阅读说明：本技术 一种Zr基块体非晶合金中氧化夹杂物细化方法 (Method for refining oxide inclusions in Zr-based bulk amorphous alloy ) 是由 王艳林 申曦 周青峰 王自东 贾云柯 陈晓华 于 2021-08-12 设计创作，主要内容包括：一种Zr基块体非晶合金中氧化夹杂物细化方法,属于非晶合金冶炼领域,在非晶合金的熔炼工艺中加入包芯线来细化夹杂物。本发明通过在熔炼时添加特制包芯线来降低Zr基块体非晶合金凝固时界面前沿的溶质浓度梯度,从而将Zr基块体非晶合金中夹杂物的平均尺寸由50μm降低到5μm,有效提高了非晶合金的韧性；同时本发明的制备方法与传统的熔炼加料、微合金化、退火、喷丸、冷轧等(传统金属材料处理方法在非晶领域的应用)方式相比,能显著细化夹杂物尺寸,既可使剪切带在整个试样中的分布更加均匀,明显降低了非晶合金中裂纹的萌生与扩展程度以提高韧性,在制备更优性能的Zr基块体非晶合金工艺中有很大的优势。(A refining method for oxide inclusions in Zr-based bulk amorphous alloy belongs to the field of amorphous alloy smelting, and cored wires are added in the smelting process of amorphous alloy to refine the inclusions. According to the invention, the specially-made core-spun wire is added during smelting to reduce the solute concentration gradient of the interface front edge when the Zr-based bulk amorphous alloy is solidified, so that the average size of inclusions in the Zr-based bulk amorphous alloy is reduced from 50 micrometers to 5 micrometers, and the toughness of the amorphous alloy is effectively improved; meanwhile, compared with the traditional modes of smelting and feeding, microalloying, annealing, shot blasting, cold rolling and the like (the traditional metal material processing method is applied to the amorphous field), the preparation method can obviously refine the size of the inclusion, can ensure that the distribution of the shear band in the whole sample is more uniform, obviously reduces the initiation and expansion degree of cracks in the amorphous alloy to improve the toughness, and has great advantages in the process of preparing the Zr-based bulk amorphous alloy with better performance.)

1. A method for refining oxide inclusions in a Zr-based bulk amorphous alloy is characterized by comprising the following steps: the inclusion is refined by adding the cored wire in the smelting process of the amorphous alloy.

2. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 1, wherein: the cored wire comprises a copper wall tube and a cored material, wherein the cored material is filled in the copper wall tube, the inner diameter of the copper wall tube is 13mm, and the wall thickness of the copper wall tube is 0.5 mm.

3. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 2, wherein: the core-spun material comprises the following substances in percentage by mass: rare earth Y15-50%, Ca 0-35%, Al 10-30% and Ti 5-25%.

4. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 3, wherein: the O content of the rare earth Y is less than or equal to 100 ppm.

5. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to any one of claims 1 to 4, wherein: the operation comprises the following steps:

the method comprises the following steps: feeding raw materials in a mode that a large material is close to the inner wall of a crucible and a small material is close to the center of the crucible;

step two: closing the furnace cover, opening a vacuum pump, and pumping the vacuum degree of the smelting furnace to be within 5 Pa;

step three: setting the power of a smelting furnace to be 30-50KW, electrically heating, and when the metal in the crucible begins to melt, increasing the power to be 60-80KW for melting;

step four: melting until sputtering occurs, reducing power to 10-30KW, turning off the vacuum pump, and simultaneously filling argon of not less than-0.05 atm into the furnace;

step five: when the smelting temperature is 950-;

step six: starting a vacuum pump, setting refining power at 100 & lt- & gt and 125KW, observing the melting and cleaning condition of the metal raw materials in the crucible through an observation hole, after the melting and cleaning condition, continuing refining until the molten liquid starts to splash, and then stopping power and reducing temperature;

step seven: hoisting a mold and a chute, operating a handle to tilt, pouring molten liquid in a crucible into the mold, cooling after pouring is finished, then opening a vent valve to break vacuum, opening a furnace door, using a crown block to lift the mold, detaching the mold, taking out a master alloy ball, putting the master alloy ball into a corresponding iron sheet turnover box, making relevant marks, and placing in a classified manner;

step eight: the master alloy ball is applied to a vacuum die-casting process to prepare a Zr-based bulk amorphous alloy product casting.

6. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 5, wherein: the mass percentages of the raw materials in the step one are as follows: 52.5 percent of Zr, 17.9 percent of Cu, 14.6 percent of Ni0, 10 percent of Al and 5 percent of Ti.

7. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 5, wherein: and feeding the cored wire in the step five into the alloy liquid at the speed of 0.05-1 m/s.

8. The method for refining oxide inclusions in the Zr-based bulk amorphous alloy according to claim 5, wherein: the addition weight of the cored wire is 0.1-1.0% of the total weight of the raw materials.

Technical Field

The invention belongs to the field of amorphous alloy smelting, and particularly relates to a method for refining oxide inclusions in a Zr-based bulk amorphous alloy.

Background

The amorphous alloy has good physical and chemical properties, the strength of the amorphous alloy is far higher than that of a common crystalline metal material, and the amorphous alloy has wide application prospects in the fields of aerospace, automobile manufacturing, precision manufacturing, biology, information and the like, and provides a new way for preparing novel high-strength alloys. With the continuous development of the bulk amorphous alloy, the preparation method thereof is gradually mature, the material types are more abundant, and the application is wider. The Zr-based amorphous alloy has the advantages of high strength, superplasticity, high elasticity, high hardness, high wear resistance, high corrosion resistance, excellent processing and forming performance and the like, the glass/amorphous forming capability is very strong, the supercooling liquid phase region is wider, the preparation method is simpler and more convenient, and the Zr-based amorphous alloy is one of the most studied amorphous alloy systems at present.

At present, the main problems restricting the development of the amorphous alloy material are as follows: in the mechanical property test, particularly under the conditions of high strain rate and low temperature, the Zr-based amorphous alloy has non-uniform deformation and is limited in a shear band, and the plasticity and the fatigue toughness are not good enough compared with other properties. Related researchers improve the performance of the bulk amorphous alloy and improve the room temperature plasticity and fatigue toughness of the bulk amorphous alloy by methods of shot blasting, high Poisson ratio amorphous design, crystalline phase toughening and the like.

The macro-brittleness phenomenon of the amorphous alloy is also related to internal defects of the material (particularly, coarse and large internal inclusions and the like), and stress concentration generated by the inclusions causes cracks to propagate from the initiation to the micro-cracks until the material finally fractures. When the sample is stressed, the micro-cracks nucleate on the inclusions firstly; the growth and expansion of the micro-cracks are directly influenced by the space between the inclusions; the propagation of the precrack is associated with the zone of accumulation of inclusions, through which the propagation of the precrack always passes. Therefore, the state of inclusions is very important for amorphous alloys.

Therefore, in order to further obtain the Zr-based amorphous alloy with better toughness, the inclusion control and refinement process is very important. Only when the Zr-based amorphous alloy with the best comprehensive performance is produced, the block amorphous alloy can be promoted to develop higher and better industrialization.

Disclosure of Invention

The invention provides a method for refining oxide inclusions in a Zr-based bulk amorphous alloy, which is used for overcoming the defects in the prior art.

The invention is realized by the following technical scheme:

a method for refining oxide inclusions in Zr-based bulk amorphous alloy is characterized in that cored wires are added in the smelting process of the amorphous alloy to refine the inclusions.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy comprises the copper wall tube and the core-spun material, wherein the core-spun material is filled in the copper wall tube, the inner diameter of the copper wall tube is 13mm, and the wall thickness of the copper wall tube is 0.5 mm.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy comprises the following steps of:

15-50% of rare earth Y, 0-35% of Ca, 10-30% of Al and 5-25% of Ti.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy has the advantage that the O content of the rare earth Y is less than or equal to 100 ppm.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy comprises the following steps:

the method comprises the following steps: feeding raw materials in a mode that a large material is close to the inner wall of a crucible and a small material is close to the center of the crucible;

step two: closing the furnace cover, opening a vacuum pump, and pumping the vacuum degree of the smelting furnace to be within 5 Pa;

step three: setting the power of a smelting furnace to be 30-50KW, electrically heating, and when the metal in the crucible begins to melt, increasing the power to be 60-80KW for melting;

step four: melting until sputtering occurs, reducing power to 10-30KW, turning off the vacuum pump, and simultaneously filling argon of not less than-0.05 atm into the furnace;

step five: when the smelting temperature is 950-;

step six: starting a vacuum pump, setting refining power at 100 & lt- & gt and 125KW, observing the melting and cleaning condition of the metal raw materials in the crucible through an observation hole, after the melting and cleaning condition, continuing refining until the molten liquid starts to splash, and then stopping power and reducing temperature;

step seven: hoisting a mold and a chute, operating a handle to tilt, pouring molten liquid in a crucible into the mold, cooling after pouring is finished, then opening a vent valve to break vacuum, opening a furnace door, using a crown block to lift the mold, detaching the mold, taking out a master alloy ball, putting the master alloy ball into a corresponding iron sheet turnover box, making relevant marks, and placing in a classified manner;

step eight: the master alloy ball is applied to a vacuum die-casting process to prepare a Zr-based bulk amorphous alloy product casting.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy comprises the following steps of: 52.5 percent of Zr, 17.9 percent of Cu, 14.6 percent of Ni0, 10 percent of Al and 5 percent of Ti.

In the method for refining the oxide inclusions in the Zr-based bulk amorphous alloy, the cored wire in the fifth step is fed into the alloy liquid at a speed of 0.05-1 m/s.

The method for refining the oxide inclusions in the Zr-based bulk amorphous alloy comprises the step of adding the cored wire in an amount of 0.1-1.0% of the total weight of the raw materials.

The invention has the advantages that: according to the invention, the specially-made core-spun wire is added during smelting to reduce the solute concentration gradient at the front edge of the interface when the Zr-based bulk amorphous alloy is solidified, so that the average size of inclusions in the Zr-based bulk amorphous alloy is reduced from 50 micrometers to 5 micrometers, and the plasticity and toughness of the amorphous alloy are effectively improved; meanwhile, compared with the traditional modes of smelting and feeding, microalloying, annealing, shot blasting, cold rolling and the like (the traditional metal material processing method is applied to the amorphous field), the preparation method can obviously refine the size of the inclusion, can ensure that the distribution of the shear band in the whole sample is more uniform, obviously reduces the initiation and expansion degree of cracks in the amorphous alloy to improve the toughness, and has great advantages in the process of preparing the Zr-based bulk amorphous alloy with better performance.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a graph a showing the morphology of inclusions in a Zr-based bulk amorphous alloy of a comparative example; FIG. b is the morphology of inclusions in the Zr-based bulk amorphous alloy of example 2;

FIG. 2 is a schematic view of the core-spun yarn structure of the present invention;

fig. 3 is a schematic view of the core-spun yarn feeding device of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The method comprises the following steps: accurately weighing 52.5kg of Zr, 17.9kg of Cu, 14.6kg of Ni14, 10kg of Al and 5kg of Ti;

step two: feeding the raw materials weighed in the step one in a manner that large materials are close to the inner wall of the crucible and small materials are close to the center of the crucible;

step three: after the charging is finished, closing the furnace cover, opening a vacuum pump, and pumping the vacuum degree of the smelting furnace to be within 5 Pa;

step four: setting the power of a smelting furnace to be 40KW, electrically heating, and increasing the power to 75KW for melting when the metal in the crucible starts to melt;

step five: melting until sputtering occurs, reducing power to 25KW, turning off the vacuum pump, and simultaneously filling argon of not less than-0.05 atm into the furnace;

step six: when the smelting temperature is 1000 ℃, a core-spun yarn (rare earth Y35%, Ca 32%, Al 10% and Ti 23%) is added into the crucible through a sealed yarn feeding mechanism additionally arranged on a furnace cover of the vacuum induction furnace for deoxidation control;

step seven: starting a vacuum pump, setting refining power to be 110KW, observing the melting and cleaning condition of the metal raw material in the crucible through an observation hole, after the melting and cleaning, continuing refining until the molten liquid starts to splash, and then cutting off power to cool;

step eight: hoisting a mold and a chute, operating a handle to tilt, pouring molten liquid in a crucible into the mold, cooling after pouring is finished, then opening a vent valve to break vacuum, opening a furnace door, using a crown block to lift the mold, detaching the mold, taking out a master alloy ball, putting the master alloy ball into a corresponding iron sheet turnover box, making relevant marks, and placing in a classified manner;

step nine: the master alloy ball is applied to a vacuum die-casting process to prepare a Zr-based bulk amorphous alloy product casting.

Example 2

The method comprises the following steps: accurately weighing 52.5kg of Zr, 17.9kg of Cu, 14.6kg of Ni14, 10kg of Al and 5kg of Ti;

step two: feeding the raw materials weighed in the step one in a manner that large materials are close to the inner wall of the crucible and small materials are close to the center of the crucible;

step three: after the charging is finished, closing the furnace cover, opening a vacuum pump, and pumping the vacuum degree of the smelting furnace to be within 5 Pa;

step four: setting the power of a smelting furnace to be 30KW, electrically heating, and increasing the power to be 60KW for melting when the metal in the crucible starts to melt;

step five: melting until sputtering occurs, reducing power to 10KW, turning off the vacuum pump, and simultaneously filling argon of not less than-0.05 atm into the furnace;

step six: when the smelting temperature is 950 ℃, a core-spun yarn (rare earth Y42%, Ca 23%, Al 17% and Ti 18%) is added into the crucible through a sealed yarn feeding mechanism additionally arranged on a furnace cover of the vacuum induction furnace for deoxidation control; step seven: starting a vacuum pump, setting refining power at 100 & lt- & gt and 125KW, observing the melting and cleaning condition of the metal raw materials in the crucible through an observation hole, after the melting and cleaning condition, continuing refining until the molten liquid starts to splash, and then stopping power and reducing temperature;

step eight: hoisting a mold and a chute, operating a handle to tilt, pouring molten liquid in a crucible into the mold, cooling after pouring is finished, then opening a vent valve to break vacuum, opening a furnace door, using a crown block to lift the mold, detaching the mold, taking out a master alloy ball, putting the master alloy ball into a corresponding iron sheet turnover box, making relevant marks, and placing in a classified manner;

step nine: the master alloy ball is applied to a vacuum die-casting process to prepare a Zr-based bulk amorphous alloy product casting.

Example 3

The method comprises the following steps: accurately weighing 52.5kg of Zr, 17.9kg of Cu, 14.6kg of Ni14, 10kg of Al and 5kg of Ti;

step two: feeding the raw materials weighed in the step one in a manner that large materials are close to the inner wall of the crucible and small materials are close to the center of the crucible;

step three: after the charging is finished, closing the furnace cover, opening a vacuum pump, and pumping the vacuum degree of the smelting furnace to be within 5 Pa;

step four: setting the power of the smelting furnace to 50KW, electrically heating, and increasing the power to 80KW for melting when the metal in the crucible starts to melt;

step five: melting until sputtering occurs, reducing power to 30KW, turning off the vacuum pump, and simultaneously filling argon of not less than-0.05 atm into the furnace;

step six: when the smelting temperature is 1250 ℃, a core-spun yarn (rare earth Y45%, Ca 27%, Al 12% and Ti 16%) is added into the crucible through a sealed yarn feeding mechanism additionally arranged on a furnace cover of the vacuum induction furnace for deoxidation control;

step seven: starting a vacuum pump, setting refining power to be 120KW, observing the melting and cleaning condition of the metal raw material in the crucible through an observation hole, after the melting and cleaning, continuing refining until the molten liquid starts to splash, and then cutting off power to cool;

step eight: hoisting a mold and a chute, operating a handle to tilt, pouring molten liquid in a crucible into the mold, cooling after pouring is finished, then opening a vent valve to break vacuum, opening a furnace door, using a crown block to lift the mold, detaching the mold, taking out a master alloy ball, putting the master alloy ball into a corresponding iron sheet turnover box, making relevant marks, and placing in a classified manner;

step nine: the master alloy ball is applied to a vacuum die-casting process to prepare a Zr-based bulk amorphous alloy product casting.

Comparative example

The amorphous alloy is prepared according to the existing traditional means.

The results of the tests performed on the amorphous alloys prepared in examples 1 to 3 and the comparative example are shown in table one.

Watch 1

As can be seen from the data in Table I, the size, quantity and distribution of the inclusions of the amorphous alloys prepared in examples 1-3 are significantly better than those of the comparative example, and as can be seen from FIG. 1, the inclusion control of the amorphous alloy prepared in example 1 is significantly better than that of comparative example 1, and the impact energy of examples 1-3 and comparative example is measured by the special detection equipment for amorphous alloy, and the results are shown in the table, i.e. the toughness of the amorphous alloys prepared in examples 1-3 is significantly better than that of the amorphous alloys prepared in comparative example; in addition, in the judgment statistics of inclusion defects of the appearance piece, the results show that the examples 1-3 are obviously superior to the comparative example, so that the performance of the amorphous alloy prepared by the method provided by the invention is obviously superior to that of the product prepared by the conventional technology, and the method is helpful for promoting the block amorphous alloy to develop towards higher and better industrialization.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.