CN115652225B - A Ni-based bulk amorphous alloy with high plasticity at room temperature and a preparation method thereof - Google Patents
A Ni-based bulk amorphous alloy with high plasticity at room temperature and a preparation method thereof Download PDFInfo
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- CN115652225B CN115652225B CN202211369785.0A CN202211369785A CN115652225B CN 115652225 B CN115652225 B CN 115652225B CN 202211369785 A CN202211369785 A CN 202211369785A CN 115652225 B CN115652225 B CN 115652225B
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 239000010453 quartz Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 238000005482 strain hardening Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000012163 sequencing technique Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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Abstract
The invention relates to a Ni-based bulk amorphous alloy with room temperature high plasticity and a preparation method thereof, wherein the structural formula of the Ni-based bulk amorphous alloy is Ni 76‑ xCoxNb4P16B4 (x=5, 10,15 and 20 at%), wherein x represents the atomic percentage of Co element in the alloy. The amorphous alloy rod is prepared by adopting Fluxing and J-sequencing technologies, has room-temperature compression plasticity of 27% when x=5 at%, and has yield strength of 2596 MPa and breaking strength of 3559 MPa. The Ni-based bulk amorphous alloy of the present invention has excellent plastic deformation ability, and at the same time, can achieve higher strength by work hardening. Therefore, the Ni-based bulk amorphous alloy has potential value in the field of application as a structural material.
Description
Technical Field
The invention relates to the field of amorphous alloy materials, in particular to a Ni-based block amorphous alloy with room temperature high plasticity and a preparation method thereof. The Ni-based bulk amorphous alloy has excellent compression plasticity and better work hardening capacity at room temperature.
Background
Bulk amorphous alloys have attracted considerable attention from researchers over the past decades due to their excellent mechanical properties such as high strength, high elastic strain limit, etc. As a candidate for structural materials, bulk amorphous alloys, while exhibiting their properties over crystalline materials, suffer from poor plasticity, which severely limits their widespread use in engineering. Therefore, the development of the bulk amorphous alloy with room temperature high plasticity has important value and significance for preventing the bulk amorphous alloy from being used as a structural material and having no sign of brittle fracture in engineering application.
Disclosure of Invention
The invention aims to provide a Ni-based bulk amorphous alloy with room temperature high plasticity, which well solves the problem of insufficient deformation capability of the amorphous alloy at room temperature.
It is another object of the present invention to provide a method for preparing the above Ni-based bulk amorphous alloy.
The preparation method of the Ni-based bulk amorphous material with large plastic deformation at room temperature comprises the following specific steps.
(1) And (3) preparing a master alloy ingot, namely weighing and loading the atoms in the structural formula of the Ni-based bulk amorphous alloy into a quartz tube according to the percentage, then connecting the quartz tube into a vacuum system, vacuumizing, introducing Ar gas for gas washing when the vacuum degree reaches about 50 Pa, repeating the gas washing operation for 4 times, and finally smelting the raw materials of each component in the quartz tube into the alloy ingot by using a flame gun.
(2) And (3) placing the alloy cast ingot smelted in the step (1) into a molten purification medium consisting of B 2O3 and CaO in a mass ratio of 3:1, and carrying out purification treatment in a furnace at a temperature of 1150 ℃ for 3 hours.
(3) And (3) filling the purified alloy cast ingot in the step (2) into a quartz tube prepared in advance, vacuumizing, and introducing Ar gas to perform gas washing when the vacuum degree reaches about 50 Pa, wherein the gas washing operation is repeated for 4 times. After the gas washing is finished, the purified alloy cast ingot is burned to a molten state by a flame gun, the alloy cast ingot is quickly inserted into a vertical sintering furnace, a vacuum control valve is opened for vacuumizing for 30 seconds, ar gas is introduced to push the molten alloy cast ingot into the bottom of a quartz tube, the temperature is kept for a certain time, and finally the alloy cast ingot is taken out and quickly quenched into water.
The Ni-based bulk amorphous alloy provided by the invention has the advantages of excellent room temperature plastic deformation capability, capability of improving the strength by work hardening, about 7% -27% of room temperature compressive plastic deformation, 2146 MPa~2596 MPa of compressive yield strength and 2188 MPa~3559 MPa of breaking strength. The invention provides a novel Ni-based bulk amorphous alloy material with room temperature high plasticity, and has wide application prospect in the field of structural materials.
Drawings
FIG. 1 is an XRD pattern of Ni-based bulk amorphous alloys in examples 1-4 of the present invention.
FIG. 2 is a plot of room temperature compressive stress versus strain for Ni-based bulk amorphous alloys in examples 1-4 of this invention.
Fig. 3 is a scanning electron microscope image of a cylindrical shear band of a Ni-based bulk amorphous alloy according to example 1 of the present invention.
Description of the embodiments
The structural formula of the Ni-based bulk amorphous alloy with room temperature high plasticity provided by the invention is Ni 76- xCoxNb4P16B4 (x=5, 10,15 and 20 at%), x is the atomic percentage of Co in the alloy, and the specific preparation steps are implemented as follows.
Examples 1-4 (x=5, 10,15 and 20 at.%) preparation of bulk amorphous alloys.
And 1, calculating the contents of nickel powder (99.8%), cobalt phosphide (98%), niobium powder (99.8%) and boron powder (99.9%) according to the atomic mass percentages of Ni 76-xCoxNb4P16B4 (x=5, 10,15 and 20 at%) corresponding to each embodiment, loading the weighed components into a quartz tube, and then accessing into a vacuum system for vacuumizing. When the vacuum degree reaches about 50 Pa, ar gas is introduced to carry out gas washing, the gas washing is repeated for 4 times, and finally, each component element contained in the quartz tube is smelted into alloy cast ingots by a flame gun.
And 2, placing the smelted alloy cast ingot into a molten purification medium consisting of B 2O3 and CaO in a mass ratio of 3:1, and carrying out purification treatment in a furnace at 1150 ℃ for 3 hours.
And 3, placing the alloy cast ingot which is already purified in the step 2 into alcohol, ultrasonically cleaning for about 30 seconds, taking out, airing and then placing into a quartz tube which is prepared in advance. And (3) vacuumizing the quartz tube through a mechanical pump, introducing Ar gas to wash the gas when the vacuum degree reaches about 50 Pa, repeating the gas washing operation for 4 times, burning the alloy cast ingot to a molten state through a burning torch, quickly inserting the alloy cast ingot into a vertical sintering furnace, immediately opening a vacuum control valve to vacuumize for 30 seconds, introducing Ar gas to push the alloy cast ingot into the bottom of the quartz tube, preserving the heat for about 45 seconds, and taking out the quartz tube to quickly quench the alloy cast ingot into water.
Properties of examples 1-4 were determined.
The structures of examples 1-4 were characterized by X-ray diffraction and the results are shown in figure 1. Examples 1-4 each had only one distinct diffuse peak for each critical dimension, which is typical of amorphous alloy structure and was judged to be amorphous without the appearance of a correspondingly sharp crystalline phase peak.
The room temperature compressive mechanical properties of examples 1-4, having a diameter of 1 mm, a length of 2mm, and an aspect ratio of 2:1, were measured with a universal mechanical tester, the compressive strain rate was 4 x 10 -4 s-1, and the stress-strain curve is shown in FIG. 2.
The cylindrical shear band morphology of example 1 after compression with a diameter of 1 mm and a length of 2 mm and an aspect ratio of 2:1 was observed with a Scanning Electron Microscope (SEM) as shown in figure 3.
Comparative analysis of mechanical Properties of examples 1-4.
The plastic strain amounts of examples 1 to 4 were 27%, 19%, 16%, and 7%, respectively, and showed a tendency to decrease with an increase in the Co content. The yield strength and the fracture strength of examples 1 to 3 gradually decrease as the content of Co element increases, and the corresponding yield strength and fracture strength slightly increase by the time of example 4. As can be seen from the scanning electron microscope of fig. 3, the fracture side surface region of example 1 exhibits dense primary and secondary shear bands, i.e., more excellent compression plasticity. The compressive stress-strain curves of examples 1-4 all exhibited significant work hardening, resulting in increased strength for each example.
Claims (4)
1. A Ni-based bulk amorphous alloy with room temperature large plasticity is characterized in that: the preparation method of the Ni-based bulk amorphous alloy with room temperature large plasticity comprises the following steps:
(1) The Ni 71Co5Nb4P16B4 bulk amorphous alloy has the raw materials used for preparing the alloy, namely nickel powder (99.8%), cobalt phosphide (98%), niobium powder (99.8%) and boron powder (99.9%);
(2) Weighing raw materials with the mass required by each component according to the proportion of each atom in the alloy chemical formula, and filling the raw materials into a quartz tube;
(3) Vacuumizing the raw materials weighed in the quartz tube in the step (2), introducing Ar gas for gas washing treatment, repeating the gas washing operation for 4 times, and smelting the raw materials in the quartz tube into alloy cast ingots by using a flame gun;
(4) Placing the alloy cast ingot smelted in the step (3) into a molten purification medium consisting of B 2O3 and CaO in a mass ratio of 3:1 for purification, wherein the temperature is controlled at 1150 ℃ for 3 hours during the purification, and the operation is repeated at intervals of 30 minutes in the last two hours;
(5) Loading the alloy cast ingot purified in the step (4) into a prefabricated quartz tube, vacuumizing for 4 times, introducing Ar gas, washing, burning the alloy cast ingot in the quartz tube to a molten state by using a flame gun, rapidly inserting the alloy cast ingot into a vertical sintering furnace, vacuumizing for 30 seconds by opening a vacuum control valve, introducing Ar gas to push the molten alloy cast ingot into the bottom of the quartz tube, preserving heat for a certain time, and finally rapidly quenching the alloy cast ingot into water.
2. The Ni-based bulk amorphous alloy with room temperature plasticity according to claim 1, wherein the vacuum degree is 50Pa when the steps (3) and (5) are vacuum-pumped.
3. The Ni-based bulk amorphous alloy with room temperature plasticity according to claim 1 or 2, wherein the quartz tube used in step (5) is composed of two parts of a thin tube and a thick tube, the thin tube corresponding to the bottom of the quartz tube.
4. The Ni-based bulk amorphous alloy with room temperature superplasticity of claim 3, wherein the vertical sintering furnace temperature of step (5) is set to 1290 ℃ and the holding time is 45 seconds.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385944A (en) * | 1980-05-29 | 1983-05-31 | Allied Corporation | Magnetic implements from glassy alloys |
| CN114075641A (en) * | 2020-08-21 | 2022-02-22 | 新疆大学 | Method for simultaneously improving iron-based amorphous strength and plasticity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100701027B1 (en) * | 2005-04-19 | 2007-03-29 | 연세대학교 산학협력단 | Single phase amorphous alloy with excellent ductility |
| JP4094030B2 (en) * | 2006-03-20 | 2008-06-04 | 独立行政法人科学技術振興機構 | Super high strength Ni-based metallic glass alloy |
| WO2008030502A2 (en) * | 2006-09-05 | 2008-03-13 | California Institute Of Technology | Amorphous fe and co based metallic foams and methods of producing the same |
| CN1962920A (en) * | 2006-11-21 | 2007-05-16 | 浙江大学 | Ni-Nb-Zr bulk amorphous alloy |
| CN103917673B (en) * | 2011-08-22 | 2016-04-13 | 加利福尼亚技术学院 | Bulk nickel-based metallic glass containing chromium and phosphorus |
| CN102605300B (en) * | 2012-03-13 | 2014-05-07 | 中国科学院宁波材料技术与工程研究所 | High-strength and high-plasticity bulk amorphous magnetic alloy and preparation method thereof |
| WO2014070898A1 (en) * | 2012-10-30 | 2014-05-08 | Glassimetal Technology, Inc. | Bulk nickel-based chromium and phosphorus bearing metallic glasses with high toughness |
| US9957596B2 (en) * | 2013-12-23 | 2018-05-01 | Glassimetal Technology, Inc. | Bulk nickel-iron-based, nickel-cobalt-based and nickel-copper based glasses bearing chromium, niobium, phosphorus and boron |
| CN109930086A (en) * | 2019-03-04 | 2019-06-25 | 新疆大学 | A kind of iron-base block amorphous state alloy and preparation method thereof with high corrosion resistance |
| TR201904074A2 (en) * | 2019-03-19 | 2019-04-22 | Afyon Kocatepe Ueniversitesi Rektoerluegue | NICKEL-BASED LARGE-VOLUME METALLIC GLASS ALLOYS WITH HIGH RATE REFRACTORY METAL AND BORON |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385944A (en) * | 1980-05-29 | 1983-05-31 | Allied Corporation | Magnetic implements from glassy alloys |
| CN114075641A (en) * | 2020-08-21 | 2022-02-22 | 新疆大学 | Method for simultaneously improving iron-based amorphous strength and plasticity |
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