CN107287535A - A kind of big plastic high-strength degree zirconium-based bulk amorphous alloy and preparation method - Google Patents
A kind of big plastic high-strength degree zirconium-based bulk amorphous alloy and preparation method Download PDFInfo
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- CN107287535A CN107287535A CN201710484012.XA CN201710484012A CN107287535A CN 107287535 A CN107287535 A CN 107287535A CN 201710484012 A CN201710484012 A CN 201710484012A CN 107287535 A CN107287535 A CN 107287535A
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- 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
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- 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
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- 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
- C22C1/11—Making amorphous alloys
Abstract
A kind of big plastic high-strength degree zirconium-based bulk amorphous alloy and preparation method, are constituted with common metal zirconium, copper, nickel, aluminium and trace rare-earth element erbium, and its composition form is（Zr63.36Cu14.52Ni10.12Al12）1‑xErx, wherein 0≤x≤10%；The zirconium-based bulk amorphous alloy is made according to atomic molar ratio dispensing, smelting, suction casting；The zirconium-based bulk amorphous alloy rare earth elements erbium has the effect of activeness and quietness.The zirconium-based bulk amorphous alloy of the present invention has excellent plastic deformation ability, while reaching very high intensity by excellent work hardening capacity.In addition, the zirconium-based bulk amorphous alloy of the present invention also has strong amorphous formation ability and heat endurance, with low glass transformation temperature, be conducive to being formed at a lower temperature.Therefore, the zirconium-based bulk amorphous alloy has potential application value.
Description
Technical field
The present invention relates to amorphous alloy material field, using common metal zirconium, copper, nickel, aluminium as major components, pass through addition
The zirconium-based bulk amorphous alloy with big plasticity and high intensity is obtained with the content of adjustment trace rare-earth element erbium.
Background technology
Non-crystaline amorphous metal is under big cooldown rate, to cross crystallization process, and solidification forms institute under glass transition temperature
The amorphous alloy of meaning.Be compared to crystal alloy, amorphous alloy possess crystal alloy without performance or do not reach requirement
Some performances, its intensity is significantly larger than crystal alloy, but is exactly, because non-crystaline amorphous metal has very high intensity, almost to approach
In theoretical strength, so its plasticity is relatively low, it may occur that the brittle fracture without sign, if this materials application arrived
Disaster will easily be triggered in practice.It is exactly because its modeling as a kind of rising and very promising structural material
Property the too poor extensive use that seriously govern them, therefore, how to increase the plasticity of non-crystaline amorphous metal turns into this field for many years
Come the emphasis studied.
In the exploration of nearest decades, around the plasticity for how improving non-crystaline amorphous metal, many scientific research personnel propose very
Multi-method, such as prepare composite, addition increasing tougheness element etc..Can suitably it be improved by the method for preparing composite
Plasticity, but also reduce the intensity of non-crystaline amorphous metal simultaneously, the complex process of this method and whard to control, sometimes also by a variety of conditions
Limitation, be not preferable toughness reinforcing mode.
Previous research work shows that the first method for usually improving non-crystaline amorphous metal plasticity and toughness of addition increasing tougheness is simple and effect is bright
Aobvious, the especially addition of rare earth element can not only increase toughness, can also increase intensity, be a kind of preferable toughness reinforcing mode.
It therefore, it can add rare earth element er in alloy system, the block with big plasticity, high intensity obtained in the way of composition design
Body non-crystaline amorphous metal.Essential element is all cheap common metal in the present invention, therefore is with a wide range of applications.
The content of the invention
Good amorphous formation ability and heat endurance had both been kept it is an object of the invention to provide a kind of, its power is improved again
Performance is learned, the zirconium-based bulk amorphous alloy of activeness and quietness is enabled in particular to.
Another object of the present invention is just to provide a kind of preparation method for obtaining above-mentioned zirconium-based bulk amorphous alloy.
The present invention is a kind of big plastic high-strength degree zirconium-based bulk amorphous alloy, and its component is
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%.
The preparation method of above-described big plastic high-strength degree zirconium-based bulk amorphous alloy, its step is：
（1）Dispensing：According to the atomic molar ratio dispensing required for composition formula, described composition formula：
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%, weighs each component；
（2）Melting：By step（1）The required raw material claimed is put into vacuum high-frequency electromagnetic induction heating furnace, adjusts vacuum magnetcisuspension
The vacuum of floating smelting furnace is to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8
×10-4Pa, carries out the melting of foundry alloy, and melt back 3~5 times is well mixed each component, foundry alloy is obtained after cooling
Ingot；
（3）Inhale casting：Non-crystalline material sample is prepared using copper mold casting：By step 2) prepare
（Zr63.36Cu14.52Ni10.12Al12）1-xErxFoundry alloy is put into magnetic levitation melting cold-crucible, adjusts vacuum magnetic suspension smelting furnace
Vacuum to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8 × 10-4Pa,
By foundry alloy remelting, under 7 ~ 10kV of induced voltage after 1 ~ 5min of melting, induced voltage is down under 5 ~ 8kV by negative pressure copper
Aluminium alloy is inhaled and casts bar by mould suction casting method.
The zirconium-based bulk amorphous alloy that the present invention is provided the advantage is that compared with existing block amorphous alloy：Have
Excellent plastic deformation ability, while very high intensity has been reached by strong processing hardening phenomenon, the compression modeling of its room temperature
Property strain be 10% ~ 50%, compression yield strength is 1400 ~ 1700MPa, and compression strength is 1500 ~ 3000MPa, and fracture strength is
1400~3000MPa；With strong amorphous formation ability and heat endurance, supercooled liquid phase sector width T=80~100 DEG C；Have
Low glass transformation temperature（Tg=360~400 DEG C）, be conducive to being formed at a lower temperature.The invention provides one kind
New structural material, has broad application prospects in structural material field.In addition, the preparation method technique letter that the present invention is provided
It is single, it is easy to accomplish batch production.
Brief description of the drawings
Fig. 1 is the as cast condition XRD of the zirconium-based bulk amorphous alloy obtained, and Fig. 2 is is obtained zirconium-based bulk amorphous alloy
Room temperature load-deformation curve, Fig. 3 by acquisition zirconium-based bulk amorphous alloy means of differential scanning calorimetry（DSC）) curve map, rise
Warm speed is 20K/min.
Embodiment
The present invention is a kind of big plastic high-strength degree zirconium-based bulk amorphous alloy, and its component is
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%.
The preparation method of above-described big plastic high-strength degree zirconium-based bulk amorphous alloy, its step is：
（1）Dispensing：According to the atomic molar ratio dispensing required for composition formula, described composition formula：
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%, weighs each component；
（2）Melting：By step（1）The required raw material claimed is put into vacuum high-frequency electromagnetic induction heating furnace, adjusts vacuum magnetcisuspension
The vacuum of floating smelting furnace is to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8
×10-4Pa, carries out the melting of foundry alloy, and melt back 3~5 times is well mixed each component, foundry alloy is obtained after cooling
Ingot；
（3）Inhale casting：Non-crystalline material sample is prepared using copper mold casting：By step（2）Prepare
（Zr63.36Cu14.52Ni10.12Al12）1-xErxFoundry alloy is put into magnetic levitation melting cold-crucible, adjusts vacuum magnetic suspension smelting furnace
Vacuum to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8 × 10-4Pa,
By foundry alloy remelting, under 7 ~ 10kV of induced voltage after 1 ~ 5min of melting, induced voltage is down under 5 ~ 8kV by negative pressure copper
Aluminium alloy is inhaled and casts bar by mould suction casting method.
Step described above（1）In the purity of rare earth element er be not less than 99.99wt%, Zr, Cu, Ni, Al purity are equal
It is not less than 99.9wt%.
Embodiment 1：Prepare（Zr63.36Cu14.52Ni10.12Al12）97.8Er2.2Block amorphous alloy：
（1）Dispensing：It is more than 99.9% rare earth element er of Zr, Cu, Ni, Al and purity more than 99.99% from purity, according to
The atomic molar ratio dispensing required for formula is constituted, each component is weighed；
（2）Melting：By step（1）The required raw material claimed is put into vacuum high-frequency electromagnetic induction heating furnace, adjusts vacuum magnetcisuspension
The vacuum 1 × 10 of floating smelting furnace-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8 ×
10-4Pa carries out melting, and master alloy ingot melt back 3~5 times is well mixed each component, master alloy ingot is obtained after cooling；
（3）Inhale casting：Non-crystaline amorphous metal sample is prepared using copper mold casting：By step 2) prepare
（Zr63.36Cu14.52Ni10.12Al12）97.8Er2.2Foundry alloy is put into magnetic levitation melting cold-crucible, adjusts vacuum magnetic suspension melting
The vacuum 1 × 10 of stove-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8 × 10-4Pa,
By foundry alloy remelting, under 7 ~ 10kV of induced voltage after 1 ~ 5min of melting, induced voltage is down under 5 ~ 8kV by negative pressure copper
Aluminium alloy is inhaled and casts bar by mould suction casting method.
The X-ray diffraction of various Er content alloys as shown in Figure 1（XRD）Collection of illustrative plates can prove that prepared different Er contain
The alloy of amount is completely amorphous state alloy.
The room temperature compressive stress strain curve of various Er contents zirconium-based bulk amorphous alloys is illustrated in figure 2, such as the institute of table 1
It is shown as the mechanical property parameters of the various Er contents zirconium-based bulk amorphous alloys of the present invention.It can be drawn by Fig. 2 combinations table 1：It is dilute
Earth elements Er addition can significantly increase the plasticity and intensity of zirconium-base amorphous alloy；When rare earth element er content increase to x=
When 2.2, its compression yield strength is 1532MPa, and compression strength and fracture strength are 2130MPa, and plastic strain is 25.54%, about
It is 6 times of the zirconium-based bulk amorphous alloy for being not added with rare earth element er, while being shown significantly occurring plastic period
Serrated plastic flow behavior and strong processing hardening phenomenon, show more excellent mechanical property.
The mechanical property parameters of the various Er content alloys of the present invention of table 1：
The heat analysis of various Er contents zirconium-based bulk amorphous alloys shown in Fig. 3（DSC）Figure, table 2 show the various Er of the present invention
The thermal physical property parameter of content zirconium-based bulk amorphous alloy, the glass of the zirconium-based bulk amorphous alloy it can be seen from Fig. 3 combinations table 2
Glass transition temperature Tg=389 DEG C, for other zirconium-based bulk amorphous alloys, the zirconium-based bulk amorphous alloy has relatively low
Glass transformation temperature；T=Tx-Tg=85 DEG C, with good heat endurance.
The thermal physical property parameter of the various Er contents zirconium-based bulk amorphous alloys of the present invention of table 2：
Embodiment 2：Prepare（Zr63.36Cu14.52Ni10.12Al12）97.4Er2.6Block amorphous alloy：
In the same manner as in Example 1, its compressive stress strain curve with reference to table 1 as shown in Fig. 2 can be seen that for its preparation method：When dilute
When earth elements Er contents increase to x=2.6, its compression yield strength is 1495MPa, and compression strength and fracture strength are
2538MPa, plastic strain is 34.87%, is approximately 8 times of zirconium-based bulk amorphous alloy for being not added with rare earth element er, is equally moulding
Property deformation stage shows obvious serrated plastic flow behavior and strong processing hardening phenomenon, at room temperature with excellent comprehensive
Close mechanical property.
As shown in figure 3 and table 2, glass transformation temperature Tg=389 DEG C of the zirconium-based bulk amorphous alloy, the Zirconium-based block is non-
Peritectic alloy has relatively low glass transformation temperature；T=82 DEG C, with good heat endurance.
The zirconium-based bulk amorphous alloy that the present invention is provided has excellent room-temperature mechanical property, excellent amorphous formation ability
And heat endurance, with potential application value.
Claims (3)
1. a kind of big plastic high-strength degree zirconium-based bulk amorphous alloy, it is characterized in that：Its component is
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%.
2. the preparation method of the big plastic high-strength degree zirconium-based bulk amorphous alloy described in claim 1, it is characterised in that its step
For：
（1）Dispensing：According to the atomic molar ratio dispensing required for composition formula, described composition formula：
（Zr63.36Cu14.52Ni10.12Al12）1-xErx, wherein 0≤x≤10%, weighs each component；
（2）Melting：By step（1）The required raw material claimed is put into vacuum high-frequency electromagnetic induction heating furnace, adjusts vacuum magnetcisuspension
The vacuum of floating smelting furnace is to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8
×10-4Pa, carries out the melting of foundry alloy, and melt back 3~5 times is well mixed each component, foundry alloy is obtained after cooling
Ingot；
（3）Inhale casting：Non-crystalline material sample is prepared using copper mold casting：By step 2) prepare
（Zr63.36Cu14.52Ni10.12Al12）1-xErxFoundry alloy is put into magnetic levitation melting cold-crucible, adjusts vacuum magnetic suspension smelting furnace
Vacuum to 1 × 10-3~5 × 10-3Pa, then filling high-purity argon gas makes the vacuum of vacuum chamber to 1 × 10-4~8 × 10-4Pa,
By foundry alloy remelting, under 7 ~ 10kV of induced voltage after 1 ~ 5min of melting, induced voltage is down under 5 ~ 8kV by negative pressure copper
Aluminium alloy is inhaled and casts bar by mould suction casting method.
3. the preparation method of big plastic high-strength degree zirconium-based bulk amorphous alloy according to claim 2, it is characterised in that：Institute
State step（1）In the purity of rare earth element er be not less than 99.99wt%, Zr, Cu, Ni, Al purity are not less than 99.9wt%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070801A (en) * | 2017-12-19 | 2018-05-25 | 哈尔滨工业大学 | A kind of method that inexpensive Centimeter Level zirconium-base amorphous alloy is prepared using technical grade sponge zirconium |
| CN108144988A (en) * | 2017-12-26 | 2018-06-12 | 兰州理工大学 | A kind of Zr base block amorphous alloys thermoplastic molding process determination method for parameter |
| CN108300950A (en) * | 2018-03-23 | 2018-07-20 | 兰州理工大学 | The preparation method and hot-working section formulating method of ZrCuNiAl block metal glass |
| CN108361352A (en) * | 2018-04-04 | 2018-08-03 | 深圳市锆安材料科技有限公司 | A kind of flexible gear and its manufacturing equipment and manufacturing method |
| CN109280864A (en) * | 2018-10-29 | 2019-01-29 | 湖南理工学院 | Zr-Al-Ni-Cu block metal glass with different cluster contents and performance |
| CN109338252A (en) * | 2018-11-30 | 2019-02-15 | 昆明理工大学 | A kind of zirconium base porous amorphous alloy and preparation method |
| CN109468548A (en) * | 2019-01-04 | 2019-03-15 | 盘星新型合金材料(常州)有限公司 | A kind of width supercooling liquid phase region zirconium-base amorphous alloy |
| CN110616387A (en) * | 2019-11-05 | 2019-12-27 | 兰州理工大学 | Amorphous alloy for zirconium-based amorphous flexible gear blank, special copper mold and preparation method |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN115305417A (en) * | 2022-09-16 | 2022-11-08 | 盘星新型合金材料(常州)有限公司 | Zirconium-based amorphous alloy with plasticity and hardness and preparation method thereof |
| CN116804258A (en) * | 2023-08-23 | 2023-09-26 | 南京工业大学 | Bulk zirconium-based amorphous alloy with high strength and high hardness and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070801B (en) * | 2017-12-19 | 2019-12-31 | 哈尔滨工业大学 | Method for preparing low-cost centimeter-level zirconium-based amorphous alloy by adopting industrial-level sponge zirconium |
| CN108070801A (en) * | 2017-12-19 | 2018-05-25 | 哈尔滨工业大学 | A kind of method that inexpensive Centimeter Level zirconium-base amorphous alloy is prepared using technical grade sponge zirconium |
| CN108144988A (en) * | 2017-12-26 | 2018-06-12 | 兰州理工大学 | A kind of Zr base block amorphous alloys thermoplastic molding process determination method for parameter |
| CN108300950A (en) * | 2018-03-23 | 2018-07-20 | 兰州理工大学 | The preparation method and hot-working section formulating method of ZrCuNiAl block metal glass |
| CN108361352A (en) * | 2018-04-04 | 2018-08-03 | 深圳市锆安材料科技有限公司 | A kind of flexible gear and its manufacturing equipment and manufacturing method |
| CN109280864B (en) * | 2018-10-29 | 2021-05-18 | 湖南理工学院 | Zr-Al-Ni-Cu bulk metallic glass with different cluster content and performance |
| CN109280864A (en) * | 2018-10-29 | 2019-01-29 | 湖南理工学院 | Zr-Al-Ni-Cu block metal glass with different cluster contents and performance |
| CN109338252A (en) * | 2018-11-30 | 2019-02-15 | 昆明理工大学 | A kind of zirconium base porous amorphous alloy and preparation method |
| CN109468548A (en) * | 2019-01-04 | 2019-03-15 | 盘星新型合金材料(常州)有限公司 | A kind of width supercooling liquid phase region zirconium-base amorphous alloy |
| CN110616387A (en) * | 2019-11-05 | 2019-12-27 | 兰州理工大学 | Amorphous alloy for zirconium-based amorphous flexible gear blank, special copper mold and preparation method |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN115305417A (en) * | 2022-09-16 | 2022-11-08 | 盘星新型合金材料(常州)有限公司 | Zirconium-based amorphous alloy with plasticity and hardness and preparation method thereof |
| CN116804258A (en) * | 2023-08-23 | 2023-09-26 | 南京工业大学 | Bulk zirconium-based amorphous alloy with high strength and high hardness and preparation method thereof |
| CN116804258B (en) * | 2023-08-23 | 2023-10-27 | 南京工业大学 | Bulk zirconium-based amorphous alloy with high strength and high hardness and preparation method thereof |
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