CN116254488A - High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof - Google Patents
High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof Download PDFInfo
- Publication number
- CN116254488A CN116254488A CN202211569666.XA CN202211569666A CN116254488A CN 116254488 A CN116254488 A CN 116254488A CN 202211569666 A CN202211569666 A CN 202211569666A CN 116254488 A CN116254488 A CN 116254488A
- Authority
- CN
- China
- Prior art keywords
- alloy
- metallic glass
- glass alloy
- zirconium
- work hardening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 66
- 239000005300 metallic glass Substances 0.000 title claims abstract description 47
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000005482 strain hardening Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000013526 supercooled liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004512 die casting Methods 0.000 claims description 2
- 238000005242 forging Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000008204 material by function Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000003723 Smelting Methods 0.000 claims 1
- 239000002923 metal particle Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a high-ductility zirconium-based metallic glass alloy with work hardening characteristics, a preparation method and application thereof. The CuZrAlAg-based, zrCuAl-based and CuZrTiNi-based alloys of the present invention have a Cu content of 35at% or more and contain monomer metal particles or alloy particles such as V, nb, ta, mo, W, fe, co which are insoluble in Cu, and are dispersed to obtain non-solid solution crystalline metal/alloy particle-dispersed zirconium-based metallic glass alloys which exhibit a large work hardening rate of 50MPa/1%, a large plastic strain of 5% or more and a high fracture strength of 2500MPa or more. The simultaneous expression of these characteristics is a new characteristic which is not found in any of hundreds of or more bulk metallic glasses so far, and is expected to bring about further expansion of the bulk metallic glass in the commercial field.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a high-ductility zirconium-based metallic glass alloy with a work hardening property, and a preparation method and application thereof.
Background
Heretofore, a three-dimensional bulk metallic glass having a diameter of 1 mm or more has been produced from a plurality of multi-element alloys (containing 3 or more alloy elements) having a main component (50 at% or more) such as Zr, mg, ln, ti, hf, fe, co, ni, cu, pd, pt and has been widely used.
Zirconium-based alloys are widely used as a representative metallic glass alloy system, mainly as structural and functional materials.
The atomic composition of zirconium-based metallic glasses that do not contain deleterious elements is typically composed of: 5-20at% of Al, 20-45at% of Ni and Cu, and the balance of Zr or a plurality of components of which 2-8at% of part of Zr is replaced by Ti, nb and Ta, wherein the massive metallic glass has the characteristics of strong glass forming capability, 80-90GPa of elastic modulus, 1400-1600MPa of yield strength, about 2% of large elastic strain, 1500-1800MPa of compressive fracture strength, 450-570 of Vickers hardness, 350-560MPa of fatigue strength and 700-750K of crystallization initiation temperature.
In addition to the excellent mechanical properties described above, zirconium-based metallic glasses have properties of high corrosion resistance, gloss, precision net casting workability, viscous flow workability, high electrical resistance, low thermal expansion, low thermal conductivity, and the like. These properties are special properties that any crystalline material does not possess, and thus zirconium-based metallic glasses are widely used in the fields of mechanical precision materials, housings for electronic devices such as smart phones, eyeglass frames, writing instruments, sports instruments, ornament materials, optomechanical materials, pressure sensor materials, timepiece materials, blade materials, medical instruments or device materials, and the like.
However, the existing zirconium-based metallic glasses have a significant disadvantage in that they do not exhibit work hardening behavior under both tensile and compressive stresses. Therefore, the large macroscopic plastic elongation and plastic strain of the bulk metallic glass are obviously smaller than those of the common crystalline alloy, and the result is that the metallic glass with large plastic elongation and plastic distortion does not appear so far with respect to work hardening behavior, and the novel metallic glass is expected to bring about further expansion of the application field of the metallic glass.
Disclosure of Invention
The aim of the invention is achieved by the following technical proposal
A high-ductility zirconium-based metallic glass alloy having work hardening characteristics, which comprises the composition of (Cu x Zr y Al z Ni β Ag γ Ti δ ) 100-α M α Of which (Cu) x Zr y Al z Ni β Ag γ Ti δ ) Is based onThe base alloy, M, includes at least one of V, nb, ta, cr, mo, W, fe, co.
Preferably, M comprises at least one of Ta and Nb.
The (100-alpha) and alpha are the atomic percentages of each component in the alloy, and alpha=5-15.
The x, y, z, beta, gamma and delta are the atomic percentages of each component in the base alloy, and x=35-40, y=15-60, z=0-20, beta=0-15, gamma=0-15 and delta=0-40.
The base alloy may further contain at least one of Pd, pt, or rare earth elements having an atomic percentage (based on the atomic percentage of the base alloy) of less than 1.
Preferably, the metallic glass alloy has a composition of (Cu x Zr y Al z Ag γ ) 100-α M α Where x=35-40, y=40-55, z=5-20, γ=5-15, α=4-16; more preferably, M is Ta; further preferably, the metallic glass alloy has a composition of (Cu 36 Zr 48 Al 8 Ag 8 ) 100-α M α Where α=5-15.
Preferably, the metallic glass alloy has a composition of (Cu x Zr y Al z ) 100-α M α Wherein x=35-40, y=40-60, z=5-20, α=2-10; more preferably, M comprises at least one of Ta and Nb; further preferably, the metallic glass alloy has a composition of (Cu 40 Zr 50 Al 10 ) 100-α M α Where α=3-9.
Preferably, the metallic glass alloy has a composition of (Cu x Zr y Ni β Al z ) 100-α M α Where x=35-40, y=40-60, β=0-15, z=0-20, α=5-16; more preferably, M comprises at least one of Ta and Nb; further preferably, the metallic glass alloy has a composition of (Cu 37 Zr 50 Ni 3 Al 10 ) 100-α M α Where α=6-15.
PreferablyThe metallic glass alloy has a composition of (Cu x Zr y Ni β Ti δ ) 100-α M α Where x=35-40, y=10-20, β=5-15, δ=30-40, α=3-9; more preferably, M comprises at least one of Ta and Nb; further preferably, the metallic glass alloy has a composition of (Cu 40 Zr 15 Ni 10 Ti 35 ) 100-α M α Where α=6.
The preparation method of the zirconium-based metallic glass alloy comprises the following steps:
melting alloy components (metal small blocks or powder) except the M element to prepare alloy melt, adding the M element into the alloy melt, and then cooling and solidifying the melt in a supercooled liquid state to obtain zirconium-based metallic glass alloy;
the zirconium-based metal glass alloy can be manufactured into cylindrical bars with the diameter of 2-5 mm or plates with the thickness of 2-4 mm by using the prior art methods such as a copper die differential pressure casting method, a jet casting method, a forging casting method, a locking die casting method, an inclined casting method or a casting die solution injection method.
The zirconium-based metallic glass alloy of the present invention can be used as a structural and functional material, in particular, as a mechanical precision material, an electronic equipment housing, a spectacle frame, a writing instrument, a sports instrument, an ornament material, an optomechanical material, a pressure sensor material, a timepiece material, a blade material, a medical instrument, or an equipment material.
Compared with the prior art, the invention has the following advantages and effects:
in the CuZrAlAg-based, zrCuAl-based and CuZrTiNi-based alloys of the present invention, the Cu content is 35at% or more, and monomer metal particles or alloy particles such as V, nb, ta, mo, W, fe, co which are insoluble in Cu are dispersed to prepare a non-solid solution crystalline metal/alloy particle-dispersed zirconium-based metallic glass alloy which exhibits a large work hardening rate of 50MPa/1%, a large plastic strain of 5% or more, and a high fracture strength of 2500MPa or more. The simultaneous expression of these characteristics is a new characteristic which is not found in any of hundreds of or more bulk metallic glasses so far, and is expected to bring about further expansion of the bulk metallic glass in the commercial field.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Examples
Alloy raw materials were prepared from the alloy components shown in tables 1 and 2, and after preparing a master alloy melt, the master alloy melt was cooled and solidified in a supercooled liquid state, and a sample of a cylindrical bar having a sample diameter of 2mm was prepared by copper die suction casting, and various characteristic parameters thereof were measured.
The composition of the components and the characteristic parameters of the alloy samples of the examples of the present invention are shown in Table 1, and the composition of the components and the characteristic parameters of the comparative examples are shown in Table 2.
The compressive stress-strain curve was measured by a compression test method using an instron (model) tester, and the plastic strain was evaluated from the curve.
In addition, the strain rate was 2X 10 at room temperature under tensile load and compressive load by an Instron tester -4 ～9×10 -4 The stress-elongation curve or stress-strain curve is obtained in seconds, from which the breaking strength (MPa) and the yield strength (MPa) are determined.
Other less than optimal conditions are known techniques and practices.
Tables 1 and 2 show the performance parameters of the part of the alloy materials prepared in the examples of the present invention.
Table 1: composition and characterization parameters of the alloy samples of the examples
Table 2: composition and characteristic parameters of comparative alloy samples
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A high ductility zirconium-based metallic glass alloy having work hardening properties characterized by:
in atomic percent, the composition of the component (Cu x Zr y Al z Ni β Ag γ Ti δ ) 100-α M α Of which (Cu) x Zr y Al z Ni β Ag γ Ti δ ) M comprises at least one of V, nb, ta, cr, mo, W, fe, co as a base alloy;
the (100-alpha) and alpha are the percentages of each component in the alloy, and alpha=5-15;
the x, y, z, beta, gamma and delta are the percentages of each component in the base alloy, and x=35-40, y=15-60, z=0-20, beta=0-15, gamma=0-15 and delta=0-40.
2. The metallic glass alloy of claim 1, wherein:
the M comprises at least one of Ta and Nb.
3. The metallic glass alloy of claim 1, wherein:
the base alloy contains at least one of Pd, pt or rare earth elements with atomic percent less than 1.
4. The metallic glass alloy of claim 1, wherein:
the component composition of the metallic glass alloy is (Cu x Zr y Al z Ag γ ) 100-α M α Wherein x=35-40, y=40-55, z=5-20, γ=5-15，α＝4-16。
5. The metallic glass alloy of claim 1, wherein:
the component composition of the metallic glass alloy is (Cu x Zr y Al z ) 100-α M α Where x=35-40, y=40-60, z=5-20, α=2-10.
6. The metallic glass alloy of claim 1, wherein:
the component composition of the metallic glass alloy is (Cu x Zr y Ni β Al z ) 100-α M α Where x=35-40, y=40-60, β=0-15, z=0-20, α=5-16.
7. The metallic glass alloy of claim 1, wherein:
the component composition of the metallic glass alloy is (Cu x Zr y Ni β Ti δ ) 100-α M α Where x=35-40, y=10-20, β=5-15, δ=30-40, α=3-9.
8. A method for producing a metallic glass alloy as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
and smelting alloy components except the M element to prepare alloy melt, adding the M element into the alloy melt, and then cooling and solidifying the melt in a supercooled liquid state to obtain the zirconium-based metallic glass alloy.
9. The method of manufacturing according to claim 8, wherein:
the zirconium-based metal glass alloy is prepared into a cylindrical bar with the diameter of 2-5 mm or a plate with the thickness of 2-4 mm by a copper die differential pressure casting method, a jet casting method, a forging casting method, a locking die casting method, an inclined casting method or a casting die solution jet method.
10. Use of a metallic glass alloy according to any of claims 1 to 7 for the preparation of structural and functional materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211569666.XA CN116254488A (en) | 2022-12-08 | 2022-12-08 | High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211569666.XA CN116254488A (en) | 2022-12-08 | 2022-12-08 | High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116254488A true CN116254488A (en) | 2023-06-13 |
Family
ID=86678259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211569666.XA Pending CN116254488A (en) | 2022-12-08 | 2022-12-08 | High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116254488A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958831A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院物理研究所 | Copper-zirconium based amorphous alloy, and preparation method |
| CN101787501A (en) * | 2010-02-05 | 2010-07-28 | 北京科技大学 | Bulk metal glass composite material with stretching plasticity and work hardening capacity |
| US20130255837A1 (en) * | 2012-03-29 | 2013-10-03 | Atakan Peker | Zirconium based bulk metallic glasses |
| CN114657480A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | High-plasticity phase-separated Zr-based amorphous alloy and preparation method and application thereof |
-
2022
- 2022-12-08 CN CN202211569666.XA patent/CN116254488A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958831A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院物理研究所 | Copper-zirconium based amorphous alloy, and preparation method |
| CN101787501A (en) * | 2010-02-05 | 2010-07-28 | 北京科技大学 | Bulk metal glass composite material with stretching plasticity and work hardening capacity |
| US20130255837A1 (en) * | 2012-03-29 | 2013-10-03 | Atakan Peker | Zirconium based bulk metallic glasses |
| CN114657480A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | High-plasticity phase-separated Zr-based amorphous alloy and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100701027B1 (en) | Monolithic Metallic Glasses With Enhanced Ductility | |
| CN106756647B (en) | A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel | |
| JP3805601B2 (en) | High corrosion resistance and high strength Fe-Cr based bulk amorphous alloy | |
| JP5069111B2 (en) | Al-Si-Mg-Zn-Cu alloy for aerospace and automotive castings | |
| US6918973B2 (en) | Alloy and method of producing the same | |
| CN104822852A (en) | Bulk nickel-based chromium and phosphorus bearing metallic glasses with high toughness | |
| JP5502976B2 (en) | Manufacturing method of high hardness, high corrosion resistance and high wear resistance alloy | |
| JP3860445B2 (en) | Cu-Be based amorphous alloy | |
| CN114606422B (en) | CrCoNi medium-entropy alloy and low-temperature rolling method thereof | |
| Fu et al. | Mechanical properties of metallic glass matrix composites: Effects of reinforcement character and connectivity | |
| CN109763019A (en) | A kind of high-strength high-elasticity Manic and preparation method thereof | |
| CN116254488A (en) | High-ductility zirconium-based metallic glass alloy with work hardening characteristics and preparation method and application thereof | |
| JPH0617550B2 (en) | Method for producing aluminum alloy materials with improved fatigue strength, especially bar stock | |
| JP2009084681A (en) | Stress buffer material composed of aluminum alloy | |
| KR20130110689A (en) | Work hardenable metallic glass matrix composite | |
| JP2006183104A (en) | High-strength titanium alloy having excellent cold workability | |
| Cheng et al. | Structure, castability and mechanical properties of commercially pure and alloyed titanium cast in graphite mould | |
| EP0540056B1 (en) | Compacted and consolidated material of aluminum-based alloy and process for producing the same | |
| JP2012158794A (en) | Cu-FREE, Zr-BASED METAL GLASS ALLOY | |
| JP4742268B2 (en) | High-strength Co-based metallic glass alloy with excellent workability | |
| CN116065079B (en) | High-ductility and high-heat-resistance high-entropy alloy and preparation method and application thereof | |
| JP3880245B2 (en) | High strength and high corrosion resistance Ni-based amorphous alloy | |
| CN115725912A (en) | Zirconium-based metallic glass alloy with high strength and high plastic strain as well as preparation method and application thereof | |
| JP5321999B2 (en) | Ni-based metallic glass alloy | |
| JP2021195610A (en) | Deformation-induced zirconium-based alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |