CN101067190A - High ductile malleable Pa-Cu-Si block amorphous alloy and producing method thereof - Google Patents
High ductile malleable Pa-Cu-Si block amorphous alloy and producing method thereof Download PDFInfo
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- CN101067190A CN101067190A CN 200710118933 CN200710118933A CN101067190A CN 101067190 A CN101067190 A CN 101067190A CN 200710118933 CN200710118933 CN 200710118933 CN 200710118933 A CN200710118933 A CN 200710118933A CN 101067190 A CN101067190 A CN 101067190A
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Abstract
The present invention relates to amorphous metal material technology, and is especially one kind of lumpy amorphous Pd-Cu-Si alloy with high ductility and its preparation process. The lumpy amorphous Pd-Cu-Si alloy has the chemical composition of Pd 75.5-79 at.%, Cu 5-8 at.%, and Si 15-17 at.%. Its preparation process includes glass coated purifying, air cooling and water quenching. The lumpy amorphous Pd-Cu-Si alloy has high plastic deformation capacity, high yield strength and excellent anticorrosive performance, and possesses excellent application foreground in different fields.
Description
Technical field
The invention belongs to the amorphous metallic material technical field, particularly block amorphous alloy.This material be a kind ofly have high strength, height prolongs the amorphous alloy material of toughness and fine corrosion resisting property.
Background technology
Non-crystaline amorphous metal (comprising block amorphous alloy) is meant that atomic arrangement does not exist the such long-range order of crystalline material periodically but be the alloy material of unordered close heap arrangement architecture, therefore non-crystaline amorphous metal does not have the defectives such as crystal boundary, dislocation in the crystalline material, the anisotropy that does not simultaneously also have most crystalline material and had, and be the isotropy feature.This constitutional features makes amorphous alloy material have the mechanics and the functional performance of a lot of excellences.But non-crystaline amorphous metal need obtain under condition of fast cooling, most of alloy materials all need be about in speed of cooling～and 10
6Could obtain amorphous structure under the condition of K/s, therefore most non-crystaline amorphous metals can only be prepared into strip (20-50 μ m is thick), film and fine powder, make the application of amorphous alloy material be subjected to very big restriction.Therefore to have bigger amorphous formation ability, can prepare large-sized amorphous alloys be the target that the researchist pursues always in exploitation.
In nearest more than 10 year, the exploitation size has obtained progress at full speed greater than the research of the block amorphous alloy of 1mm, at a plurality of block amorphous alloys, as ZrTiCuNiBe system, ZrAlCuNi system, FeCoCrMoCBY system, PdNiCuP system, CuZrAlAg system or the like.Size the maximum has reached 72mm in the Pd40Cu30Ni10P20 block amorphous alloy of developing at present.Non-crystaline amorphous metal has very high strength, but amount of plastic deformation is usually less, and compress variation is general all less than 1～2%.This is restricted the application of amorphous alloy material.Therefore it is very great to develop the novel block amorphous alloy or the exploration raising non-crystaline amorphous metal ductile method meaning that have than the large plastometric set ability.This will increase the deformation processing forming ability of this alloy material and the security of application greatly.Recently, exploitation has in the research of non-crystaline amorphous metal of certain plastic deformation ability and has obtained progress, has prepared the block amorphous alloy that has than the large plastometric set ability in Cu-Zr alloy system, Pd-Si alloy system, Pt-Ni-Cu-P alloy system.But according to document and patent retrieval, so far, Shang Weijian openly reports to exist to have than the large plastometric set ability and (refers generally to compress ductility be better than～5-10%) Pd-Cu-Si block amorphous alloy.
Summary of the invention
The objective of the invention is to propose a kind of Pd-Cu-Si block amorphous alloy material and its preparation method with high strength and high-ductility deformability.
Non-crystaline amorphous metal proposed by the invention is characterised in that, it is characterized in that, chemical ingredients consists of: Pd:75.5-79at%; Cu:5-8at%; Si:15-17at%.
The preparation method of high ductile malleable Pa-Cu-Si block amorphous alloy is characterized in that, according to following alloy proportion: Pd:75.5-79at%; Cu:5-8at%; Si:15-17at% carries out following steps:
1) mother alloy melting: adopt vacuum alloy melting method to be smelted into master alloy ingot by high-purity Pd, Ni, Si and the P raw material of alloying constituent proportioning;
2) glass is coated medium and be fused into liquid being higher than under the condition of melting temperature;
3) under vacuum condition, glass coated medium and be higher than under the above condition of its fusing point 200 degree and purify more than 2 hours, and molten glass coating medium liquid to reach state pure, that do not have bubble;
4) under vacuum condition alloy pig being added melten glass coats in the medium, temperature is increased to the temperature condition insulation purification down that is higher than more than alloy melting point 200 degree, in purification process, repeatedly alloy melt is cooled off until solidifying, and be warming up to the purification temperature once more, if alloy heats up when melting after solidifying once more, do not produce bubble, then can after purifying about 1 hour, continuation finish purification process;
5) the alloy melt cooling that is in molten state after will purifying obtains the Pd-Cu-Si block amorphous alloy.
The described the 2nd) step coats medium with glass and is fused into liquid under the condition of melting temperature and carries out in crucible at silica tube or alloy melting being higher than.
The described the 4th) total purification time of described alloy of step is 2～10 hours.
The described the 5th) described method of cooling of step be be in after purifying the alloy melt of molten state and coating medium on every side together slow cooling to room temperature.
The described the 5th) described method of cooling of step be be in after purifying the alloy melt of molten state and coating medium on every side together shrend to room temperature.
The described the 5th) described method of cooling of step is that the alloy melt that will be in molten state after will purifying solidifies earlier, then the alloy of purifying is melted the back rapid solidification once more or is cast into metal pattern under vacuum condition.
It is that dry glass coats medium that described glass coats medium.
Evidence: this material has the yield strength of the compressive plastic deformation ability of about 40-70%, about 1500MPa, splendid corrosion resisting property.Owing to have above-mentioned special excellent properties, make this alloy good prospects for application be arranged in various fields.
Description of drawings
Fig. 1 is the product dimensioned drawing of embodiment 1;
Fig. 2 is the product P d of embodiment 1
78.5Cu
5.5Si
16The stress under compression of block amorphous alloy-strain curve figure.
Embodiment
The preparation technology of this alloy: adopt glass to coat medium (as B
2O
3The glass coating) purifying technique purification alloy adopts air cooling, shrend or other fast cooling method to prepare amorphous alloy material then.
This alloy organizing constitutional features: amorphous structure.Its preparation process is as follows:
1) mother alloy melting: adopt vacuum alloy melting method to be smelted into master alloy ingot by high-purity Pd, Cu and the Si raw material (greater than 99.5%) of alloying constituent proportioning.
2) embodiment:
(1) adopting silica tube or alloy melting crucible is the alloy melting container, dry glass is coated medium be fused into liquid being higher than under the condition of melting temperature.
(2) under vacuum condition, glass coated medium and be higher than under the above condition of about 200 degree of its fusing point and purify more than 2 hours, make the state that molten glass coating medium liquid is pure, do not have bubble.
(3) under vacuum condition, alloy pig is added melten glass and coat in the medium, then temperature is increased to the temperature condition insulation purification down that is approximately higher than alloy melting point 200 degree.And in purification process, for several times with the alloy melt cooling until solidifying, and then be warming up to the purification temperature, after purifying about 2-4 hour, if alloy heats up when melting after solidifying once more, do not produce bubble, then can after purifying about 1 hour, continuation finish purification process.
(4) can adopt the Pd-Cu-Si block amorphous alloy of following three kinds of method preparation sizes greater than 4-8mm:
1〉be in after will purifying the alloy melt of molten state and coating medium on every side together slow cooling to room temperature.
2〉be in after will purifying the alloy melt of molten state and coating medium on every side together shrend to room temperature.
3〉alloy melt that is in molten state after will purifying solidifies earlier, then with the alloy of purifying fusing back rapid solidification (as shrend) or be cast into metal pattern once more under vacuum condition.
Adopt above-mentioned three kinds of methods to prepare bulk amorphous alloys
Embodiment 1: high ductility 78.5at%Pd-5.5at%Cu-16at%Si block amorphous alloy Pd
78.5Cu
5.5Si
16
(1) adopting silica tube is the alloy melting container, and proportionately mother alloy is prepared in the alloy raw material fusing of assignment system under the argon shield condition.
(2) with anhydrous B
2O
3Coat the medium silica tube of packing into, under 800 degree conditions, be fused into liquid.Under vacuum condition, will coat medium then and under about 900 degree conditions, purify more than 2 hours, and make the coating medium reach pure, no bubble state.
(3) under vacuum condition alloy pig is added fusion and coat in the medium, 1100 degree were being purified about 5-6 hour.Cooling is solidified approximately more than 5 times in purification process, and purifies when not having bubble to occur when melting once more again and gets final product in 1 hour.
(4) will be in the alloy melt of molten state and coating medium on every side together slow cooling to room temperature, but preparation size is greater than the block amorphous alloy of 5mm; To be in the alloy melt of molten state and coating medium on every side together shrend to room temperature, but preparation size is greater than the block amorphous alloy of 5mm or φ 4mm amorphous garden rod (see figure 1); Also the alloy after purifying can be melted back shrend cooling or is cast into the amorphous garden rod that obtains in the copper mold more than about φ 4mm under the vacuum condition once more.
(5) Zhi Bei block amorphous alloy is built the compression ductility that has up to 40%, and the engineering yield strength is higher than 1500MPa.Fig. 2 is Pd
78.5Cu
5.5Si
16The stress under compression of block amorphous alloy-strain curve figure.
Embodiment 2: high ductility 77.5at%Pd-6.0at%Cu-16.5at%Si block amorphous alloy Pd
77.5Cu
6Si
16.5
(1) adopting silica tube is the alloy melting container, and proportionately mother alloy is prepared in the alloy raw material fusing of assignment system under the argon shield condition.
(2) with anhydrous B
2O
3Coat the medium silica tube of packing into, under 900 degree conditions, be fused into liquid.Under vacuum condition, will coat medium then and under about 1000 degree conditions, purify more than 2 hours, and make the coating medium reach pure, no bubble state.
(3) under vacuum condition alloy pig is added fusion and coat in the medium, 1150 degree were being purified about 8 hours.Cooling is solidified about 5 times in purification process, and does not have bubble to occur when melting once more.
(4) will be in the alloy melt of molten state and coating medium on every side together slow cooling to room temperature, but preparation size is greater than the block amorphous alloy of 8mm; To be in the alloy melt of molten state and coating medium on every side together shrend to room temperature, but preparation size is greater than block amorphous alloy or the φ 4mm amorphous garden rod of 5mm; Also the alloy after purifying can be melted back shrend cooling or is cast into the amorphous garden rod that obtains in the copper mold more than about φ 4mm under the vacuum condition once more.
(5) Zhi Bei block amorphous alloy has and is higher than 60% compression ductility, and yield strength is higher than 1600MPa.
Embodiment 3: high ductility 76.5at%Pd-7.0at%Cu-16.5at%Si block amorphous alloy Pd
76.5Cu
7Si
16.5
(1) adopting silica tube is the alloy melting container, and proportionately mother alloy is prepared in the alloy raw material fusing of assignment system under the argon shield condition.
(2) with anhydrous B
2O
3Coat the medium silica tube of packing into, under 900 degree conditions, be fused into liquid.Under vacuum condition, will coat medium then and under about 1000 degree conditions, purify more than 2 hours, and make the coating medium reach pure, no bubble state.
(3) under vacuum condition alloy pig is added fusion and coat in the medium, 1150 degree were being purified about 8 hours.Cooling is solidified about 5 times in purification process, and does not have bubble to occur when melting once more.
(4) will be in the alloy melt of molten state and coating medium on every side together slow cooling to room temperature, but preparation size is greater than the block amorphous alloy of 5mm; To be in the alloy melt of molten state and coating medium on every side together shrend to room temperature, but preparation size is greater than block amorphous alloy or the φ 3mm amorphous garden rod of 5mm; Also the alloy after purifying can be melted back shrend cooling or is cast into the amorphous garden rod that obtains in the copper mold more than about φ 4mm under the vacuum condition once more.
(5) Zhi Bei block amorphous alloy is built to have and is higher than 40% compression ductility, and yield strength is higher than 1600MPa.
Embodiment 4: high ductility 76.0at%Pd-7.0at%Cu-17.0at%Si block amorphous alloy Pd
76Cu
7Si
17
(1) adopting silica tube is the alloy melting container, and proportionately mother alloy is prepared in the alloy raw material fusing of assignment system under the argon shield condition.
(2) with anhydrous B
2O
3Coat the medium silica tube of packing into, under 900 degree conditions, be fused into liquid.Under vacuum condition, will coat medium then and under about 1050 degree conditions, purify more than 2 hours, and make the coating medium reach pure, no bubble state.
(3) under vacuum condition alloy pig is added fusion and coat in the medium, 1150 degree were being purified about 8 hours.Cooling is solidified about 5 times in purification process, and does not have bubble to occur when melting once more.
(4) will be in the alloy melt of molten state and coating medium on every side together slow cooling to room temperature, but preparation size is greater than the block amorphous alloy of 5mm; To be in the alloy melt of molten state and coating medium on every side together shrend to room temperature, but preparation size is greater than block amorphous alloy or the φ 3mm amorphous garden rod of 5mm; Also the alloy after purifying can be melted back shrend cooling or is cast into the amorphous garden rod that obtains in the copper mold more than about φ 4mm under the vacuum condition once more.
(5) Zhi Bei block amorphous alloy is built to have and is higher than 30% compression ductility, and yield strength is higher than 1600MPa.
Embodiment 5: high ductility 79.0at%Pd-5.0at%Cu-16.0at%Si block amorphous alloy Pd
79Cu
5Si
16
(1) adopting silica tube is the alloy melting container, and proportionately mother alloy is prepared in the alloy raw material fusing of assignment system under the argon shield condition.
(2) with anhydrous B
2O
3Coat the medium silica tube of packing into, under 800 degree conditions, be fused into liquid.Under vacuum condition, will coat medium then and under about 1000 degree conditions, purify more than 2 hours, and make the coating medium reach pure, no bubble state.
(3) under vacuum condition alloy pig is added fusion and coat in the medium, 1100 degree were being purified about 8 hours.Cooling is solidified about 5 times in purification process, and does not have bubble to occur when melting once more.
(4) will be in the alloy melt of molten state and coating medium on every side together slow cooling to room temperature, but preparation size is greater than the block amorphous alloy of 5mm; To be in the alloy melt of molten state and coating medium on every side together shrend to room temperature, but preparation size is greater than block amorphous alloy or the φ 3mm amorphous garden rod of 5mm; Also the alloy after purifying can be melted back shrend cooling or is cast into the amorphous garden rod that obtains in the copper mold more than about φ 4mm under the vacuum condition once more.
(5) Zhi Bei block amorphous alloy is built to have and is higher than 30% compression ductility, and yield strength is higher than 1500MPa.
Claims (8)
1, a kind of high ductile malleable Pa-Cu-Si block amorphous alloy is characterized in that, chemical ingredients consists of: Pd:75.5-79at%; Cu:5-8at%; Si:15-17at%.
2, a kind of preparation method of high ductile malleable Pa-Cu-Si block amorphous alloy is characterized in that, according to following alloy proportion: Pd:75.5-79at%; Cu:5-8at%; Si:15-17at% carries out following steps:
1) mother alloy melting: adopt vacuum alloy melting method to be smelted into master alloy ingot by high-purity Pd, Ni, Si and the P raw material of alloying constituent proportioning;
2) glass is coated medium and be fused into liquid being higher than under the condition of melting temperature;
3) under vacuum condition, glass coated medium and be higher than under the above condition of its fusing point 200 degree and purify more than 2 hours, and molten glass coating medium liquid to reach state pure, that do not have bubble;
4) under vacuum condition alloy pig being added melten glass coats in the medium, temperature is increased to the temperature condition insulation purification down that is higher than more than alloy melting point 200 degree, in purification process, repeatedly alloy melt is cooled off until solidifying, and be warming up to the purification temperature once more, if alloy heats up when melting after solidifying once more, do not produce bubble, then can after purifying about 1 hour, continuation finish purification process;
5) the alloy melt cooling that is in molten state after will purifying obtains the Pd-Cu-Si block amorphous alloy.
3, the preparation method of Pd-Cu-Si block amorphous alloys as claimed in claim 2 is characterized in that, the described the 2nd) step coats medium with glass and is fused into liquid under the condition of melting temperature and carries out in crucible at silica tube or alloy melting being higher than.
4, the preparation method of Pd-Cu-Si block amorphous alloys as claimed in claim 2 is characterized in that, the described the 4th) total purification time of described alloy of step is 2～10 hours.
5, the preparation method of high-toughness binary-cube non-crystal alloy as claimed in claim 2 is characterized in that, the described the 5th) described method of cooling of step be be in after purifying the alloy melt of molten state and coating medium on every side together slow cooling to room temperature.
6, the preparation method of high-toughness binary-cube non-crystal alloy as claimed in claim 2 is characterized in that, the described the 5th) described method of cooling of step be be in after purifying the alloy melt of molten state and coating medium on every side together shrend to room temperature.
7, the preparation method of high-toughness binary-cube non-crystal alloy as claimed in claim 2, it is characterized in that, the described the 5th) described method of cooling of step is that the alloy melt that will be in molten state after will purifying solidifies earlier, then the alloy of purifying is melted the back rapid solidification once more or is cast into metal pattern under vacuum condition.
8, the preparation method of high-toughness binary-cube non-crystal alloy as claimed in claim 2 is characterized in that, it is that dry glass coats medium that described glass coats medium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320723A (en) * | 2013-05-28 | 2013-09-25 | 江苏迈盛新材料有限公司 | Repeated fusion-solidification treating method for raising alloy amorphous forming ability |
| WO2019056595A1 (en) * | 2017-09-25 | 2019-03-28 | 北京科技大学 | Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor |
-
2007
- 2007-06-15 CN CNB2007101189330A patent/CN100537821C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320723A (en) * | 2013-05-28 | 2013-09-25 | 江苏迈盛新材料有限公司 | Repeated fusion-solidification treating method for raising alloy amorphous forming ability |
| WO2019056595A1 (en) * | 2017-09-25 | 2019-03-28 | 北京科技大学 | Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor |
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