CN117470887A - Alloy component determination method of centimeter-level liquid metal with amorphous forming capability and application thereof - Google Patents
Alloy component determination method of centimeter-level liquid metal with amorphous forming capability and application thereof Download PDFInfo
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 108
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- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 17
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- 239000010949 copper Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 39
- 238000003723 Smelting Methods 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 32
- 229910052726 zirconium Inorganic materials 0.000 claims description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 238000005520 cutting process Methods 0.000 claims description 8
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- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010314 arc-melting process Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
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- 230000001681 protective effect Effects 0.000 claims description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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Abstract
The invention discloses an alloy component determination method of centimeter-level liquid metal with amorphous forming capability and application thereof, wherein the scheme can simplify the amorphous forming capability characterization flow and has wider range of using an alloy system; the traditional method for representing the amorphous forming capability needs to prepare a master alloy ingot through arc melting, prepare liquid metal bars or plates with different sizes by adopting a rapid solidification process, then cut a liquid metal sample for XRD detection, so as to represent that the liquid metal component can form an amorphous critical dimension; according to the scheme, the master alloy ingot is prepared through arc melting, the master alloy ingot is cut/opened to observe the notch, the amorphous phase/crystalline phase proportion relation is directly judged, and the cooling rate is adjusted by controlling the total mass of the master alloy ingot, so that the method is suitable for liquid metal alloys of different systems, the amorphous forming capacity characterization flow is greatly simplified, the method also has the advantages of low raw material consumption, low cost and short time, and the liquid metal alloy component development efficiency is greatly improved.
Description
Technical Field
The invention relates to the technical field of liquid metal materials, in particular to a method for determining alloy components of liquid metal with centimeter-level amorphous forming capacity and application thereof.
Background
Liquid metals, also known as amorphous alloys or metallic glasses, are typically produced by quenching an alloy melt. Under the quenching condition, atoms are not much frozen as three-dimensional periodic arrangement is carried out, so that a unique arrangement mode of long-range disorder and short-range order is formed, and defects such as dislocation, grain boundary, segregation and the like are avoided. Thus, amorphous alloys have a range of unique properties such as good corrosion resistance, elastic limit up to 2%, high strength (in the order of GPa), good wear resistance, etc. The material has wide application prospect as structural materials, catalytic materials, soft magnetic materials, coating materials, micro-nano devices, biomedical materials and the like. Currently, liquid metal alloy systems that have been developed by researchers include bulk liquid metal alloys of magnesium, titanium, iron, nickel, copper, zirconium, palladium, platinum, gold, rare earth, and the like.
The amorphous forming ability (also referred to as glass forming ability) of an alloy refers to the ability of an alloy melt to form amorphous alloy solids without crystallization during cooling of the alloy melt. The greater the amorphous forming capability, the greater the critical dimensions of the fully amorphous alloy component that can be produced. Only if sufficient amorphous forming ability is ensured, a member meeting the requirements of the specifications can be produced. However, most liquid metal alloy compositions can produce fully amorphous alloy components of smaller dimensions. Therefore, a liquid metal alloy composition having a part of the centimeter-level amorphous forming ability has important research value in the application field. Meanwhile, in the industrial mass production process, the critical dimension of the prepared liquid metal component is often smaller than that of laboratory small-batch preparation due to the purity of the metal raw material and the poor alloy preparation environment. Therefore, the development of liquid metal alloy systems and compositions with high amorphous forming capability is of great significance for promoting industrial application.
At present, researchers have developed liquid metal alloys of a series of centimeter-sized dimensions, for example, zr-based liquid metal alloys such as ZrTiNiCuBe, zrAlNiCu (Y/Lu/Dy) and zrall (Co/Ni/Cu) Ag, etc., can produce amorphous samples of 20mm or more critical dimensions, ti-based liquid metal alloys such as tizrcup, etc., can produce amorphous samples of 10mm or more critical dimensions, mg-based liquid metals such as MgCuAg (Y/Dy/Ce), etc., can produce amorphous samples of 30mm or more critical dimensions, and Pd-based liquid metals such as PdCuNiP, etc., can produce amorphous samples of 75mm or more critical dimensions.
The main steps of the traditional amorphous alloy forming capability characterization are as follows: (1) Designing alloy components, and preparing pure metal raw materials according to the nominal alloy components; (2) Preparing a master alloy ingot by arc melting, and preparing bars or plates with different sizes by adopting a copper mold cooling casting process; (3) Cutting the alloy sample, performing XRD detection, and determining the critical dimension of the completely amorphous casting sample; (4) By comparing the critical dimensions of fully amorphous cast samples of different compositions, alloy compositions with higher amorphous forming ability were sought. However, with this method, for alloy components having high amorphous forming ability, it is necessary to prepare an alloy casting having a thickness of 30mm or more, and a large amount of metal raw materials are required to be charged, and the cost is extremely high; in order to determine critical dimensions, various different sized molds are required, casting is repeated to produce castings of different sizes, and XRD detection is required for each casting to determine whether it is completely amorphous, which requires a lot of raw materials and power consumption, and a lot of manpower and time. It generally takes about a week to determine the critical dimensions of 4 high amorphous forming capability liquid metal alloy compositions, which is extremely inefficient.
Disclosure of Invention
In view of the above, the invention aims to provide an alloy component determination method of centimeter-level high amorphous forming capability liquid metal, which is reliable to implement and flexible to operate, and an application thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for determining alloy composition of a centimeter-level high amorphous forming capability liquid metal, comprising:
a. pure metal raw material proportioning is carried out according to preset liquid metal alloy initial components, master alloy raw materials with different total masses are respectively prepared, then a vacuum arc melting process is adopted to melt master alloy, and then the master alloy ingot with different total masses is obtained after cooling along with a furnace in a water-cooled copper crucible;
b. c, cutting/shearing the master alloy ingot prepared in the step a, observing the relative amorphous phase/crystalline phase content of each master alloy ingot section, and taking the total mass corresponding to the master alloy ingot with the relative amorphous phase/crystalline phase content meeting moderate requirements as the reference mass of the ingredients in the subsequent step;
c. designing a new component system of the liquid metal alloy to obtain a plurality of new component systems of the liquid metal alloy with different components and/or the content of the components, then proportioning according to the determined standard mass of the nominal components of the alloy, smelting the master alloy by adopting a vacuum arc smelting process, and then cooling in a water-cooled copper crucible along with a furnace to obtain master alloy ingots of the plurality of new component systems; wherein, the number of mother alloy ingots with new components is determined by the number of smelting pits in the water-cooled copper crucible;
d. c, cutting/shearing the master alloy ingot prepared in the step c, observing the relative content of amorphous phase/crystalline phase of each master alloy ingot section, judging the influence of a new component system on the amorphous forming capacity, and obtaining a judging result;
e. and further adjusting a liquid metal alloy component system according to a judging result, and then sequentially carrying out batching, arc melting and observation on a master alloy ingot section until a liquid metal alloy component system with amorphous phase content of the master alloy ingot section meeting preset requirements is obtained, so that the liquid metal alloy component system with amorphous forming capability higher than that of an initial component is obtained.
In step a of this embodiment, an initial component alloy with a high amorphous forming ability is generally selected, and the critical diameter of the rod of the fully amorphous alloy, which can be prepared by a copper die casting process, is generally more than 1 cm.
As a possible implementation manner, the solution further includes:
f. and c, repeating the steps a to e to obtain a liquid metal alloy component system with amorphous forming capability meeting preset requirements.
As a preferred implementation option, the liquid metal alloy of the present embodiment is preferably zirconium-based, titanium-based, iron-based, nickel-based, copper-based, palladium-based, magnesium-based, or rare earth-based.
As a preferred implementation option, in step a of the present embodiment, pure metal raw material blending is preferably performed according to preset initial components of the liquid metal alloy, and 5 to 40g of master alloy raw materials with different total masses are respectively configured.
As a preferred implementation choice, when the liquid metal alloy is a zirconium-based system, preferably, 10-40 g of zirconium-based system master alloy raw materials with different total masses are configured.
As a preferred implementation option, in step b of the scheme, the total mass corresponding to the master alloy ingot with the relative content of amorphous phase/crystalline phase of 60% -90% is preferably taken as the reference mass of the ingredients in the subsequent step.
As a preferred implementation choice, preferably, when the liquid metal alloy is a zirconium-based system, the total mass corresponding to the master alloy ingot with the relative content of amorphous phase/crystalline phase of 70% -80% is taken as the reference mass of the ingredients in the subsequent steps.
As a preferred implementation option, in step c of the present embodiment, parameters of the vacuum arc melting process for melting the master alloy are as follows: vacuum degree of 9X 10 -4 Argon is filled into the smelting atmosphere below Pa and used as shielding gas, the argon pressure is 0.04-0.05 MPa, and the smelting temperatures of different liquid metal alloy systems are not completely the same.
As a preferred implementation choice, when the liquid metal alloy is a zirconium-based liquid metal alloy system, the smelting temperature is 900-1400 ℃, the single smelting time is 1-3 minutes, and the smelting times are not less than 4.
As a preferred implementation option, it is preferred that in step c of this embodiment, the number of ingots of the new composition obtained simultaneously is dependent on the number of melting pits in the water-cooled copper crucible. The water-cooled copper crucible of the general vacuum arc melting furnace can be subjected to 4-6 smelting pits, and can be personalized customization to obtain 8-12 smelting pits.
As a preferred implementation choice, in step d of the present embodiment, preferably, the determination result points to an improved correlation of the new component to the initial component of the amorphous/crystalline phase relative content of the master alloy ingot section;
if the relative content of amorphous phase/crystalline phase of the section of the new component master alloy ingot is increased compared with that of the initial component, the new component can improve the amorphous forming capability of the alloy,
if the relative content of amorphous/crystalline phase in the ingot section of the new composition master alloy is reduced from that of the initial composition, the new composition reduces the amorphous forming ability of the alloy.
In step d of this embodiment, the component with the highest relative amorphous/crystalline content is selected for the next step (step e) of the study.
As a preferred implementation choice, in step e of this embodiment, the component with the highest increase in the relative content of amorphous phase/crystalline phase is selected according to the determination result, and the liquid metal alloy component system is preferably further adjusted.
As a preferred implementation choice, in the steps b, d and e of the present embodiment, the method for observing the relative amorphous phase/crystalline phase content of the master alloy ingot section is preferably as follows: direct observation, metallographic sample preparation observation or XRD phase detection.
As a preferred implementation option, in step e of this embodiment, preferably, until a liquid metal alloy component system is obtained with a master alloy ingot section amorphous phase content close to 100% to a preset requirement, a liquid metal alloy component system with an amorphous forming capability higher than the initial component is obtained.
In step f of the scheme, if new liquid metal components with higher amorphous forming ability are further searched, the batching quality of the master alloy can be further improved: when the amorphous phase content of the section of the alloy ingot is close to 100%, the amorphous forming capability is improved, and the amorphous phase content of the section cannot be reflected. Therefore, the quality of master alloy ingredients is improved, and the quality range is improved according to different selected alloy systems. And (c) obtaining a master alloy ingot section amorphous phase/crystalline phase relative content of 60-90% according to the new design mass, wherein the suitable amorphous phase/crystalline phase relative content of the master alloy ingot of the zirconium-based liquid metal alloy system is 70-80%, determining the master alloy ingot as the new reference mass, and repeating the steps a-e again.
Based on the above, the invention also provides a preparation method of an alloy component of the liquid metal with centimeter-level amorphous forming capability, wherein the component system is determined by the determination method.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that:
(1) The scheme can simplify the amorphous forming capacity characterization flow, and the range of using an alloy system is wider; the traditional method for representing the amorphous forming capability needs to prepare a master alloy ingot through arc melting, prepare liquid metal bars or plates with different sizes by adopting a rapid solidification process, then cut a liquid metal sample for XRD detection, thereby representing that the liquid metal component can form amorphous critical dimensions. According to the scheme, the master alloy ingot is prepared through arc melting, the master alloy ingot is cut/opened to observe the notch, the amorphous phase/crystalline phase proportion relation is directly judged, and the cooling rate is adjusted by controlling the total mass of the master alloy ingot, so that the method is suitable for liquid metal alloys with different systems and components, and therefore the amorphous forming capacity characterization flow is greatly simplified.
(2) According to the scheme, the exploration time of alloy components with high amorphous forming capacity can be greatly shortened, the liquid metal alloy is smelted and cooled through the water-cooled copper crucible, at least 4 alloy components can be tested at one time, and if 8-10 smelting pits can be obtained through personalized customization of the water-cooled copper crucible, 8-10 alloy components can be tested at one time. Each component of the traditional method for representing the amorphous forming capability is subjected to arc melting of a master alloy ingot, then is cast into a large-size copper mold for rapid solidification, and a plurality of casting samples with different sizes are generally required to be cast for each component to determine the critical dimension. Typically, the amorphous forming ability of a centimeter-sized liquid metal alloy of 4 different compositions is characterized by conventional standard methods, requiring about 2 weeks, whereas with the method of the present invention, only about 4 hours are required; thus, the time for the present solution to explore alloy compositions with high amorphous forming capability is greatly shortened compared to conventional standard methods.
(3) According to the scheme, the cost of raw materials can be greatly reduced, liquid metal bars with different sizes are required to be prepared by the traditional method for determining the amorphous forming capability, and the critical dimension of the liquid metal bars with high amorphous forming capability can reach more than 30 mm. Taking zirconium-based liquid metal as an example, casting bars with a diameter of 30mm requires consumption of 200-300g of raw material. The invention only needs to smelt into 20-40g of mother alloy ingot by electric arc, and the consumption of alloy raw materials is small. Meanwhile, by adopting the traditional detection method, copper molds with different cavity sizes are required to be prepared through a copper mold casting process, and the large-size copper mold is very expensive, so that the cooling of the liquid metal in the scheme is directly realized by water-cooling the copper crucible in the arc melting furnace, the cost of preparing the copper mold is saved, and the raw material cost is remarkably saved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows an example of the present embodiment, zr 56 Al 10 Cu 16 Ni 13 Nb 4 Y 1 A photograph of a section of a zirconium-based liquid metal master alloy ingot, wherein, fig. 1 (a), fig. 1 (b) and fig. 1 (c) are respectively 10g, 20g and 30g of total mass of the master alloy;
FIG. 2 is a schematic diagram showing Zr in the present embodiment, the total mass of the master alloy being 20g x Al 11 Cu 16 Ni 12 Nb 4 Y x Photographs of the section of the zirconium-based liquid metal master alloy ingot;
FIG. 3 is a schematic diagram of Zr in the embodiment 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 Photograph of cross section morphology of fracture of the alloy ingot during optimization;
FIG. 4 is a fracture XRD pattern of 30g zirconium-based alloy ingots with three different Ti additions in the example of the present scheme.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is specifically noted that the following examples are only for illustrating the present invention, but do not limit the scope of the present invention. Likewise, the following examples are only some, but not all, of the examples of the present invention, and all other examples, which a person of ordinary skill in the art would obtain without making any inventive effort, are within the scope of the present invention.
The liquid metal alloy system suitable for the alloy component determination method of the liquid metal with the centimeter-level high amorphous forming capability is wider, and can be zirconium-based, titanium-based, iron-based, nickel-based, copper-based, palladium-based, magnesium-based, rare earth-based and other systems, and the method is described by taking zirconium-based liquid metal as an example and comprises the following steps of:
(1) Preparation of zirconium-based liquid metal master alloy
The method comprises the steps of selecting an initial component alloy of zirconium-based liquid metal with higher amorphous forming capability, wherein the critical diameter of a bar of the completely amorphous alloy which can be prepared by adopting a copper die casting process is more than 1 cm. Preparing pure metal raw materials according to initial alloy components, respectively preparing 10-30 g of raw materials with different total mass of master alloy, smelting the master alloy by adopting a vacuum arc smelting process, and cooling in a water-cooled copper crucible along with a furnace to obtain master alloy ingots with different total mass;
(2) Determining a reference mass of a master alloy ingot
Cutting/shearing the master alloy ingot, observing the relative amorphous phase/crystalline phase content of the master alloy ingot sections with different masses, and taking the total mass of the master alloy with moderate relative amorphous phase/crystalline phase content as the reference mass of the ingredients in the subsequent steps; the relative amorphous/crystalline phase content is generally 60% to 90%. The suitable amorphous phase/crystalline phase relative content of the master alloy ingot of the zirconium-based liquid metal alloy system is 70-80%.
(3) Design and preparation of new zirconium-based liquid metal alloy
Designing new zirconium-based liquid metal alloy components, proportioning according to the nominal alloy components and the determined reference mass, and smelting master alloy by adopting a vacuum arc smelting process, wherein the smelting process comprises the following steps: vacuum degree of 9X 10 -4 Argon is filled below Pa and used as shielding gas, the argon pressure is 0.04-0.05 MPa, and the smelting temperature is different according to the liquid metal alloy systemThe difference is that the smelting temperature of the zirconium-based liquid metal alloy system is 900-1400 ℃, the single smelting time is 1-3 minutes, and the smelting times are not less than 4. A plurality of new-component mother alloy ingots can be obtained simultaneously by cooling the ingot in a water-cooled copper crucible along with the furnace, and the number of the new-component mother alloy ingots obtained simultaneously depends on the number of smelting pits in the water-cooled copper crucible. The water-cooled copper crucible of the general vacuum arc melting furnace can be subjected to 4-6 smelting pits, and can be personalized customization to obtain 8-12 smelting pits.
(4) Determining the effect of new alloy compositions on amorphous forming ability
Mother alloy ingots are cut/sheared, the relative amorphous phase/crystalline phase content of the section of each mother alloy ingot is observed, and the influence of new components on amorphous forming capacity is judged. If the relative content of the amorphous phase/crystalline phase of the section of the new component master alloy ingot is higher than that of the original component, the new component can improve the amorphous forming capability of the alloy, and if the relative content of the amorphous phase/crystalline phase of the section of the new component master alloy ingot is lower than that of the original component, the new component reduces the amorphous forming capability of the alloy. The composition with the highest increase in amorphous/crystalline phase relative content was selected for further investigation.
(5) Repeatedly searching zirconium-based liquid metal alloy component with high amorphous forming capability
According to the result, further designing new components, repeating the steps of batching, arc melting, observing the section of the master alloy ingot and the like until the amorphous phase content of the section of the master alloy ingot is close to 100%, wherein the amorphous forming capacity of the selected new components of the liquid metal is obviously higher than that of the initial components; if new components of the liquid metal with higher amorphous forming capability are further searched, the batching quality of the master alloy can be further improved, and the steps (1) - (4) are repeated until the new alloy components meeting the forming capability requirement are determined.
Further, the following examples of implementation provide a comparative illustration of the above scheme:
example 1
The liquid metal alloy with high amorphous forming ability explored in the embodiment is ZrAlCuNiNbY- (Ti) system zirconium-based liquid metal alloy composition, which comprises the following steps:
(1) Preparation of ZrAlCuNiNbY series zirconium-based liquid metal master alloy
Select Zr with higher amorphous forming ability 56 Al 10 Cu 16 Ni 13 Nb 4 Y 1 The zirconium-based liquid metal is an alloy with initial components, and the critical diameter of a bar of the completely amorphous alloy which can be prepared by adopting a copper mold casting process exceeds 2 cm; and (3) preparing pure metal raw materials according to initial alloy components, respectively preparing 10g, 20g and 30g of raw materials with different total mass of master alloy, smelting the master alloy by adopting a vacuum arc smelting process, and cooling in a water-cooled copper crucible along with a furnace to obtain 3 master alloy ingots with different total mass.
(2) Determining a reference mass of a master alloy ingot
Cutting/shearing the master alloy ingot, observing the relative amorphous phase/crystalline phase content of the master alloy ingot sections with different masses, and taking the total mass of the master alloy with the relative amorphous phase/crystalline phase content of 70% -80% as the reference mass of the ingredients in the subsequent steps. Wherein FIG. 1 is Zr of 10g, 20g, 30g master alloy total mass 56 Al 10 Cu 16 Ni 13 Nb 4 Y 1 As can be seen from the photographs of the section of the zirconium-based liquid metal master alloy ingot, the total mass of the section of the master alloy ingot with the mass of 10g exceeds 95 percent, the relative content of the section of the master alloy ingot with the mass of 20g is 70-80 percent, and the relative content of the section of the master alloy ingot with the mass of 30g is less than 20 percent. Thus, zr is determined 56 Al 10 Cu 16 Ni 13 Nb 4 Y 1 The reference mass of the zirconium-based liquid metal master alloy ingot was 20g.
(3) Design and preparation of new zirconium-based liquid metal alloy
The new alloy composition of the zirconium-based liquid metal is designed and shown in table 1. Proportioning according to the nominal components of the alloy and the reference mass of 20g, and smelting the master alloy by adopting a vacuum arc smelting process, wherein the smelting process comprises the following steps: vacuum degree of 9X 10 -4 Argon is filled below Pa and used as protective gas, the argon pressure is 0.04-0.05 MPa, the smelting temperature is 900-1400 ℃, the single smelting time is 1-3 minutes, and the smelting times are the sameNot less than 4 times. And cooling in a water-cooled copper crucible along with the furnace, so that a plurality of new-component mother alloy ingots can be obtained simultaneously. In the experiment, 4 new-component mother alloy ingots can be obtained simultaneously, and more mother alloy ingots with different components can be obtained simultaneously through personalized customization of the water-cooled copper crucible.
(4) Determining the effect of new alloy compositions on amorphous forming ability
Cutting/shearing the master alloy ingot, and directly observing the relative amorphous phase/crystalline phase content of each master alloy ingot section to judge the influence of the new components on the amorphous forming capability. The specific conditions are shown in Table 1, from which it can be seen that with Zr 56 Al 10 Cu 16 Ni 13 Nb 4 Y 1 Zr compared with the initial component 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 、Zr 56.5 Al 12 Cu 16 Ni 11 Nb 4 Y 0.5 、Zr 55 Al 10 Cu 16 Ni 13 Nb 4 Y 2 The relative content of amorphous phase/crystalline phase of the section of the mother alloy ingot with the new components is improved compared with that of the original components, which shows that the new components can improve the amorphous forming capability of the alloy, and Zr 56.5 Al 9 Cu 16 Ni 14 Nb 4 Y 0.5 、Zr 56 Al 10 Cu 16 Ni 12 Nb 4 Y 2 、Zr 56 Al 9 Cu 16 Ni 13 Nb 4 Y 2 、Zr 56 Al 9 Cu 16 Ni 11 Nb 4 Y 2 Fe 2 、Zr 56 Al 9 Cu 16 Ni 9 Nb 4 Y 2 Fe 4 The relative content of amorphous phase/crystalline phase of the section of the mother alloy ingot with the new component is reduced compared with that of the original component, which shows that the new component reduces the amorphous forming capability of the alloy. Wherein Zr is 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 The alloy fracture has a ductile fracture morphology, and the amorphous phase content is close to 100%, as shown in fig. 2, so the composition is selected as the research object in the scheme.
TABLE 1 observations of 20g of different Zr-based alloy compositions and fracture morphology thereof
(5) Repeatedly searching zirconium-based liquid metal alloy component with high amorphous forming capability
Due to Zr 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 The amorphous phase content of the alloy fracture is close to 100%, so that the reference quality needs to be re-established. The total mass of the master alloy is improved from 20g to 30g, and 30g of Zr can be found by repeated proportioning, arc melting and observation of the section of the master alloy ingot 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 The amorphous phase content of the alloy fracture is 60-70%. The master alloy reference mass of the new composition was thus determined to be 30g.
Further design new components, in Zr 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 The alloy was further added with 2at.%, 4at.%, 6at.% Ti to replace Nb or Ni, the specific composition is shown in table 2. The steps of proportioning, arc melting, observing the section of the master alloy ingot and the like are repeated, and the surface morphology of the section of the master alloy ingot with different components is shown in figure 3. As can be seen from FIG. 3, 2at.% Ti replaces Zr of 2at.% Nb 56.5 Al 11 Cu 16 Ni 12 Nb 2 Y 0.5 Ti 2 When the alloy is 30g, the fracture is in a ductile fracture morphology, and the amorphous phase content is close to 100%. While 4at.% Ti replaces Zr of 4at.% Nb 56.5 Al 11 Cu 16 Ni 12 Y 0.5 Ti 4 The surface roughness of the alloy at 30g shows delamination without typical glassy fracture, which indicates a significant decrease in alloy forming ability, zr after increasing Ti content to 6 at% 56.5 Al 11 Cu 16 Ni 10 Y 0.5 Ti 6 The fracture surface of (c) was rougher, indicating a significant further decrease in amorphous forming ability. Thus, zr is determined 56.5 Al 11 Cu 16 Ni 12 Nb 2 Y 0.5 Ti 2 The alloy is the optimal component.
TABLE 2 observations of 30g of different Zr-based alloy compositions and fracture morphology thereof
In order to verify the reliability of determination of the amorphous phase content of the liquid metal alloy fracture by a direct observation method, XRD detection was performed on the fracture of 30g of liquid metal alloy ingots with three different Ti addition amounts, and the result is shown in FIG. 4, from which it can be known that 30g of Zr 56.5 Al 11 Cu 16 Ni 12 Nb 2 Y 0.5 Ti 2 The XRD pattern of the parent alloy ingot shows typical diffuse scattering peaks of amorphous state, proving that the alloy is of completely amorphous structure. Compared with 30g of Zr 56.5 Al 11 Cu 16 Ni 12 Nb 4 Y 0.5 The amorphous content of the fracture of the master alloy ingot is 60-70%, which proves that the amorphous forming capability of the alloy after component regulation is obviously improved. And total mass of 30g of Zr 56.5 Al 11 Cu 16 Ni 12 Y 0.5 Ti 4 With Zr 56.5 Al 11 Cu 16 Ni 10 Y 0.5 Ti 6 The XRD pattern of the alloy ingot shows obvious crystallization peaks, and the crystallization peak intensity of the alloy is obviously increased along with the increase of the Ti content, which shows that the amorphous forming capability of the alloy is reduced due to the fact that the Ti content exceeds 2at percent.
The foregoing description is only a partial embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent devices or equivalent processes using the descriptions and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for determining alloy composition of a centimeter-level high amorphous forming capability liquid metal, comprising:
a. pure metal raw material proportioning is carried out according to preset liquid metal alloy initial components, master alloy raw materials with different total masses are respectively prepared, then a vacuum arc melting process is adopted to melt master alloy, and then the master alloy ingot with different total masses is obtained after cooling along with a furnace in a water-cooled copper crucible;
b. c, cutting/shearing the master alloy ingot prepared in the step a, observing the relative amorphous phase/crystalline phase content of each master alloy ingot section, and taking the total mass corresponding to the master alloy ingot with the relative amorphous phase/crystalline phase content meeting moderate requirements as the reference mass of the ingredients in the subsequent step;
c. designing a new component system of the liquid metal alloy to obtain a plurality of new component systems of the liquid metal alloy with different components and/or the content of the components, then proportioning according to the determined standard mass of the nominal components of the alloy, smelting the master alloy by adopting a vacuum arc smelting process, and then cooling in a water-cooled copper crucible along with a furnace to obtain master alloy ingots of the plurality of new component systems;
d. c, cutting/shearing the master alloy ingot prepared in the step c, observing the relative content of amorphous phase/crystalline phase of each master alloy ingot section, judging the influence of a new component system on the amorphous forming capacity, and obtaining a judging result;
e. and further adjusting a liquid metal alloy component system according to a judging result, and then sequentially carrying out batching, arc melting and observation on a master alloy ingot section until a liquid metal alloy component system with amorphous phase content of the master alloy ingot section meeting preset requirements is obtained, so that the liquid metal alloy component system with amorphous forming capability higher than that of an initial component is obtained.
2. The method for determining alloy composition of a centimeter-level high amorphous forming ability liquid metal according to claim 1, further comprising:
f. and c, repeating the steps a to e to obtain a liquid metal alloy component system with amorphous forming capability meeting preset requirements.
3. The method for determining the alloy composition of a centimeter-level high amorphous forming ability liquid metal according to claim 1 or 2, wherein the liquid metal alloy is a zirconium-based, titanium-based, iron-based, nickel-based, copper-based, palladium-based, magnesium-based or rare earth-based system.
4. The method for determining alloy composition of liquid metal with centimeter-level high amorphous forming ability according to claim 1 or 2, wherein in step a, pure metal raw material proportioning is carried out according to preset initial liquid metal alloy composition, and master alloy raw materials with different total masses are respectively prepared in 5-40 g;
when the liquid metal alloy is a zirconium-based system, 10-40 g of zirconium-based system master alloy raw materials with different total masses are prepared.
5. The method for determining alloy components of a centimeter-level high amorphous forming ability liquid metal according to claim 1 or 2, wherein in the step b, the total mass corresponding to a master alloy ingot with the relative amorphous/crystalline phase content of 60% -90% is taken as the reference mass of the ingredients in the subsequent step;
when the liquid metal alloy is a zirconium-based system, taking the total mass corresponding to a master alloy ingot with the relative content of amorphous phase/crystalline phase of 70-80% as the reference mass of the ingredients in the subsequent step.
6. The method for determining alloy composition of liquid metal with high centimeter-level amorphous forming ability according to claim 1 or 2, wherein in the step c, parameters of the vacuum arc melting process for melting master alloy are as follows: vacuum degree of 9X 10 -4 Argon is filled into the smelting atmosphere below Pa and used as a protective gas, the argon pressure is 0.04-0.05 MPa, and the smelting temperatures of different liquid metal alloy systems are not completely the same;
when the liquid metal alloy is a zirconium-based liquid metal alloy system, the smelting temperature is 900-1400 ℃, the single smelting time is 1-3 minutes, and the smelting times are not less than 4.
7. The method for determining alloy composition of a centimeter-level high amorphous forming ability liquid metal according to claim 1 or 2, wherein in the step d, the determination result points to an improved correlation of the new composition to the master alloy ingot section amorphous phase/crystalline phase relative content than the initial composition;
if the relative content of amorphous phase/crystalline phase of the section of the new component master alloy ingot is increased compared with that of the initial component, the new component can improve the amorphous forming capability of the alloy,
if the relative content of amorphous phase/crystalline phase of the section of the new component master alloy ingot is reduced compared with that of the initial component, the new component reduces the amorphous forming capability of the alloy;
in step e, according to the judging result, the component with the highest relative content of amorphous phase/crystalline phase is selected to further adjust the component system of the liquid metal alloy.
8. The method for determining alloy composition of centimeter-level high amorphous forming ability liquid metal according to claim 1 or 2, wherein in step b, step d, and step e, the method for observing the relative amorphous/crystalline phase content of the master alloy ingot section is as follows: direct observation, metallographic sample preparation observation or XRD phase detection.
9. The method for determining the alloy composition of a centimeter-level high amorphous forming ability liquid metal according to claim 1 or 2, wherein in the step e, until a liquid metal alloy composition system with amorphous phase content of a master alloy ingot section close to 100% to a preset requirement is obtained, a liquid metal alloy composition system with amorphous forming ability higher than that of the initial composition is obtained.
10. Preparation of an alloy composition of a liquid metal with high amorphous forming capacity in cm-scale, characterized in that its composition system is determined by the determination method according to one of claims 1 to 9.
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