阅读说明：本技术 一种高通量制备与高通量表征不同成分钼合金的方法 (Method for preparing molybdenum alloy with different components in high flux and characterizing molybdenum alloy with different components in high flux ) 是由 孙院军 陈灿 李天宇 丁向东 张国君 于 2019-11-21 设计创作，主要内容包括：本发明公开了一种高通量制备与高通量表征不同成分钼合金的方法,包括工业化流程高通量制备不同成分钼合金,按照成分梯度取质量比的钼粉,硝酸镧、硝酸铈或硝酸镧与硝酸铈配制溶液,进行液固掺杂,并将掺杂物经干燥、碾碎和过筛后制得掺杂粉末；将掺杂粉末按照成分梯度分层封装进胶套中,捣实后进行等静压、烧结,锻造的棒材；进行高通量表征不同成分钼合金性能,钼合金棒材沿成分过渡区和纯净区平均切段,去应力退火得样品；过渡区样品标点,硬度和成分测试,得硬度-成分数据；纯净区样品拉伸力学性能测试,得不同掺杂量的钼合金应力应变数据。该方法为机器学习提供大量数据。(The invention discloses a method for preparing molybdenum alloys with different components in a high-flux manner and characterizing the molybdenum alloys with different components in a high-flux manner, which comprises the steps of preparing the molybdenum alloys with different components in a high-flux manner in an industrial process, taking molybdenum powder with a mass ratio according to component gradient, preparing solution from lanthanum nitrate, cerium nitrate or lanthanum nitrate and cerium nitrate, carrying out liquid-solid doping, and drying, crushing and sieving dopants to prepare doped powder; packing the doped powder into a rubber sleeve layer by layer according to component gradient, tamping, performing isostatic pressing and sintering, and forging the bar; performing high-throughput characterization on the performance of the molybdenum alloy with different components, averagely cutting the molybdenum alloy rod along a component transition region and a pure region, and performing stress relief annealing to obtain a sample; marking points on the transition region sample, and testing hardness and components to obtain hardness-component data; and testing the tensile mechanical property of the pure area sample to obtain the stress-strain data of the molybdenum alloy with different doping amounts. The method provides a large amount of data for machine learning.)

1. A method for preparing molybdenum alloy with different components in high flux and characterizing the molybdenum alloy with different components in high flux is characterized by comprising the following steps:

step 1, preparing molybdenum alloys with different components in an industrial process at high flux:

11) taking molybdenum powder and lanthanum nitrate and cerium nitrate or lanthanum nitrate and cerium nitrate according to the component gradient, preparing the lanthanum nitrate, the cerium nitrate and the lanthanum nitrate and the cerium nitrate into a solution, carrying out liquid-solid doping on the solution and the molybdenum powder, and drying, grinding and sieving a dopant to prepare doped powder;

12) packaging the doped powder into a rubber sleeve layer by layer according to component gradient, and performing isostatic pressing after tamping;

13) sintering the molybdenum alloy rod subjected to isostatic pressing, and forging the molybdenum alloy rod obtained by sintering to finally obtain a molybdenum alloy rod;

step 2, high-throughput characterization of the performance of molybdenum alloys with different components:

21) averagely cutting the obtained molybdenum alloy rod along a composition transition region and a pure region, processing a sample into a rectangular strip, and performing stress relief annealing to obtain a molybdenum alloy rod sample;

22) marking the transition area of the molybdenum alloy bar sample, performing hardness test along the direction vertical to the bar to obtain the hardness value of the area, and measuring the components of the area to obtain hardness-component data;

and (4) carrying out tensile mechanical property test on the pure area sample subjected to heat treatment to obtain the stress-strain data of the molybdenum alloy with different doping amounts.

2. The method for high throughput preparation and high throughput characterization of molybdenum alloys of different compositions as claimed in claim 1, wherein the doped powder composition gradient comprises three groups, respectively:

the doping content of lanthanum oxide is 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and 0.9%;

the doping content of cerium oxide is 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and 0.9%;

the lanthanum oxide and the cerium oxide are doubly doped with equal mass fractions, and the lanthanum oxide and the cerium oxide are respectively 0%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% and 0.45%.

3. The method for high-throughput preparation and high-throughput characterization of molybdenum alloys with different compositions as claimed in claim 1, wherein in the step 11), the liquid-solid doping process comprises weighing lanthanum nitrate, cerium nitrate, lanthanum nitrate and cerium nitrate according to mass ratio, adding deionized water and stirring respectively to dissolve lanthanum nitrate or cerium nitrate particles completely, adding alcohol, stirring the solution to mix them uniformly, adding the weighed molybdenum powder into the mixed solution of lanthanum nitrate, cerium nitrate and lanthanum nitrate and cerium nitrate, stirring uniformly, placing into an air-blast drying oven for full drying, grinding and sieving to obtain the doped powder.

4. The method for high throughput characterization of molybdenum alloys of different composition as claimed in claim 1 wherein the doped powders are sequentially loaded into the mold in ascending or descending order of doping content, each loading being followed by an artificial tamping.

5. High throughput manufacturing and high throughput characterization of molybdenum alloys of different composition according to claim 1, wherein the isostatic pressure is 180 MPa.

6. High throughput manufacturing and high throughput characterization of molybdenum alloys of different composition according to claim 1, characterized in that the molybdenum alloy rods are stress relief annealed at 850 ℃ for 40 min.

7. The method for high throughput preparation and high throughput characterization of molybdenum alloys of different compositions according to claim 1, wherein the pure regions of the molybdenum alloy rod are graded doped powder regions; the transition region is a mixed region between doping powders with different doping amounts.

8. The method for high-throughput preparation and high-throughput characterization of molybdenum alloys of different compositions according to claim 1, wherein in step 22), the hardness test is performed along a direction perpendicular to the bars, a plurality of points are taken on a line and tested, the distance between each point is not more than 1mm, and then the average value is taken to obtain the hardness value of the area.

Technical Field

The invention belongs to the technical field of powder metallurgy, and relates to a method for high-throughput preparation and high-throughput characterization of molybdenum alloys with different components in an industrial process.

Background

Molybdenum is a rare refractory metal, has high melting point and elastic modulus, good electric and heat conducting performance, low thermal expansion coefficient, and good acid and alkali resistance and liquid metal corrosion resistance, is widely applied to various fields such as aerospace, mechanical manufacturing, power electronics, ferrous metallurgy, medical appliances, illumination, energy chemical industry, military industry and the like, and is an indispensable high-temperature-resistant material. With the development of science and technology, particularly the demand of national defense is higher and higher, higher requirements are put forward on the comprehensive performance of the molybdenum alloy.

However, research and development of materials are a long process, the traditional research and development method of new materials is a trial and error method, and scientific researchers determine the composition of the material components based on own knowledge and relevant experience accumulation. Reviewing the development and application history of the entire industrial technology and materials, the development of new generation materials generally requires a considerable amount of time. Therefore, shortening the period from research and development to application of materials, accelerating the research and development speed of materials, and reducing the research and development cost of materials become important for research in various countries.

The "materials genome initiative (GMI)" was proposed in 2011 in the united states, specifically "doubling the speed of discovery, development, manufacture and use of advanced materials". Once published, the American material genome project immediately draws international wide attention, and China, European Union, Japan, India and the like follow up in succession, and respective material genome projects are proposed successively.

As the most important ring of the material genetic engineering center, high-throughput experiments can accelerate the research and development of materials by thousands of times, not only can make up the relation between the deficiency of theoretical calculation and models and the calculation of different scales of the architecture, supplement the data of basic material physics, chemistry and materials science, but also can build the internal relation among components, tissues and processes related to material performance, and further can provide basic data parameters for calculation simulation, thereby realizing the effect of accelerating the screening and optimization of materials.

The report of the molybdenum alloy in the field of high-flux experiments is few, and in order to quickly obtain ideal alloy performance, the patent provides an industrial high-flux preparation method of the molybdenum alloy and a subsequent high-flux characterization method.

Disclosure of Invention

One of the purposes of the invention is to provide a method for preparing molybdenum alloys with different components in an industrialized process at high flux, and molybdenum alloy rods with different component gradients are produced at high flux through industrialized equipment and processes. The production of the alloy completely adopts the production process of rare earth molybdenum alloy of certain molybdenum alloy production enterprises in China, and the produced high-flux molybdenum alloy has good integrity, thereby providing a block material with authenticity performance for subsequent high-flux analysis.

The invention also aims to provide a method for high-throughput characterization of the performance of molybdenum alloys with different components, and provides data for machine learning by characterizing the relationship between the hardness and the components of a component transition region and the mechanical properties of a single component region.

The purpose of the invention is realized by the following technical scheme:

the invention provides a method for preparing molybdenum alloy with different components in a high flux and characterizing the molybdenum alloy with different components in a high flux, which comprises the following steps:

step 1, preparing molybdenum alloys with different components in an industrial process at high flux:

11) taking molybdenum powder and lanthanum nitrate and cerium nitrate or lanthanum nitrate and cerium nitrate according to the component gradient, preparing the lanthanum nitrate, the cerium nitrate and the lanthanum nitrate and the cerium nitrate into a solution, carrying out liquid-solid doping on the solution and the molybdenum powder, and drying, grinding and sieving a dopant to prepare doped powder;

12) packaging the doped powder into a rubber sleeve layer by layer according to component gradient, and performing isostatic pressing after tamping;

13) sintering the molybdenum alloy rod subjected to isostatic pressing, and forging the molybdenum alloy rod obtained by sintering to finally obtain a molybdenum alloy rod;

step 2, high-throughput characterization of the performance of molybdenum alloys with different components:

21) averagely cutting the obtained molybdenum alloy rod along a composition transition region and a pure region, processing the sample into a rectangular strip, and performing stress relief annealing to obtain a molybdenum alloy rod sample;

22) marking the transition area of the molybdenum alloy bar sample, performing hardness test along the direction vertical to the bar to obtain the hardness value of the area, and measuring the components of the area to obtain hardness-component data;

and (4) carrying out tensile mechanical property test on the pure area sample subjected to heat treatment to obtain the stress-strain data of the molybdenum alloy with different doping amounts.

In the method, the doped powder component gradient comprises three groups, which are respectively:

the doping content of lanthanum oxide is 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and 0.9%;

the doping content of cerium oxide is 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and 0.9%;

the lanthanum oxide and the cerium oxide are doubly doped with equal mass fractions, and the lanthanum oxide and the cerium oxide are respectively 0%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% and 0.45%.

In the above method, in the step 11), the liquid-solid doping process includes weighing lanthanum nitrate, cerium nitrate, lanthanum nitrate and cerium nitrate according to a mass ratio, adding an appropriate amount of deionized water and stirring respectively to completely dissolve lanthanum nitrate or cerium nitrate particles, adding alcohol, stirring the solution to mix uniformly, adding the weighed molybdenum powder into the mixed solution of lanthanum nitrate, cerium nitrate and lanthanum nitrate and cerium nitrate, stirring uniformly, placing into a forced air drying oven to dry sufficiently, and grinding and sieving to obtain the doped powder.

In the method, the doped powder is sequentially filled into a die from large to small or from small to large according to the doping content, and artificial tamping is needed after each powder is filled.

In the above method, the isostatic pressure is 180 MPa.

In the method, the molybdenum alloy bar is subjected to stress relief annealing at 850 ℃ for 40 min.

In the method, the pure areas of the molybdenum alloy rod are doped powder areas with various gradients; the transition region is a mixed region between doping powders with different doping amounts.

In the method, in the step 22), the hardness test is performed along the direction perpendicular to the bar, a plurality of points are taken on one line for testing, the distance between each point is not more than 1mm, and then the average value is taken, so that the hardness value of the area is obtained.

The molybdenum alloy prepared by the method uses as few raw materials as possible to prepare a molybdenum alloy rod which has multiple groups of components, combines industrial production and has alloy performance consistent with real block materials.

The invention has the following advantages:

1) the invention combines the high flux thought with the industrial production on the powder metallurgy molybdenum alloy for the first time; the molybdenum alloy rod with multiple groups of components and the alloy performance consistent with that of the real block material is produced, and the problem of difference between the performance of the small-mass block material and the performance of the real block material produced by the conventional high-throughput experiment is solved.

2) Each molybdenum alloy rod prepared by the method has multiple groups of components, pure areas and transition areas with different components, can obtain 30 groups of tensile data with different components and multiple groups of component-hardness data, can provide a large amount of data for machine learning, and accelerates the research and development speed of new materials.

Drawings

FIGS. 1a-1c are schematic diagrams of a compacted form of the powder of the invention and the sequence;

FIG. 2 is a schematic illustration of the forging of a bar according to the present invention;

FIG. 3 is a schematic view of sample processing;

FIGS. 4a and 4b are diagrams of quantitative analysis of transition region components;

FIGS. 5a and 5b are graphs showing the results of hardness analysis of the transition zone;

FIG. 6 is a schematic drawing showing the dimensions of a tensile sample of a molybdenum rod;

FIG. 7 is a tensile stress-strain curve of a pure region of a lanthanum-doped molybdenum alloy;

FIG. 8 is a tensile stress-strain curve of a pure region of a cerium-doped molybdenum alloy;

FIG. 9 is a tensile stress-strain curve of pure lanthanum-cerium co-doped molybdenum alloy region.

Detailed Description

The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.

The invention provides a method for high-throughput preparation and high-throughput characterization of molybdenum alloys with different components in an industrial process, which comprises the following steps:

(1) preparing molybdenum alloys with different components by adopting an industrial process with high flux:

respectively weighing molybdenum powder, lanthanum nitrate and cerium nitrate and a mixture of the lanthanum nitrate and the cerium nitrate according to data obtained by mass ratio calculation, respectively adding deionized water to fully dissolve the molybdenum powder, then adding alcohol, respectively adding the weighed molybdenum powder into a mixed solution of the lanthanum nitrate, the cerium nitrate and the lanthanum nitrate and cerium nitrate according to component gradients, stirring, carrying out liquid-solid doping on the molybdenum powder and a lanthanum nitrate solution or a cerium nitrate solution, putting the mixture into a forced air drying oven for full drying after uniform stirring, and preparing doped powder with different component gradients after crushing and sieving.

The different doped powders are sequentially filled into a die from small to large or from small to large according to the component gradient, in one embodiment, the doped powders are packaged into a rubber sleeve with the diameter of 18mm, the powder filling amount of the die is 1000g, and the weight of each component can be properly adjusted. In order to ensure that the sample is not broken in the sintering process and the subsequent forging process, the sample needs to be manually lifted after each gradient of doping powder is filled; and (4) carrying out isostatic pressing after complete assembly, wherein the isostatic pressing pressure is 180MPa, and obtaining the molybdenum alloy rod. Sintering the molybdenum alloy rod after isostatic pressing, and forging the molybdenum alloy rod obtained by sintering.

(2) High-throughput characterization of molybdenum alloys of different compositions;

performing stress relief annealing on the obtained molybdenum alloy rod at 850 ℃ for 40min to obtain a molybdenum alloy rod sample; marking the transition region of the molybdenum alloy bar sample, performing hardness test along the direction vertical to the bar to obtain the hardness value of the region, and measuring the components of the region by using a plasma emission spectrometer (ICP-AES) to obtain hardness-component data, wherein the hardness-component data comprises the relation between the hardness and the components of different components in the transition region and the relation between the mechanical properties and the components of different components in the pure region.

And (4) carrying out tensile mechanical property test on the pure area sample subjected to heat treatment to obtain the stress-strain data of the molybdenum alloy with different doping amounts.

The following different examples are given to further illustrate the invention.

Tables 1-3 show compositional gradient tables of molybdenum powder doped with lanthanum oxide, molybdenum powder doped with cerium oxide, molybdenum powder doped with lanthanum oxide and cerium oxide, and the like in mass fraction double doping in the examples.

TABLE 1 doping with La₂O₃Ingredient table

TABLE 2 doping with CeO₂Ingredient table

TABLE 3 La₂O₃、CeO₂Blending ingredient table