阅读说明：本技术 高通量块体合金制备装置、方法及应用 (High-throughput block alloy preparation device, method and application ) 是由 李明星 闻平 孟磊 汪卫华 柳延辉 于 2019-02-22 设计创作，主要内容包括：本发明涉及一种有效的高通量块体合金的制备装置和方法。在现有先进的感应熔炼技术基础上,调控和设计变频电源、电容器、感应线圈和加热坩埚的技术参量,研制出可单批次熔炼合金块材100个以上的实验室用高真空感应炉。该设备最高熔炼温度可达1800-2000℃,能实现监控温度和多个样品形貌的实时记录。从而为高通量实验手段的发展奠定材料基础,加快了合金的开发速度。(The invention relates to an effective high-flux bulk alloy preparation device and method. On the basis of the existing advanced induction melting technology, the technical parameters of a variable frequency power supply, a capacitor, an induction coil and a heating crucible are regulated and designed, and the laboratory high-vacuum induction furnace capable of melting more than 100 alloy blocks in a single batch is developed. The maximum melting temperature of the device can reach 1800-2000 ℃, and the real-time recording of the monitoring temperature and the shapes of a plurality of samples can be realized. Thereby laying a material foundation for the development of high-flux experimental means and accelerating the development speed of the alloy.)

1. An apparatus for preparing a high throughput bulk alloy, the apparatus comprising:

a vacuum chamber comprising an upper end gas inlet and a lower end gas extraction port;

the crucible is used for containing alloy raw materials;

the graphite sleeve is arranged outside the crucible to protect the crucible;

the high-frequency induction heating coil is arranged outside the crucible graphite sleeve;

the cooling body is arranged at the bottom of the crucible and used for cooling the crucible and the sample after heating;

the temperature measuring instrument is arranged at the top of the vacuum chamber, measures the temperature of the sample in real time and transmits the temperature data to the controller;

one end of the feedback controller receives a temperature signal from the infrared thermometer, and the other end of the feedback controller outputs a current control signal to the power supply;

the lower end of the power supply is connected with the heating coil to provide current, and the upper end of the power supply is connected with the feedback controller;

the camera is arranged at the top of the vacuum chamber and used for observing and recording the heating and cooling processes of the sample; and

a vacuum pump.

2. The apparatus of claim 1, wherein the crucible is a porous crucible;

the crucible material is selected from one or more of the following: graphite, alumina, zirconia, calcium oxide; preferably graphite;

the number of the crucible holes is 50-500, preferably 50-200, and more preferably 50-100;

the diameter of the crucible hole is 3-8 mm, preferably 4-7 mm, and more preferably 5-6 mm;

and/or

The depth of the crucible hole is 3-8 mm, preferably 4-7 mm, and most preferably 5 mm.

3. A device according to claim 1 or 2, wherein the thermometer is an infrared thermometer.

4. The device according to any one of claims 1 to 3, wherein the material of the cooling body is selected from one or more of the following: red copper, stainless steel; preferably red copper.

5. The device according to any one of claims 1 to 4, characterized in that the cooling body is provided with a lifting device; preferably, the lifting device is connected to an external motor through a wire.

6. The apparatus according to any one of claims 1 to 5, wherein the vacuum pump comprises a pre-mechanical pump and a molecular pump set, the pre-mechanical pump and the molecular pump set are connected with the pumping port at the lower end of the vacuum chamber through a butterfly valve, the pre-mechanical pump provides a low vacuum environment for the molecular pump, and the molecular pump provides a high vacuum environment for the vacuum chamber;

preferably, the vacuum pump further comprises a side-pumping mechanical pump, and the side-pumping mechanical pump is connected with the pumping port at the lower end of the vacuum chamber through a pumping valve and is used for pumping the waste gas in the vacuum chamber.

7. A method for producing an alloy, characterized by using the apparatus according to any one of claims 1 to 6;

preferably, the preparation method comprises the following steps:

(1) mixing the raw materials with different components according to percentage, and filling the raw materials into small holes of a crucible in sequence;

(2) putting the filled crucible into a stainless steel vacuum chamber, and adding a graphite sleeve;

(3) vacuumizing the vacuum chamber through a vacuum pump, and filling protective gas through a gas inlet; opening the camera, the temperature measuring instrument and the feedback controller, and heating by using a high-frequency induction heating coil; meanwhile, shooting and recording are carried out by the camera, and the temperature measuring instrument transmits the temperature data to the feedback controller in real time; the feedback controller realizes the control of the temperature of the sample by changing the current of the high-frequency induction coil;

(4) and stopping heating after all the samples are melted, connecting the cooling body with the bottom of the crucible, cooling the samples, and recording the cooling process by the camera.

8. The method of claim 7, wherein in step (3), the shielding gas is selected from one or more of: argon and nitrogen; argon is preferred.

9. The method according to claim 8, wherein in the step (3), the heating current of the high-frequency induction coil is 0-70A.

10. Use of an alloy preparation device according to any one of claims 1 to 6 for preparing an alloy bulk product.

Technical Field

The invention belongs to the field of condensed state physics and material science, and particularly relates to a high-flux bulk alloy preparation device, a method and application.

Background

The alloy is a substance with metal characteristics, which is synthesized by two or more than two metals or non-metals through a certain method, and is widely applied to the fields of infrastructure construction, transportation, aerospace, processing and manufacturing, advanced weapons, ocean exploration, energy, medical treatment and health and the like. In recent decades, with the development of science and technology, the special requirements for alloys are more and more prominent. Such as superalloys, corrosion resistant alloys, hydrogen storage alloys, shape memory alloys, and the like. Therefore, the development efficiency of the alloy material is accelerated, and the realization of high-flux preparation of the alloy block material is of great significance.

The method of 'material genome' is an important means for realizing the efficient development of alloy materials at present. The method comprises two main parts of high-throughput preparation and characterization, wherein the high-throughput preparation refers to the preparation of a plurality of materials with different components or different structures at one time, so that the time and labor required by material preparation are greatly saved; the high-throughput characterization is to rapidly and accurately measure physical and chemical properties of a plurality of materials with different components or different structures on the basis of high-throughput preparation so as to obtain unified and standardized material big data. High throughput material preparation is therefore a prerequisite and basis. Since only high throughput material preparation is achieved, it is possible to screen out new materials that meet specific requirements by rapid characterization. At present, the main alloy high-throughput preparation method is a vapor deposition method, and single-batch multi-sample preparation is realized by preparing a film material with component gradient. However, it is difficult to actually screen out a new material having practical significance by combining films. For alloy materials, the vast majority of applications require the use of bulk materials. In addition to the chemical composition, the microstructure of the material also has an equally crucial influence on the properties of the material. The film material and the block material have great difference in size, and the materials with the same components are obviously different in microstructure, so that the characteristics and the performance of the block material cannot be directly displayed in many cases by combining the film material, the experimental efficiency is reduced, and many alloy materials with excellent performance are missed.

The preparation method of the high-flux material is an important basis for realizing a high-flux experimental means, but currently, the preparation method only stays at the stage of preparing the high-flux thin film material. High throughput preparation of bulk materials, particularly bulk alloys, has not been an effective method. For single block alloys, there are mainly resistance furnace melting, arc melting and induction melting. For the one-time smelting of a plurality of block alloys with different components (namely, high-throughput preparation), if the block alloys are smelted by a resistance furnace, the temperature and the temperature rise rate of a sample are difficult to be quickly and accurately regulated, and the formation and regulation of the microstructure of the high-throughput block alloy are not facilitated. The size of the electric arc melting is difficult to cover the crucible for containing the whole high-flux block alloy, the temperature of the sample cannot be accurately regulated, and the requirements on heat resistance and heat conduction of the crucible are high. The induction melting is induction heating equipment with highest metal material heating efficiency, fastest speed, low consumption, energy conservation and environmental protection. When a strong magnetic flux whose polarity is instantaneously changed is generated in the coil and an object to be heated such as a metal is placed in the coil, the magnetic flux penetrates the entire object to be heated, and a large eddy current is generated in the opposite direction to the heating current in the object to be heated. Since the resistance exists in the object to be heated, a large amount of joule heat is generated to rapidly raise the temperature of the object itself, thereby achieving the purpose of heating all metal materials. By adjusting the current in the coil, the temperature of the metal can be quickly and effectively controlled, so that the block alloy can be effectively and controllably prepared.

However, the apparatus and method for induction melting of high throughput bulk alloys also face a number of problems. Firstly, the high-flux preparation starts late, and corresponding matched equipment and design are deficient; secondly, high-flux preparation needs to accurately control the temperature of the sample, and a self-feedback system for controlling the temperature of the sample and the current of the induction coil is difficult to solve; at the same time, the need to re-match crucibles that meet high throughput preparation is met. Therefore, no means and device for preparing high-throughput block alloy exists at present.

Disclosure of Invention

Accordingly, it is an object of the present invention to overcome the deficiencies of the prior art and to provide an efficient apparatus and method for the production of high throughput bulk alloys. Thereby laying a foundation for the development of high-flux experimental means and the acceleration of the development speed of the alloy.

To achieve the above object, a first aspect of the present invention provides an apparatus for preparing a high-flux bulk alloy, the apparatus comprising:

a vacuum chamber comprising an upper end gas inlet and a lower end gas extraction port;

the crucible is used for containing alloy raw materials;

the graphite sleeve is arranged outside the crucible to protect the crucible;

the high-frequency induction heating coil is arranged outside the crucible graphite sleeve;

the cooling body is arranged at the bottom of the crucible and used for cooling the crucible and the sample after heating;

the temperature measuring instrument is arranged at the top of the vacuum chamber, measures the temperature of the sample in real time and transmits the temperature data to the controller;

one end of the feedback controller receives a temperature signal from the infrared thermometer, and the other end of the feedback controller outputs a current control signal to the power supply;

the lower end of the power supply is connected with the heating coil to provide current, and the upper end of the power supply is connected with the feedback controller;

the camera is arranged at the top of the vacuum chamber and used for observing and recording the heating and cooling processes of the sample; and

a vacuum pump.

The apparatus according to the first aspect of the present invention, wherein the crucible is a porous crucible;

the crucible material is selected from one or more of the following: graphite, alumina, zirconia, calcium oxide; preferably graphite;

the number of the crucible holes is 50-500, preferably 50-200, and more preferably 50-100;

the diameter of the crucible hole is … 3-8 … mm, preferably … 4-7 … mm, and more preferably … 5-6 … mm; and/or

The depth of the crucible hole is 3-8 mm, preferably 4-7 mm, and most preferably 5 mm.

The apparatus according to the first aspect of the invention, wherein the cooling body is provided with a lifting device; preferably, the lifting device is connected to an external motor through a wire.

The device according to the first aspect of the present invention, wherein the vacuum pump comprises a pre-mechanical pump and a molecular pump set, the pre-mechanical pump and the molecular pump set are connected with the pumping port at the lower end of the vacuum chamber through a butterfly valve, the pre-mechanical pump provides a low vacuum environment for the molecular pump, and the molecular pump provides a high vacuum environment for the vacuum chamber;

preferably, the vacuum pump further comprises a side-pumping mechanical pump, and the side-pumping mechanical pump is connected with the pumping port at the lower end of the vacuum chamber through a pumping valve and is used for pumping the waste gas in the vacuum chamber.

A second aspect of the present invention provides a method for producing an alloy, using the apparatus of the first aspect;

preferably, the preparation method comprises the following steps:

(1) mixing the raw materials with different components according to percentage, and filling the raw materials into small holes of a crucible in sequence;

(2) putting the filled crucible into a stainless steel vacuum chamber, and adding a graphite sleeve;

(3) vacuumizing the vacuum chamber through a vacuum pump, and filling protective gas through a gas inlet; opening the camera, the temperature measuring instrument and the feedback controller, and heating by using a high-frequency induction heating coil; meanwhile, shooting and recording are carried out by the camera, and the temperature measuring instrument transmits the temperature data to the feedback controller in real time; the feedback controller realizes the control of the temperature of the sample by changing the current of the high-frequency induction coil;

(4) and stopping heating after all the samples are melted, connecting the cooling body with the bottom of the crucible, cooling the samples, and recording the cooling process by the camera.

The production method according to the second aspect of the present invention, wherein, in the step (3), the protective gas is selected from one or more of: argon and nitrogen; argon is preferred.

The manufacturing method according to the second aspect of the present invention, wherein in the step (3), a heating current of the high-frequency induction coil is 0 to 70A.

The third aspect of the invention provides the use of the alloy preparation apparatus of the first aspect for preparing an alloy bulk product.

The invention provides a preparation device of a high-flux bulk alloy, which comprises the following components:

-a stainless steel vacuum chamber;

-a specially made perforated crucible for containing a graded composition of bulk alloy starting material;

-a graphite sleeve disposed outside the crucible to protect the crucible;

-a high frequency induction heating coil disposed outside the crucible graphite sleeve;

a cooling body with a lifting device, which is arranged at the bottom of the crucible and is used for the purpose of heating and cooling the crucible and the sample, wherein the lifting device is connected with an external motor through a lead.

-a high frequency power supply connected at a lower end to the heating coil for supplying current and at an upper end to the feedback controller;

an infrared thermometer placed on top of the stainless steel vacuum chamber for measuring the temperature of the sample in real time and transmitting the temperature data to the controller;

a recording feedback controller, one end of which receives the temperature signal from the infrared thermometer and the other end of which outputs a current control signal to the high-frequency power supply;

a camera arranged on the top of the stainless steel vacuum chamber for observing and recording the heating and cooling process of the sample;

a prime mechanical pump and a molecular pump set which are connected with the pumping port at the lower end of the stainless steel vacuum chamber through a butterfly valve, wherein the prime mechanical pump provides a low vacuum environment for the molecular pump, and the molecular pump provides a high vacuum environment for the stainless steel vacuum chamber;

a high-purity argon bottle connected with the upper gas inlet of the stainless steel vacuum chamber through a gas charging valve;

a bypass pump connected with the lower end of the stainless steel vacuum chamber through an air exhaust valve and used for extracting the waste gas in the stainless steel vacuum chamber.

The invention provides a method for preparing a block alloy with high flux, which is an induction melting method carried out on the device for preparing the block alloy with high flux, and specifically comprises the following steps:

1) preparing high-flux alloy raw materials: raw materials with different components are prepared according to percentage and are sequentially filled into the small holes of the crucible. Each orifice corresponds to a designed component, containing all of the ingredients of the material. The size of each raw material can be larger than 3mm, and rod-shaped or powdery raw materials can be used;

2) putting the crucible in the step 1) into a stainless steel vacuum chamber, and adding a graphite sleeve;

3) vacuumizing the stainless steel vacuum chamber to 10Pa by using a side pumping mechanical pump, and closing a valve connected with the side pumping mechanical pump and the stainless steel vacuum chamber; continuously vacuumizing the stainless steel vacuum chamber to a vacuum degree equal to or higher than 10 by a pre-mechanical pump and a molecular pump set^-3Pa, closing the butterfly valve connecting the fore mechanical pump and the molecular pump set with the stainless steel vacuum chamber; then high-purity (99.999 percent) argon is filled in the reactor under 0.02 MPa; opening the camera, the infrared thermometer and the feedback system; heating with high-frequency induction coil under set current (0-70A); at the same time, the camera takes a picture and records, the infrared thermometerTransmitting the temperature data to a feedback system in real time; the feedback system changes the current of the high-frequency induction coil in real time to realize the control of the temperature of the sample;

4) after all samples are melted, the current of the high-frequency induction coil returns to zero; and meanwhile, starting the lifting device to connect the cooling body with the bottom of the crucible so as to rapidly cool the sample. And meanwhile, the camera records the whole cooling process, so that the subsequent analysis of each sample microstructure is facilitated.

The preparation method of the high-flux bulk alloy is to regulate and design technical parameters of a variable frequency power supply, a capacitor, an induction coil and a heating crucible on the basis of the existing advanced induction melting technology, and develop the laboratory high-vacuum induction furnace capable of melting more than 100 alloy bulk materials in a single batch. The maximum melting temperature of the device can reach 1800-2000 ℃, and the real-time recording of the monitoring temperature and the shapes of a plurality of samples can be realized.

The present invention may have, but is not limited to, the following beneficial effects:

1. more than 100 alloy blocks with different components can be smelted in a single batch, while the traditional induction smelting can only smelt the alloy blocks with one component at a time, so that the preparation efficiency and speed of the material are greatly improved;

2. the melting temperature can reach 1800-; the sample is prevented from being oxidized to a certain degree;

3. the alloy structure is efficiently regulated and controlled in batch, and the performance optimization of the alloy block is realized;

4. obtaining the change of a large number of microstructures along with components and process parameters, and establishing a component-process-structure-performance database of the system;

5. promote the generalization of the technology, and can be widely used in the research fields of various alloys such as high-temperature alloy, rare earth alloy material, high-entropy alloy, shape memory alloy and the like, and develop a novel alloy material with excellent comprehensive performance.

Drawings

Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

fig. 1 shows a schematic diagram of a high flux bulk alloy heating section apparatus according to an embodiment of the invention.

FIG. 2 shows a physical diagram of a tailored crucible of a high flux bulk alloy apparatus according to an embodiment of the invention.

Fig. 3 shows a schematic of phase formation and microstructure of a bulk alloy.

FIG. 4 shows a front view of a high flux bulk alloy host apparatus according to an embodiment of the invention.

Fig. 5 shows a left side view of a high flux bulk alloy host device according to an embodiment of the invention.

Description of reference numerals:

1. a stainless steel vacuum chamber; 2. specially manufacturing a crucible; 3. a graphite sleeve; 4. a high-frequency induction coil; 5. a cooling body; 6. a lifting device; 7. a high frequency power supply; 8. an infrared thermometer; 9. a record feedback system; 10. a camera; 11. an intake valve; 12. an air extraction valve; 13. alloy raw materials; 14. cooling the lifting rod; 15. a pressure gauge; 16. an upper observation window; 17. a front observation window; 18. heating the electrode; 19. a gate valve; 20. a molecular pump; 21. a lifting rod; 22. heating the electrode interface; 23. and a temperature measuring electrode interface.

Detailed Description

The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.

The reagents and instrumentation used in the following examples are as follows: reagent:

zr, Cu, Al, Fe, Co, Ni, Ti, Au, Co, V, Y, available from Beijing Jiaming platinum nonferrous metals Co., Ltd.

The instrument comprises the following steps:

an infrared thermometer, purchased from photoelectricity, Inc. of Peking, Phytology, Inc.