CN103898422A - Al-Ni-Er series aluminum-based amorphous alloy material and preparation method thereof - Google Patents
Al-Ni-Er series aluminum-based amorphous alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an Al-Ni-Er series aluminum-based amorphous alloy material and a preparation method thereof and belongs to the technical field of nonferrous metals. The molar atom content percentages of components in the alloy material are as follows: 80-95% of Al, 1-15% of Ni and 3-18% of Er. The preparation method of the alloy material comprises the steps of firstly removing oxide skins of the metals Al, Ni and Er, and cleaning and mixing to obtain mother alloy raw materials; secondly, performing electric arc melting on the mother alloy raw materials 3-6 times by using titanium as an oxygen absorbent under the condition of taking argon as a protective gas so as to guarantee homogeneous alloy components, and next, naturally cooling under the protection of the argon atmosphere to obtain an evenly smelted mother alloy; finally, heating for resmelting to the range of 900-1400K under the atmosphere of the argon protective gas, and after the mother alloy is melted completely, spraying the mother alloy melt to the surface of a copper roll, and cooling to obtain an amorphous thin tape. The amorphous alloy is good in stability, high in tensile strength, low in component cost, and simple in preparation method, and thus has wide application prospect in the field of forming light aluminum alloy materials.
Description
Technical field
The invention belongs to non-ferrous metal technical field, be specifically related to a kind of Al-Ni-Er aluminum-based amorphous alloy material and preparation method thereof.
Background technology
Since Duwes prepared Au-Si by the method for melt spinning method first and was non-crystaline amorphous metal the sixties in 20th century, the preparation of amorphous alloy and application have caused domestic and international material supplier author's very big interest.In recent years, along with the maturation gradually of ferromegnetism AMORPHOUS ALLOY, and the developing rapidly of space flight and aviation and transportation means lightness, people start attention to turn to the research work of high-strength low-density material, especially al based amorphous alloy and nano combined al based amorphous alloy, as emerging engineering materials, with its high strength, low density, the good excellent properties such as solidity to corrosion and wear resistance, arouse widespread concern, development in recent years is very rapid.
Prepare at present al based amorphous alloy and mainly adopt quench and mechanical alloying method.Quench is rapid solidification method, and that commonly uses now has three kinds: melt-quenching method, gas atomization, surface melting and reinforcement, wherein the most frequently used preparation method is melt-quenching method.The successful preparation of aluminium-based amorphous alloy, has broken through aluminium alloy and has been difficult to form amorphous obstacle, has realized variation prepared by aluminum alloy organization (amorphous, nanocrystalline, nanometer/amorphous multiphase structure etc.), has increased substantially the performance of aluminium alloy.Research shows, the non-crystaline amorphous metal that is 84～86% containing Al atomic percent, and its tensile strength intensity can reach 1000MPa, exceedes the order of magnitude of the ultra-high-strength aluminum alloy 700MPa in crystalline material, is 2～4 times of general conventional aluminum strength of alloy.
Weigh amorphous formation ability one of the most direct method be to measure the critical size (thickness) of non-crystaline amorphous metal.The critical size of non-crystaline amorphous metal is larger, also just means that the amorphous formation ability of this alloy is stronger.Research shows, by appropriate design, in non-crystaline amorphous metal system, composition constituent element is more, and the amorphous formation ability of non-crystaline amorphous metal is also just stronger to a certain extent.But because al based amorphous alloy system amorphous formation ability is undesirable, the ternary aluminium-based amorphous alloy thickness obtaining is at present only strip or the powdered samples of 30～100 μ m left and right mostly.In addition, amorphous alloy material belongs to metastable state, and in laser heating process, in the time reaching crystallization temperature, nuclear power overcomes potential barrier to be reset, and crystallization occurs, and is converted into crystalline material, and therefore weighing thermostability is also an important indicator of non-crystaline amorphous metal.Mostly use differential thermal analysis (DSC) to measure the glass transition temperature (T of non-crystaline amorphous metal for the evaluation of amorphous thermostability
g) and crystallization temperature (T
x), T
gand T
xhigher, non-crystaline amorphous metal thermally-stabilised also just better.But the crystallization temperature of most of al based amorphous alloy only has between 400～500K, low glass forming ability and thermostability have all limited the application of al based amorphous alloy greatly.Therefore improving Al-based Amorphous Alloys glass forming ability and thermostability, improve the critical size of al based amorphous alloy, is current problem demanding prompt solution.
Summary of the invention
The Al-Ni-Er that the object of the present invention is to provide a kind of reasonable mixture ratio of components, has a good amorphous formation ability is al based amorphous alloy material and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
A kind of Al-Ni-Er aluminum-based amorphous alloy material of the present invention, in described alloy material, mole atom content per-cent of each component is as follows:
Al：80-95%，
Ni：1-15%，
Er：3-18%。
The preparation method of a kind of Al-Ni-Er aluminum-based amorphous alloy material of the present invention, comprises the following steps: the first step: batching
After metal A l, Ni, Er are carried out to oxide skin disengaging and cleaning, prepare burden and mix after following atom content per-cent is scaled to mass percent, obtaining mother alloy raw material;
Al：80-95%，
Ni：1-15%，
Er：3-18%。
Second step: prepare mother alloy
Taking titanium as oxygen absorbent, taking argon gas, under the condition of protection gas, the mother alloy raw material that the first step is prepared adopts arc melting 3～6 times to ensure that alloying constituent is even, and then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting;
The 3rd step: get rid of band and make non-crystaline amorphous metal
The mother alloy that second step is made carry out oxide skin depart from process and clean after; use single roller quick solidification apparatus; mother alloy is positioned in the silica tube of lower end grinding out that is wound with induction heating wire coil; under the atmosphere of argon shield gas, heat remelting to 900-1400K; after mother alloy melts completely; the copper roller surface cool that is 8-20m/s to linear velocity by mother alloy melt jet, makes amorphous thin ribbon, and melt jet pressure is 0.01～0.03MPa.
The present invention has following beneficial effect:
(1) a kind of Al-Ni-Er aluminum-based amorphous alloy that the present invention proposes, transition element Ni in alloy and rare earth element er have more special outer electronic structure (d or f orbitals are not full of completely), form stable hybridized orbital with Al atom, improve the linkage force between alloy constituent element, in addition because the size of transition element Ni and rare earth element er and Al atom differs larger, improve the density of the random stacking provisions of alloy, increase the viscosity of alloy, the motion of constituent element atom while having suppressed to solidify, thereby improve amorphous conversion temp and the crystallization temperature of non-crystaline amorphous metal, thereby be convenient to form metastable non-crystaline amorphous metal.
(2) a kind of Al-Ni-Er aluminum-based amorphous alloy that the present invention proposes, due to adding of rare earth element er, significantly reduces the enthalpy of mixing between each element in alloy system, thereby has comprehensively improved the amorphous formation ability of alloy; Can be prepared thickness and reached the amorphous thin ribbon of 280 μ m by melt-quenching method, be 1～2 times of general aluminium-based amorphous alloy strip thickness.
(3) a kind of Al-Ni-Er aluminum-based amorphous alloy that the present invention proposes, composition cost is low, and preparation method is simple, can adopt technical pure metal A l, Ni and Er as raw material, and tensile strength is up to 1200MPa,
It is had broad application prospects at formation light aluminum alloy Material Field.
Brief description of the drawings
Fig. 1 the present invention is the Al that embodiment 1 obtains
85ni
8er
7amorphous alloy ribbon XRD figure spectrum analysis result figure;
Fig. 2 the present invention is the Al that embodiment 1 obtains
85ni
8er
7the DSC tracing analysis result figure of amorphous alloy ribbon;
The Al that Fig. 3 embodiment of the present invention 1 obtains
85ni
8er
7the TEM photo of amorphous alloy ribbon.
Embodiment
Below in conjunction with embodiment, content of the present invention is described further.
Embodiment 1:Al
85ni
8er
7the preparation of amorphous alloy ribbon
1) select commercially available pure Al, Ni, Er metal blocks to make raw material, first pure metal block surface being carried out to oxide skin disengaging and ultrasonic surface cleans, according to atom percentage content Al85%, Ni8%, Er7% prepares burden, and uses electronic balance to take quality and is respectively Al20.4049g, Ni4.7181g, Er10.4169g, mixes alloy block afterwards;
2) taking titanium as oxygen absorbent, taking argon gas under the condition of protection gas, by the 1st) the mother alloy raw material for preparing of step adopts arc melting 6 times, to ensure that alloying constituent is even, then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting;
3) by the 2nd) mother alloy that makes of step is through surperficial mechanical grinding with after cleaning; be placed in the silica tube that is wound with wire coil of lower end ground; heating remelting is to 1000K; after mother alloy melts completely; mother alloy melt jet is made to amorphous alloy ribbon to the copper roller surface cool of rotation; heat remelting and get rid of band process and carry out under argon gas atmosphere protection, copper roller linear velocity is 16m/s, and melt jet pressure is 0.03MPa.
The thickness of preparation is the Al of 280 μ m according to the method described above
85ni
8er
7band is through X ray diffracting spectrum (XRD), and transmission electron microscope (TEM) and differential thermal analyzer (DSC) are analyzed.For crystalline material, XRD figure spectrum signature is the spectral line with one group of sharp peak; And non-crystalline material, XRD figure spectrum is for having the spectral line of " steamed bun peak " feature.See through transmission electron microscope (TEM) and analyze knownly, in TEM image, there is no the contrast in crystalline material, and electron diffraction pattern be also that non-crystalline material is peculiar be made up of several concentric " halos ", the border of each halo is very fuzzy.Known by XRD and tem analysis, Al
85ni
8er
7band is amorphous alloy material; By dsc analysis, Al
85ni
8er
7band crystallization temperature T
x=510K, has good thermostability.By Resarch on A New Type, Al
85ni
8er
7the tensile strength of band, up to 1200MPa, has good mechanical property.
Embodiment 2:Al
85ni
9er
6amorphous alloy ribbon
Select commercially available pure Al, Ni, Er metal blocks to make raw material, first pure metal block surface being carried out to oxide skin disengaging and ultrasonic surface cleans, according to atom percentage content Al85%, Ni9%, Er6% prepares burden, and uses electronic balance to take quality and is respectively Al20.9840g, Ni4.8337g, Er9.1822g, mixes alloy block afterwards; Taking titanium as oxygen absorbent, taking argon gas as protecting under the condition of gas, the mother alloy raw material employing arc melting that the first step is prepared 6 times, to ensure that alloying constituent is even, then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting; The mother alloy that second step is made is through surperficial mechanical grinding with after cleaning, be placed in the silica tube that is wound with wire coil of lower end ground, heating remelting, to 950K left and right, after mother alloy melts completely, makes Al by mother alloy melt jet to the copper roller surface cool of rotation
85ni
9er
6amorphous alloy ribbon, heats remelting and gets rid of band process and carry out under argon gas atmosphere protection, and copper roller linear velocity is 20m/s, and melt jet pressure is 0.02MPa.The Al of preparation according to the method described above
85ni
9er
6band is non-crystalline material through XRD, TEM, DSC detection validation.
Embodiment 3:Al
86ni
9er
5amorphous alloy ribbon
Select commercially available pure Al, Ni, Er metal blocks to make raw material, first pure metal block surface being carried out to oxide skin disengaging and ultrasonic surface cleans, according to atom percentage content Al86%, Ni9%, Er5% prepares burden, and uses electronic balance to take quality and is respectively Al22.00391g, Ni5.0177g, Er7.9431g, mixes alloy block afterwards; Taking titanium as oxygen absorbent, taking argon gas as protecting under the condition of gas, the mother alloy raw material employing arc melting that the first step is prepared 6 times, to ensure that alloying constituent is even, then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting; The mother alloy that second step is made is through surperficial mechanical grinding with after cleaning, be placed in the silica tube that is wound with wire coil of lower end ground, heating remelting, to 1100K left and right, after mother alloy melts completely, makes Al by mother alloy melt jet to the copper roller surface cool of rotation
86ni
9er
5amorphous alloy ribbon, heats remelting and gets rid of band process and carry out under argon gas atmosphere protection, and copper roller linear velocity is 17m/s, and melt jet pressure is 0.02MPa.The Al of preparation according to the method described above
86ni
9er
5band is non-crystalline material through XRD, TEM, DSC detection validation.
Embodiment 4:Al
86ni
6er
8amorphous alloy ribbon
Select commercially available pure Al, Ni, Er metal blocks to make raw material, first pure metal block surface being carried out to oxide skin disengaging and ultrasonic surface cleans, according to atom percentage content Al86%, Ni6%, Er8% prepares burden, and uses electronic balance to take quality and is respectively Al20.2494g, Ni3.0735g, Er11.6769g, mixes alloy block afterwards; Taking titanium as oxygen absorbent, taking argon gas as protecting under the condition of gas, the mother alloy raw material employing arc melting that the first step is prepared 6 times, to ensure that alloying constituent is even, then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting; The mother alloy that second step is made is through surperficial mechanical grinding with after cleaning, be placed in the silica tube that is wound with wire coil of lower end ground, heating remelting, to 1150K left and right, after mother alloy melts completely, makes Al by mother alloy melt jet to the copper roller surface cool of rotation
86ni
6er
8amorphous alloy ribbon, heats remelting and gets rid of band process and carry out under argon gas atmosphere protection, and copper roller linear velocity is 15m/s, and melt jet pressure is 0.01MPa.The Al of preparation according to the method described above
86ni
6er
8band is non-crystalline material through XRD, TEM, DSC detection validation.
Embodiment 5:Al85Ni6Er9 amorphous alloy ribbon
Select commercially available pure Al, Ni, Er metal blocks to make raw material, first pure metal block surface being carried out to oxide skin disengaging and ultrasonic surface cleans, according to atom percentage content Al85%, Ni6%, Er9% prepares burden, and uses electronic balance to take quality and is respectively Al19.3376g, Ni2.9696g, Er12.6926g, mixes alloy block afterwards; Taking titanium as oxygen absorbent, taking argon gas as protecting under the condition of gas, the mother alloy raw material employing arc melting that the first step is prepared 6 times, to ensure that alloying constituent is even, then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting; The mother alloy that second step is made is through surperficial mechanical grinding with after cleaning; be placed in the silica tube that is wound with wire coil of lower end ground; heating remelting is to 1180K left and right; after mother alloy melts completely; mother alloy melt jet is made to Al85Ni6Er9 amorphous alloy ribbon to the copper roller surface cool of rotation; heat remelting and get rid of band process and carry out under argon gas atmosphere protection, copper roller linear velocity is 19m/s, and melt jet pressure is 0.03MPa.The Al85Ni6Er9 band of preparation is non-crystalline material through XRD, TEM, DSC detection validation according to the method described above.
Claims (2)
1. an Al-Ni-Er aluminum-based amorphous alloy material, is characterized in that: in described alloy material, mole atom content per-cent of each component is as follows:
Al：80-95%，
Ni：1-15%，
Er：3-18%。
2. a preparation method for Al-Ni-Er aluminum-based amorphous alloy material, is characterized in that: comprise the following steps:
The first step: batching
After metal A l, Ni, Er are carried out to oxide skin disengaging and cleaning, prepare burden and mix after following atom content per-cent is scaled to mass percent, obtaining mother alloy raw material;
Al：80-95%，
Ni：1-15%，
Er：3-18%；
Second step: prepare mother alloy
Taking titanium as oxygen absorbent, taking argon gas, under the condition of protection gas, the mother alloy raw material that the first step is prepared adopts arc melting 3～6 times to ensure that alloying constituent is even, and then naturally cooling under argon gas atmosphere protection, prepares the uniform mother alloy of melting;
The 3rd step: get rid of band and make non-crystaline amorphous metal
The mother alloy that second step is made carry out oxide skin depart from process and clean after; use single roller quick solidification apparatus; mother alloy is positioned in the silica tube of lower end grinding out that is wound with induction heating wire coil; under the atmosphere of argon shield gas, heat remelting to 900-1400K; after mother alloy melts completely; the copper roller surface cool that is 8-20m/s to linear velocity by mother alloy melt jet, makes amorphous thin ribbon, and melt jet pressure is 0.01～0.03MPa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388843A (en) * | 2014-12-23 | 2015-03-04 | 内蒙古科技大学 | Al-MR-TM-TE aluminum-based amorphous alloy and preparation method thereof |
| CN109399765A (en) * | 2017-08-16 | 2019-03-01 | 南京理工大学 | Utilize the method for amorphous alloy electrochemical degradation azo dyes |
| CN111500908A (en) * | 2020-06-05 | 2020-08-07 | 威海万丰镁业科技发展有限公司 | Ultrahigh-strength ultrafine-grained TiB2Reinforced Al-Zn-Mg-Cu composite material and preparation |
| CN111575629A (en) * | 2020-05-18 | 2020-08-25 | 神华准能资源综合开发有限公司 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
| CN114686785A (en) * | 2022-03-03 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | High-thermal stability aluminum-based metal glass and preparation method thereof |
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| CN1431333A (en) * | 2003-01-20 | 2003-07-23 | 山东大学 | Aluminium base amorphous alloy and its preparing method |
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| CN1431333A (en) * | 2003-01-20 | 2003-07-23 | 山东大学 | Aluminium base amorphous alloy and its preparing method |
Non-Patent Citations (1)
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| 王丹等: "Er对Al-Ni-Er-Zr非晶合金动力学特性的影响", 《中国稀土学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388843A (en) * | 2014-12-23 | 2015-03-04 | 内蒙古科技大学 | Al-MR-TM-TE aluminum-based amorphous alloy and preparation method thereof |
| CN109399765A (en) * | 2017-08-16 | 2019-03-01 | 南京理工大学 | Utilize the method for amorphous alloy electrochemical degradation azo dyes |
| CN111575629A (en) * | 2020-05-18 | 2020-08-25 | 神华准能资源综合开发有限公司 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
| CN111575629B (en) * | 2020-05-18 | 2022-07-26 | 神华准能资源综合开发有限公司 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
| CN111500908A (en) * | 2020-06-05 | 2020-08-07 | 威海万丰镁业科技发展有限公司 | Ultrahigh-strength ultrafine-grained TiB2Reinforced Al-Zn-Mg-Cu composite material and preparation |
| CN114686785A (en) * | 2022-03-03 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | High-thermal stability aluminum-based metal glass and preparation method thereof |
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