing the amorphous alloy in the steps S1, S2 and S3, the alloy melt is subjected to overheating treatment, and the overheating treatment is performed according to the same schedule.
3. The process for preparing low residual thermal stress amorphous alloy according to claim 2,
the step S1 includes the following sub-steps:
s11, measuring the viscosity of the selected reference alloy melt at the normal casting temperature, and using the measured viscosity as a viscosity standard for selecting the casting temperature of the alloy melt with different components;
s12, under the condition of not changing the content of metal elements, preparing a series of low-viscosity alloys by increasing the content of non-metal elements forming low-melting-point alloys with the metal elements and simultaneously reducing the proportion of the content of non-metal elements forming high-melting-point alloys with the metal elements;
s13, heating and melting the master alloy of the series of alloys, measuring the change of the viscosity of the series of alloy melts along with the temperature in the process of cooling, and establishing the relation of the viscosity of the alloy melts, the casting temperature and the components.
4. The process for preparing amorphous alloy with low residual thermal stress according to claim 1, wherein said step S2 comprises the following sub-steps:
s21, increasing the temperature of the cooling water and/or increasing the thickness of the cooling copper sleeve to reduce the cooling capacity of the cooling roller and increase the solidification temperature of the alloy melt;
s22, melting the amorphous alloy with the selected components, then carrying out overheating treatment, and then reducing the temperature to the set casting temperature;
s23, continuously casting the alloy melt onto the surface of a cooling roller copper sleeve rotating at a high speed through a nozzle under the conditions of a plurality of set different cooling water temperatures and cooling copper sleeve thicknesses to obtain an amorphous alloy thin strip, and measuring the solidification temperature of the alloy melt on the cooling roller copper sleeve in situ; with the reduction of the cooling capacity, the solidification temperature of the alloy melt rises, and when a crystal phase begins to appear in the amorphous alloy thin strip, the solidification temperature of the previous amorphous alloy which can obtain complete amorphous alloy is the highest solidification temperature; thereby obtaining the relation of the cooling condition-supercooling solidification temperature-casting temperature-composition of the series of alloy melts;
in the step S3, the cooling condition corresponding to the highest solidification temperature is selected based on the relationship obtained in the step S2.
5. The process for preparing low residual thermal stress amorphous alloy according to any of claims 1-4,
the amorphous alloy is made of Fe base, FeNi base or FeCo base in an amorphous alloy system.
6. The process for preparing low residual thermal stress amorphous alloy according to claim 5,
the material of the amorphous alloy is FeSiB series in an amorphous alloy system.
7. The process for preparing low residual thermal stress amorphous alloy according to claim 6,
the amorphous alloy is made of Fe80PxSi15-xB5An alloy, wherein x is the atomic percent content, and x = 5-10.
8. The process for preparing low residual thermal stress amorphous alloy according to claim 4,
in the substep S22 of the step S2, the temperature of the overheating treatment is 80 to 120 ℃ higher than the set casting temperature, and the time of the overheating treatment is 50 to 90 min.
9. The process for preparing amorphous alloy with low residual thermal stress as claimed in claim 5, wherein the casting temperature of the alloy melt is reduced by >0 ≦ 120 ℃.
10. The process for preparing amorphous alloy with low residual thermal stress as claimed in claim 6, wherein the casting temperature of the alloy melt is reduced by >0 ≦ 120 ℃.
11. The process for preparing amorphous alloy with low residual thermal stress as claimed in claim 7, wherein the casting temperature of the alloy melt is reduced by >0 ≦ 120 ℃.
12. The process for preparing amorphous alloy with low residual thermal stress as claimed in claim 8, wherein the casting temperature of the alloy melt is reduced by >0 ≦ 120 ℃.
13. The process for preparing the amorphous alloy with low residual thermal stress according to any one of claims 8 to 12, wherein the supercooling solidification temperature of the alloy melt is increased by more than 0 ℃ and less than or equal to 145 ℃.
14. The process for preparing the amorphous alloy with low residual thermal stress according to claim 8, wherein the amorphous alloy is in the shape of a thin strip.
15. The process for preparing the amorphous alloy with low residual thermal stress according to claim 8, wherein the amorphous alloy is prepared by a high-speed planar flow casting method; the linear speed of the copper sleeve surface of the cooling roller is 18-30 m/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349539.7A CN111014599B (en) | 2019-12-24 | 2019-12-24 | Process method for preparing low residual thermal stress amorphous alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349539.7A CN111014599B (en) | 2019-12-24 | 2019-12-24 | Process method for preparing low residual thermal stress amorphous alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111014599A CN111014599A (en) | 2020-04-17 |
| CN111014599B true CN111014599B (en) | 2021-07-13 |
Family
ID=70213049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911349539.7A Active CN111014599B (en) | 2019-12-24 | 2019-12-24 | Process method for preparing low residual thermal stress amorphous alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111014599B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000271714A (en) * | 1999-01-20 | 2000-10-03 | Alps Electric Co Ltd | Production of amorphous soft magnetic alloy injection formed body and molding die for amorphous soft magnetic alloy injection formed body |
| WO2004092428A3 (en) * | 2003-04-14 | 2005-03-24 | Liquidmetal Technologies Inc | Continuous casting of bulk solidifying amorphous alloys |
| WO2012005975A1 (en) * | 2010-06-28 | 2012-01-12 | Mcconway & Torley, Llc | Improved ferro-alloys |
| CN105970119A (en) * | 2016-07-13 | 2016-09-28 | 江苏非晶电气有限公司 | Technique for enhancing amorphous forming ability of alloy melt |
| CN106424616A (en) * | 2016-09-30 | 2017-02-22 | 江苏非晶电气有限公司 | Preparation method of non-crystalline solid alloy thin strip for reducing alloy melt pouring temperature |
| CN110093571A (en) * | 2019-05-22 | 2019-08-06 | 江苏集萃安泰创明先进能源材料研究院有限公司 | A method of regulation amorphous alloy micro-structure |
| CN110181007A (en) * | 2019-06-11 | 2019-08-30 | 江苏中科启航新材料工业研究院有限公司 | A kind of process of regulation iron-based amorphous alloy ribbon material thickness |
| CN110195188A (en) * | 2019-06-11 | 2019-09-03 | 江苏中科启航新材料工业研究院有限公司 | A method of it reducing melt cast temperature and prepares iron-based amorphous alloy ribbon material |
| CN110216249A (en) * | 2019-06-11 | 2019-09-10 | 江苏中科启航新材料工业研究院有限公司 | A kind of preparation method of the Fe-based amorphous alloy strip of high thermal stability |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484747A (en) * | 2013-05-28 | 2014-01-01 | 江苏迈盛新材料有限公司 | Method for preparing iron-based amorphous alloy with supersoft ferromagnetic property |
| CN107326158B (en) * | 2017-05-24 | 2019-04-23 | 南京腾元软磁有限公司 | A kind of process improving iron content in amorphous Fe silicon boron alloy strip |
| CN108018504B (en) * | 2017-12-21 | 2020-05-08 | 青岛云路先进材料技术股份有限公司 | Iron-based amorphous alloy and preparation method thereof |
-
2019
- 2019-12-24 CN CN201911349539.7A patent/CN111014599B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000271714A (en) * | 1999-01-20 | 2000-10-03 | Alps Electric Co Ltd | Production of amorphous soft magnetic alloy injection formed body and molding die for amorphous soft magnetic alloy injection formed body |
| WO2004092428A3 (en) * | 2003-04-14 | 2005-03-24 | Liquidmetal Technologies Inc | Continuous casting of bulk solidifying amorphous alloys |
| WO2012005975A1 (en) * | 2010-06-28 | 2012-01-12 | Mcconway & Torley, Llc | Improved ferro-alloys |
| CN105970119A (en) * | 2016-07-13 | 2016-09-28 | 江苏非晶电气有限公司 | Technique for enhancing amorphous forming ability of alloy melt |
| CN106424616A (en) * | 2016-09-30 | 2017-02-22 | 江苏非晶电气有限公司 | Preparation method of non-crystalline solid alloy thin strip for reducing alloy melt pouring temperature |
| CN110093571A (en) * | 2019-05-22 | 2019-08-06 | 江苏集萃安泰创明先进能源材料研究院有限公司 | A method of regulation amorphous alloy micro-structure |
| CN110181007A (en) * | 2019-06-11 | 2019-08-30 | 江苏中科启航新材料工业研究院有限公司 | A kind of process of regulation iron-based amorphous alloy ribbon material thickness |
| CN110195188A (en) * | 2019-06-11 | 2019-09-03 | 江苏中科启航新材料工业研究院有限公司 | A method of it reducing melt cast temperature and prepares iron-based amorphous alloy ribbon material |
| CN110216249A (en) * | 2019-06-11 | 2019-09-10 | 江苏中科启航新材料工业研究院有限公司 | A kind of preparation method of the Fe-based amorphous alloy strip of high thermal stability |
Non-Patent Citations (1)
| Title |
|---|
| Fe73.5Si13.5B9Nb3Cu1纳米晶合金的粘度特征;李强等;《金属功能材料》;20170415;第24卷(第2期);P7-12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111014599A (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105970119B (en) | A kind of process improving alloy melt amorphous formation ability | |
| TWI685575B (en) | Low thermal expansion alloy with excellent low temperature stability, its manufacturing method, low thermal expansion alloy powder, and laminated forming member | |
| Bhattacharjee et al. | Texture evolution during cross rolling and annealing of high-purity nickel | |
| CN106424616A (en) | Preparation method of non-crystalline solid alloy thin strip for reducing alloy melt pouring temperature | |
| He et al. | Liquid–liquid structure transition and nucleation in undercooled Co-B eutectic alloys | |
| CN101215679A (en) | Nonmagnetic iron-base block amorphous alloy and preparation method thereof | |
| CN110181007B (en) | Process method for regulating thickness of iron-based amorphous alloy strip | |
| CN110195188B (en) | Method for preparing iron-based amorphous alloy strip by reducing melt pouring temperature | |
| CN110216249B (en) | Preparation method of iron-based amorphous alloy thin strip with high thermal stability | |
| CN111014600B (en) | Process method for reducing difference between casting temperature and solidification temperature of amorphous alloy melt | |
| CN111014599B (en) | Process method for preparing low residual thermal stress amorphous alloy | |
| Wang et al. | MnS precipitation behavior of high-sulfur microalloyed steel under sub-rapid solidification process | |
| CN110976794B (en) | Process method for increasing thickness of amorphous alloy strip | |
| Lai et al. | Phase selection and re-melting-induced anomalous eutectics in undercooled Ni–38 wt% Si alloys | |
| US9963763B2 (en) | Production of metallic glass by melt deposition | |
| Liu et al. | Effects of pulse magneto-oscillation on GCr15 bearing steel continuous casting billet | |
| Firdosy et al. | Laser-Deposited Soft Magnetic Fe–Ni–Mo Alloy: A Processing—Microstructure Study | |
| Sugioka et al. | Study on the effect of melt convection on phase separation structures in undercooled CuCo alloys using an electromagnetic levitator superimposed with a static magnetic field | |
| CN110976796B (en) | Preparation method of amorphous alloy thin strip capable of reducing residual thermal stress | |
| CN110976793B (en) | Process method for regulating and controlling casting temperature of amorphous alloy melt | |
| CN110976795B (en) | Alloy melt solidification temperature regulation and control method based on cooling rate | |
| Xie et al. | Non-isothermal crystallization kinetics and magnetic properties of FeCoNiCrZr metallic glass | |
| Chen et al. | Plasticity and rejuvenation of aged metallic glasses by ultrasonic vibrations | |
| CN1327990C (en) | Method and apparatus for producing amorphous alloy sheet, and amorphous alloy sheet produced using the same | |
| US10589349B2 (en) | Production of metallic glass objects by melt deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220630 Address after: 512026 building 56, Huangshaping Innovation Park, guanshaocheng phase I, Wujiang District, Shaoguan City, Guangdong Province Patentee after: Chuangming (Shaoguan) Green Energy Materials Technology Research Institute Co.,Ltd. Address before: 213034 No. 242, Zhongfang Huayuan, Chunjiang Town, Xinbei District, Changzhou City, Jiangsu Province Patentee before: JIANGSU JICUI ANTAI CHUANGMING ADVANCED ENERGY MATERIALS RESEARCH INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right |