CN103668010A - A series of Zr-Al-Ni-Cu block amorphous alloys having cellular microstructures - Google Patents

A series of Zr-Al-Ni-Cu block amorphous alloys having cellular microstructures Download PDF

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CN103668010A
CN103668010A CN201310640750.0A CN201310640750A CN103668010A CN 103668010 A CN103668010 A CN 103668010A CN 201310640750 A CN201310640750 A CN 201310640750A CN 103668010 A CN103668010 A CN 103668010A
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mother alloy
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melting
alloy
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CN103668010B (en
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蔡安辉
熊翔
刘咏
安伟科
周果君
罗云
李铁林
李小松
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Hunan Institute of Science and Technology
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Abstract

The invention belongs to the field of novel materials, and discloses a series of Zr-Al-Ni-Cu block amorphous alloys having cellular microstructures. According to the Zr-Al-Ni-Cu block amorphous alloys, Zr (99.99 wt%), Al (99.99 wt%), Ni (99.99 wt%) and Cu (99.99 wt%) are smelted through a vacuum smelting method, and are prepared into amorphous alloy samples having a diameter of 3 mm through a suction casting method. The Zr-Al-Ni-Cu block amorphous alloys have the cellular microstructures and are ideal precursors used for preparing Zr-Al-Ni-Cu block amorphous foam materials.

Description

A series of Zr-Al-Ni-Cu block amorphous alloys with born of the same parents' shape microtexture
Technical field
The present invention relates to the Zr-Al-Ni-Cu block amorphous alloy of a series of born of the same parents' of having shape microtextures.
Background technology
Zirconium-based bulk amorphous alloy has that amorphous formation ability is good, recoverable strain is large, resistance to corrosion is high, ultimate compression strength is high, temperature-room type plasticity and biocompatibility that particularly some zirconium-base amorphous alloy shows, these features make it in structure and technical field of biological material, have great application prospect.At present, adopt high power transmission electron microscope can observe the existence that has the Cluster Structures of atom or nanoscale in non-crystaline amorphous metal, but also do not prepare the non-crystaline amorphous metal with micro-meter scale microtexture.Therefore and the temperature-room type plasticity of non-crystaline amorphous metal and its internal microstructure are closely bound up, prepare the zirconium-based bulk amorphous alloy with special micro-meter scale microtexture and have very important significance.
Summary of the invention
The object of the present invention is to provide the Zr-Al-Ni-Cu block amorphous alloy of a series of born of the same parents' of having shape microtextures.
The object of the invention is to be achieved through the following technical solutions: the Zr-Al-Ni-Cu block amorphous alloy of a series of born of the same parents' of having shape microtextures, is characterized in that: comprise the steps:
Figure 767431DEST_PATH_IMAGE001
block Cu, Zr, Al and the Ni that is 99.99wt% by purity is by Zr-Al-Ni-Cu alloying constituent proportion ingredient;
Figure 474224DEST_PATH_IMAGE002
the crucible of the material preparing being put into electric arc furnace, is evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.45 normal atmosphere, and then melting Ti carries out air-breathing;
Figure 288597DEST_PATH_IMAGE003
molten alloy 5 times takes out mother alloy after vacuum chamber is cooling, crucible is cleaned up and mother alloy is broken;
Figure 111059DEST_PATH_IMAGE004
the part mother alloy that fragmentation is good is put into the crucible of electric arc furnace, and install the water cooled copper mould that die cavity diameter is 3mm;
Figure 440409DEST_PATH_IMAGE005
be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting, can obtain the non-crystaline amorphous metal that diameter is 3mm.
Described alloying constituent is respectively Zr 65al 8.7cu 14.4ni 11.9, Zr 64al 10.1cu 11.7ni 14.2, Zr 63.5al 10.7cu 10.7ni 15.1, Zr 62al 10cu 15ni 13, Zr 61.5al 10.7cu 13.65ni 14.15, Zr 60.5al 12.1cu 10.95ni 16.45(at%), can form diameter is the amorphous sample of 3mm, and its inside has the microtexture of born of the same parents' shape.
The product that the present invention makes use respectively X-ray diffractometer (XRD) and differential scanning calorimeter (DTA) test material amorphous structure, with the mixed solution of hydrofluoric acid and nitric acid, the cross section of non-crystaline amorphous metal sample is carried out to the microtexture on cross section that scanning electronic microscope for burn into (SEM) analytical sample corroded, find that product that the present invention makes is all amorphous include the born of the same parents' shape microtexture that is of a size of 3～20 microns completely.
  
Embodiment
According to specific embodiment, the invention will be further described below:
Embodiment 1
According to Zr 65al 8.7cu 14.4ni 11.9(at%) alloying constituent, takes zirconium 15.2474 ± 0.0001g, aluminium 0.6036 ± 0.0001g, copper 2.3530 ± 0.0001g and nickel 1.7959 ± 0.0001g with analytical balance, puts into the copper crucible of vacuum arc fumace, is evacuated to 1 * 10 -3pa, be filled with the pressure that argon gas makes vacuum chamber and reach 0.45 normal atmosphere, melting Ti carry out air-breathing after, then molten alloy is 5 times, after vacuum chamber is cooling, mother alloy is taken out, crucible is cleaned up and by mother alloy fragmentation, the good part mother alloy of fragmentation is put into the crucible of electric arc furnace, and install the water cooled copper mould that die cavity diameter is 3mm, be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting and obtain the sample that diameter is 3mm.Then with water-cooled at a slow speed diamond custting machine from taking off the sample that length is 2mm in the middle of sample, by its cross section polish, polishing corroding with the mixed solution of hydrofluoric acid and nitric acid.By XRD and DTA technology for detection, find that this product is for non-crystalline state completely, the cross section after corroding by sem analysis finds to have the clear born of the same parents' shape microtexture that is of a size of 20 microns.
Embodiment 2
According to Zr 61.5al 10.7cu 13.65ni 14.15(at%) alloying constituent, takes zirconium 14.7700 ± 0.0001g, aluminium 0.7601 ± 0.0001g, copper 2.2836 ± 0.0001g and nickel 2.1863 ± 0.0001g with analytical balance, puts into the copper crucible of vacuum arc fumace, is evacuated to 1 * 10 -3pa, be filled with the pressure that argon gas makes vacuum chamber and reach 0.45 normal atmosphere, melting Ti carry out air-breathing after, then molten alloy is 5 times, after vacuum chamber is cooling, mother alloy is taken out, crucible is cleaned up and by mother alloy fragmentation, the good part mother alloy of fragmentation is put into the crucible of electric arc furnace, and install the water cooled copper mould that die cavity diameter is 3mm, be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting and obtain the sample that diameter is 3mm.Then with water-cooled at a slow speed diamond custting machine from taking off the sample that length is 2mm in the middle of sample, by its cross section polish, polishing corroding with the mixed solution of hydrofluoric acid and nitric acid.By XRD and DTA technology for detection, find that this product is for non-crystalline state completely, the cross section after corroding by sem analysis finds to have the clear born of the same parents' shape microtexture that is of a size of 8 microns.
Embodiment 3
According to Zr 60.5al 12.1cu 10.95ni 16.45(at%) alloying constituent, takes zirconium 14.7041 ± 0.0001g, aluminium 0.8698 ± 0.0001g, copper 1.8539 ± 0.0001g and nickel 2.5722 ± 0.0001g with analytical balance, puts into the copper crucible of vacuum arc fumace, is evacuated to 1 * 10 -3pa, be filled with the pressure that argon gas makes vacuum chamber and reach 0.45 normal atmosphere, melting Ti carry out air-breathing after, then molten alloy is 5 times, after vacuum chamber is cooling, mother alloy is taken out, crucible is cleaned up and by mother alloy fragmentation, the good part mother alloy of fragmentation is put into the crucible of electric arc furnace, and install the water cooled copper mould that die cavity diameter is 3mm, be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting and obtain the sample that diameter is 3mm.Then with water-cooled at a slow speed diamond custting machine from taking off the sample that length is 2mm in the middle of sample, by its cross section polish, polishing corroding with the mixed solution of hydrofluoric acid and nitric acid.By XRD and DTA technology for detection, find that this product is for non-crystalline state completely, the cross section after corroding by sem analysis finds to have the clear born of the same parents' shape microtexture that is of a size of 12 microns.
Embodiment 4
According to Zr 63.5al 10.7cu 10.7ni 15.1(at%) alloying constituent, takes zirconium 15.1492 ± 0.0001g, aluminium 0.7550 ± 0.0001g, copper 1.7782 ± 0.0001g and nickel 2.3176 ± 0.0001g with analytical balance, puts into the copper crucible of vacuum arc fumace, is evacuated to 1 * 10 -3pa, be filled with the pressure that argon gas makes vacuum chamber and reach 0.45 normal atmosphere, melting Ti carry out air-breathing after, then molten alloy is 5 times, after vacuum chamber is cooling, mother alloy is taken out, crucible is cleaned up and by mother alloy fragmentation, the good part mother alloy of fragmentation is put into the crucible of electric arc furnace, and install the water cooled copper mould that die cavity diameter is 3mm, be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting and obtain the sample that diameter is 3mm.Then with water-cooled at a slow speed diamond custting machine from taking off the sample that length is 2mm in the middle of sample, by its cross section polish, polishing corroding with the mixed solution of hydrofluoric acid and nitric acid.By XRD and DTA technology for detection, find that this product is for non-crystalline state completely, the cross section after corroding by sem analysis finds to have the clear born of the same parents' shape microtexture that is of a size of 3 microns.
  

Claims (3)

1. a series of Zr-Al-Ni-Cu block amorphous alloys with born of the same parents' shape microtexture, is characterized in that: comprise the steps:
Figure 184258DEST_PATH_IMAGE001
block Cu, Zr, Al and the Ni that is 99.99wt% by purity is by Zr-Al-Ni-Cu alloying constituent proportion ingredient;
Figure 938587DEST_PATH_IMAGE002
the crucible of the material preparing being put into electric arc furnace, is evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.45 normal atmosphere, and then melting Ti carries out air-breathing;
Figure 737916DEST_PATH_IMAGE003
molten alloy 5 times takes out mother alloy after vacuum chamber is cooling, crucible is cleaned up and mother alloy is broken;
Figure 261301DEST_PATH_IMAGE004
the part mother alloy that fragmentation is good is put into the crucible of electric arc furnace, and install the water cooled copper mould that diameter of bore is 3mm;
be evacuated down to 1 * 10 -3the argon gas that is filled with again purity >99.99wt% after Pa makes the pressure of vacuum chamber reach 0.2 normal atmosphere, and then melting Ti carries out air-breathingly, and mother alloy is carried out to melting and inhale casting, can obtain the non-crystaline amorphous metal that diameter is 3mm.
2. preparation method according to claim 1, is characterized in that: described alloying constituent is respectively Zr 65al 8.7cu 14.4ni 11.9, Zr 64al 10.1cu 11.7ni 14.2, Zr 63.5al 10.7cu 10.7ni 15.1, Zr 62al 10cu 15ni 13, Zr 61.5al 10.7cu 13.65ni 14.15, Zr 60.5al 12.1cu 10.95ni 16.45(at%).
3. alloy according to claim 2, is characterized in that: the sample that the formed diameter of described alloying constituent is 3mm is non-crystalline state, and its inside comprises born of the same parents' shape microtexture.
CN201310640750.0A 2013-12-04 2013-12-04 A series of Zr Al Ni Cu block amorphous alloys with born of the same parents' shape microstructure Expired - Fee Related CN103668010B (en)

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CN104762497A (en) * 2015-05-05 2015-07-08 湖南理工学院 Zr-Al-Ni-Cu bulk amorphous alloy series with indoor temperature compressive plasticity and high strength
CN104775082A (en) * 2015-05-05 2015-07-15 湖南理工学院 Zr-Al-Ni-Cu bulk metallic glass achieving room temperature compression superplasticity
CN107829049A (en) * 2017-11-08 2018-03-23 湖南理工学院 The zirconium-based bulk amorphous alloy and its preparation technology of a kind of titaniferous
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

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Publication number Priority date Publication date Assignee Title
CN104762497A (en) * 2015-05-05 2015-07-08 湖南理工学院 Zr-Al-Ni-Cu bulk amorphous alloy series with indoor temperature compressive plasticity and high strength
CN104775082A (en) * 2015-05-05 2015-07-15 湖南理工学院 Zr-Al-Ni-Cu bulk metallic glass achieving room temperature compression superplasticity
CN107829049A (en) * 2017-11-08 2018-03-23 湖南理工学院 The zirconium-based bulk amorphous alloy and its preparation technology of a kind of titaniferous
CN107829049B (en) * 2017-11-08 2022-01-18 湖南理工学院 Titanium-containing zirconium-based block amorphous alloy and preparation process thereof
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
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

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