CN104532072A - Al-ETM-LTM-TE aluminum-based amorphous alloy and preparation method thereof - Google Patents
Al-ETM-LTM-TE aluminum-based amorphous alloy and preparation method thereof Download PDFInfo
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- CN104532072A CN104532072A CN201410808402.4A CN201410808402A CN104532072A CN 104532072 A CN104532072 A CN 104532072A CN 201410808402 A CN201410808402 A CN 201410808402A CN 104532072 A CN104532072 A CN 104532072A
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- etm
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Abstract
The invention discloses an Al-ETM-LTM-TE aluminum-based amorphous alloy and a preparation method thereof. The Al-ETM-LTM-TE aluminum-based amorphous alloy comprises the following components in atomic percentage: 85-94% of Al, 0-8% of ETM, 0-8% of LTM and 0-1% of TE, wherein ETM is Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W; LTM is Mn, Fe, Co, Ni, Cu and Zn; and TE refers to trace elements, such as B, Si, Ga, Ge, As, Se, Sb or Te and the like. The preparation method of the alloy comprises the following steps of proportioning the nominal components, repeatedly melting by vacuum induction for 3-4 times to prepare a master alloy with uniform components; carrying out melt-spinning under the protection of high-purity Ar to prepare amorphous strips under the conditions that the linear speed of a copper roller is 35-50 m/s, the injection pressure of the melt is 0.1-0.3 MPa and the degree of vacuum is 2-10<-3> Pa. The Al-ETM-LTM-TE aluminum-based amorphous alloy has the advantages of reasonable component ration, strong amorphous forming capability and high thermal stability, and the preparation method is simple and is suitable for industrial production.
Description
Technical field
The invention belongs to non-crystalline material preparation field, be specifically related to a kind of Al-ETM-LTM-TE polybasic aluminum Alloy And Preparation Method.
Background technology
Nineteen sixty-five, people's first passage melt pole cold process such as Predecki and Giessen have prepared aluminium-based amorphous alloy Al-Si.By 1981, the people such as Inoue successfully prepared non-crystal structure aluminium alloy system Al-Fe-B and Al-Co-B completely, but the amorphous of this composition is not paid attention to because be highly brittle.Non-crystaline amorphous metal series of having got back afterwards Al-Fe-Si, Al-Fe-Si, but still very crisp, so it is believed that fragility is a kind of feature of amorphous aluminum alloy.But Inoue in 1987 obtains the amorphous with excellent toughness in Al-Ni-Si and Al-Ni-Ge alloy system, then in Al-ETM-LTM series ternary alloy system, prepare the amorphous aluminum alloy system with excellent toughness.
Amorphous aluminum alloy, because having the strong and excellent performance such as anti-corrosion of high ratio, will play a significant role in space flight, aviation, national defence, transport, dual-use equipment etc.In the last few years, amorphous aluminum alloy caused the common concern of investigation of materials person as a kind of novel non-crystaline amorphous metal.The main restriction of current restriction al based amorphous alloy application is that amorphous alloy forming ability is more weak, not deep enough and thorough to its theoretical investigation, therefore, still cannot prepare the amorphous aluminum alloy of large-size, the exploitation of the amorphous aluminum alloy that toughness is good are few especially, and production cost is high.
Summary of the invention
The technical issues that need to address of the present invention are just the defect overcoming prior art, al based amorphous alloy material and the preparation method provide that a kind of component is reasonable, technique is simple, being convenient to suitability for industrialized production.
For reaching above-mentioned purpose, a kind of Al-ETM-LTM-TE al based amorphous alloy of the present invention, the atomic percent of its each component is: Al 85.0-94.0%, ETM 0.0-8.0%, LTM 0.0-8.0%, RE 0-1.0%, wherein said ETM is Ti, V, Cr, Zr, Nb, Mo, Hf, Ta or W, described LTM is Mn, Fe, Co, Ni, Cu or Zn, and TE is trace element, is B or Si.
Wherein said al based amorphous alloy tissue has quench solidification tissue, and its solidified structure is the amorphous structure of complete and homogeneous.
Wherein said al based amorphous alloy amorphous ribbon thickness is 30-50um, and wide is 3-5mm, and long is 0.1-0.3m.
Wherein said al based amorphous alloy comprises Al
88ti
8fe, Al
88cr
8co
4, Al
88v
8ni
4and Al
88nb
8cu
4.
Prepare a method for described Al-ETM-LTM-TE al based amorphous alloy, comprise the following steps:
(1) metal simple-substance of each respective quality, is taken by the final each described atomic percent of alloy;
(2), in vacuum induction melting furnace, put into described each metal, fusion process carries out 5-9 time repeatedly, ensures that the fusing of alloy is even, under Ar gas shielded, is cooled to master alloy ingot;
(3), by described master alloy ingot put into silica tube, under Ar gas shielded, get rid of band with carrying out sample after high-frequency induction melting, the linear velocity of copper roller is 35-50m/s, and the injection temperature of melt is 1273-1473 DEG C, and spraying pressure is 0.1-0.3MPa.
Wherein said each raw metal purity is respectively Al >=99.99%, ETM >=99.99%, LTM >=99.99%, TE >=99.99%.
First carry out mechanical grinding surface before wherein said each metal adds described vacuum induction melting furnace and adopt anhydrous normal butyl alcohol, acetone, deionized water alternately air-dry stand-by after cleaning 3 times under ultrasound condition successively.
The stack order of wherein said each metal in described vacuum induction melting furnace is that the metal that density is large puts surface layer, and during fusing, melt can form convection current.
Wherein said master alloy ingot first carries out mechanical grinding and removes the oxide skin on its surface and repeatedly adopt anhydrous normal butyl alcohol, acetone and deionized water and air-dry stand-by after carry out cleaning 3 times under ultrasound condition before melting.
The invention difference from existing technology is that the present invention achieves following technique effect:
(1), in the present invention, because ETM, LTM and TE are additive, can the amorphous formation ability of reinforced aluminum, make certain alloy can form complete amorphous structure;
(2), the present invention adopts single roller to get rid of band technology to prepare high-purity continuous band al based amorphous alloy, speed of cooling reaches al based amorphous alloy and is formed, and utilize this technology can carry out the continuous seepage of a large amount of band, method is simple, simple operation, is applicable to suitability for industrialized production;
(3), the al based amorphous alloy toughness of material that obtains of the present invention is good, shows excellent corrosion resisting property, is applicable to the substrate coating of the facilities such as aerospacecraft, aircraft, guided missile, boats and ships, dual-use equipment.
Accompanying drawing explanation
Fig. 1 is al based amorphous alloy Al provided by the invention
88ti
7.9fe
4b
0.1, Al
88cr
8co
4, Al
88v
8ni
4and Al
88nb
8cu
4x-ray diffractogram;
Fig. 2,3,4 and 5 are respectively amorphous Sample A l provided by the invention
88ti
7.9fe
4b
0.1, Al
88cr
8co
4, Al
88v
8ni
4and Al
88nb
8cu
4selected area electron diffraction figure and bright field image;
Fig. 6 is al based amorphous alloy Al provided by the invention
88ti
7.9fe
4b
0.1, Al
88cr
8co
4, Al
88v
8ni
4and Al
88nb
8cu
4dSC tracing analysis result figure, temperature rise rate is 20K/min.
Embodiment
Below in conjunction with embodiment, to above-mentioned being described in more detail with other technical characteristic and advantage of the present invention.
Embodiments of the invention adopt pure metal block materials, and its metal simple-substance atomic percent is in the alloy Al 85-94%, ETM 0-8%, and LTM 0-8%, TE 0-1% is raw material, prepares the Al-ETM-LTM system polybasic aluminum base noncrystal alloy of Multiple components.The raw material that the present invention adopts is commercially available high-purity reguline metal, is respectively Al >=99.99%, ETM >=99.99%, LTM >=99.99%, TE >=99.99% according to its purity of massfraction.
Embodiment 1
The present embodiment relates to a kind of Al
88ti
7.9fe
4b
0.1amorphous alloy and preparation method thereof.
(1), according to alloying constituent Al
88ti
7.9fe
4b
0.1atomic percentage each metal simple-substance raw materials quality that converts takes raw material than Al:79.76wt.%, Ti:12.7wt.%, Fe:7.5wt.%, B:0.04wt.%, adds its component alloys ensure nominal alloy proportion according to alloy melting scaling loss experience.During batching, pure metal is through mechanical grinding surface, and repeatedly adopts anhydrous normal butyl alcohol, acetone, deionized water alternately air-dry stand-by after cleaning 3 times under ultrasound condition successively;
(2), in vacuum induction melting furnace put into each pure metal (metal that density is large puts face, and during fusing, melt can form convection current) according to density difference, melting is carried out 5-7 time repeatedly, ensures that the fusing of alloy is even;
(3), described alloy block first carry out before melting mechanical grinding remove its surface oxide skin and and repeatedly adopt anhydrous normal butyl alcohol, acetone, deionized water alternately air-dry stand-by after cleaning 3 times under ultrasound condition successively;
(4), under argon shield, mother alloy is put into silica tube high-frequency induction melting and is carried out sample and get rid of band, and the linear velocity of copper roller is 35-50m/s, and the injection temperature of melt is 1273-1473 DEG C, and spraying pressure is 0.1-0.3MPa.
The composition obtained by above-mentioned technique is Al
88ti
8fe
4b
0.1through X-ray diffraction and transmission electron microscope photo, band (thickness is 40um, and wide is 4mm, and length is 0.2 meter), shows that prepared band is complete amorphous structure; Band of the present invention is without obvious glass transformation temperature T to utilize differential scanning calorimeter analytical results to show
g, beginning crystallization temperature is 577.6K.
Embodiment 2
The present embodiment relates to a kind of Al
88cr
8co
4amorphous alloy and preparation method thereof.
According to alloying constituent Al
88cr
8co
4atomic percentage each metal simple-substance raw materials quality that converts takes raw material than Al:78.46wt.%, Cr:13.74wt.%, Co:7.8wt.%, and adds its component alloys according to alloy melting scaling loss experience and ensure nominal alloy proportion.Then preparing composition according to the method for embodiment 1 and step is Al
88cr
8co
4through X-ray diffraction and transmission electron microscope photo, band (thickness is 30um, and wide is 3mm, and length is 0.1 meter) shows that prepared band is complete amorphous structure; Band of the present invention is without obvious glass transformation temperature T to utilize differential scanning calorimeter analytical results to show
g, beginning crystallization temperature is 560.4K.
Embodiment 3
The present embodiment relates to a kind of Al
88v
8ni
4amorphous alloy and preparation method thereof.
According to alloying constituent Al
88v
8ni
4atomic percentage converts each metal simple-substance raw materials quality Al:78.71wt.%, and V:13.51wt.%, Ni:7.78wt.% take raw material, and adds its component alloys according to alloy melting scaling loss experience and ensure nominal alloy proportion.Then preparing composition according to the method for embodiment 1 and step is Al
88v
8ni
4band (thickness is 50um, 5 wide be mm, length is 0.3 meter) show that prepared band is complete amorphous structure through X-ray diffraction and transmission electron microscope photo; Band of the present invention is without obvious glass transformation temperature T to utilize differential scanning calorimeter analytical results to show
g, beginning crystallization temperature is 529.9K.
Embodiment 4
The present embodiment relates to a kind of Al
88nb
8cu
4amorphous alloy and preparation method thereof.
According to alloying constituent Al
88nb
8cu
4atomic percentage each metal simple-substance raw materials quality that converts takes raw material than Al:70.4wt.%, Nb:22.0wt.%, Cu:7.6wt.%, and adds its component alloys according to alloy melting scaling loss experience and ensure nominal alloy proportion.Then preparing composition according to the method for embodiment 1 and step is Al
88nb
8cu
4through X-ray diffraction and transmission electron microscope photo, band (thickness is 30um, and wide is 3mm, and length is 0.2 meter) shows that prepared band is complete amorphous structure; Band of the present invention is without obvious glass transformation temperature T to utilize differential scanning calorimeter analytical results to show
g, beginning crystallization temperature is 492.6K.
The amorphous band that above embodiment obtains is through doubling 180 repeatedly
0all do not rupture, spontaneous corrosion current density is at 1-5X10
-7a/cm
2scope.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (9)
1. an Al-ETM-LTM-TE al based amorphous alloy, it is characterized in that the atomic percent of its each component is: Al 85.0-94.0%, ETM 0.0-8.0%, LTM 0.0-8.0%, RE 0-1.0%, wherein said ETM are Ti, V, Cr, Zr, Nb, Mo, Hf, Ta or W, and described LTM is Mn, Fe, Co, Ni, Cu or Zn, TE is trace element, is B or Si.
2. Al-ETM-LTM-TE al based amorphous alloy according to claim 1, is characterized in that: described al based amorphous alloy tissue has quench solidification tissue, and its solidified structure is the amorphous structure of complete and homogeneous.
3. Al-ETM-LTM-TE al based amorphous alloy as claimed in claim 1, it is characterized in that: described al based amorphous alloy amorphous ribbon thickness is 30-50um, wide is 3-5mm, and long is 0.1-0.3m.
4. Al-ETM-LTM-TE al based amorphous alloy according to claim 1, is characterized in that: described al based amorphous alloy comprises Al
88ti
8fe, Al
88cr
8co
4, Al
88v
8ni
4and Al
88nb
8cu
4.
5. prepare a method for Al-ETM-LTM-TE al based amorphous alloy according to any one of claim 1-4, it is characterized in that comprising the following steps:
(1) metal simple-substance of each respective quality, is taken by the final each described atomic percent of alloy;
(2), in vacuum induction melting furnace, put into described each metal, fusion process carries out 5-9 time repeatedly, ensures that the fusing of alloy is even, under Ar gas shielded, is cooled to master alloy ingot;
(3), by described master alloy ingot put into silica tube, under Ar gas shielded, get rid of band with carrying out sample after high-frequency induction melting, the linear velocity of copper roller is 35-50m/s, and the injection temperature of melt is 1273-1473 DEG C, and spraying pressure is 0.1-0.3MPa.
6. the preparation method of Al-ETM-LTM-TE al based amorphous alloy according to claim 5, is characterized in that: described each raw metal purity is respectively Al >=99.99%, ETM >=99.99%, LTM >=99.99%, TE >=99.99%.
7. the preparation method of Al-ETM-LTM-TE al based amorphous alloy according to claim 5, is characterized in that: first carry out mechanical grinding surface before described each metal adds described vacuum induction melting furnace and adopt anhydrous normal butyl alcohol, acetone, deionized water alternately air-dry stand-by after cleaning 3 times under ultrasound condition successively.
8. the preparation method of Al-ETM-LTM-TE al based amorphous alloy according to claim 5, is characterized in that: the stack order of described each metal in described vacuum induction melting furnace is that the metal that density is large puts surface layer, and during fusing, melt can form convection current.
9. the preparation method of Al-ETM-LTM-TE al based amorphous alloy according to claim 5, is characterized in that: described master alloy ingot first carries out mechanical grinding and removes the oxide skin on its surface and air-dry stand-by after repeatedly adopting anhydrous normal butyl alcohol, acetone and deionized water to carry out cleaning 3 times successively under ultrasound condition before melting.
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CN104862540A (en) * | 2015-05-08 | 2015-08-26 | 苏州立瓷电子技术有限公司 | High-strength and corrosion-resistance aluminum-titanium alloy material for electrician and preparation method thereof |
CN105018819A (en) * | 2015-08-05 | 2015-11-04 | 启东市佳宝金属制品有限公司 | Light alloy |
CN105441727A (en) * | 2015-11-20 | 2016-03-30 | 太仓新浏精密五金有限公司 | High-temperature-resistant aluminum alloy hardware part |
CN105538829A (en) * | 2015-12-15 | 2016-05-04 | 常熟市良益金属材料有限公司 | Corrosion resistant alloy material |
CN106835001A (en) * | 2017-01-20 | 2017-06-13 | 中国人民解放军装甲兵工程学院 | A kind of powder cored filament material that Al Ni Zr Cr amorphous coatings are prepared for HVAS |
CN107236878A (en) * | 2017-06-23 | 2017-10-10 | 巢湖市兰天大诚门窗幕墙有限公司 | High-strength aluminum alloy composite gate |
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CN110819928A (en) * | 2019-11-01 | 2020-02-21 | 河海大学 | Powder core wire for preparing Al-Mo-Ni amorphous coating resistant to marine environment corrosion |
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RU2725494C1 (en) * | 2019-09-18 | 2020-07-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Sintered ligature from powder materials for alloying aluminum alloys |
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CN104862540A (en) * | 2015-05-08 | 2015-08-26 | 苏州立瓷电子技术有限公司 | High-strength and corrosion-resistance aluminum-titanium alloy material for electrician and preparation method thereof |
CN105018819A (en) * | 2015-08-05 | 2015-11-04 | 启东市佳宝金属制品有限公司 | Light alloy |
CN105441727A (en) * | 2015-11-20 | 2016-03-30 | 太仓新浏精密五金有限公司 | High-temperature-resistant aluminum alloy hardware part |
CN105538829A (en) * | 2015-12-15 | 2016-05-04 | 常熟市良益金属材料有限公司 | Corrosion resistant alloy material |
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CN106835001B (en) * | 2017-01-20 | 2019-05-21 | 中国人民解放军装甲兵工程学院 | A kind of powder cored filament material preparing Al-Ni-Zr-Cr amorphous coating for high-speed arc spraying technology |
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CN108588587A (en) * | 2018-04-28 | 2018-09-28 | 内蒙古科技大学 | A kind of Al-Ce-ETM systems al based amorphous alloy and preparation method thereof |
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RU2725494C1 (en) * | 2019-09-18 | 2020-07-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Sintered ligature from powder materials for alloying aluminum alloys |
CN110819928A (en) * | 2019-11-01 | 2020-02-21 | 河海大学 | Powder core wire for preparing Al-Mo-Ni amorphous coating resistant to marine environment corrosion |
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 |
CN113981335B (en) * | 2021-10-29 | 2022-09-23 | 盘星新型合金材料(常州)有限公司 | Microelement modified Be-free block amorphous alloy and preparation method and application thereof |
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