CN103866209B - Zirconium-based alloy ingot and preparation method thereof as well as prepared zirconium-based amorphous alloy - Google Patents
Zirconium-based alloy ingot and preparation method thereof as well as prepared zirconium-based amorphous alloy Download PDFInfo
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Abstract
The invention relates to the technical field of alloy ingots, and in particular relates to a zirconium-based alloy ingot and a preparation method thereof as well as a prepared zirconium-based amorphous alloy. The preparation method of the zirconium-based alloy ingot comprises two steps, namely, a vacuum arc melting method and a vacuum high frequency melting method, wherein the vacuum arc melting method comprises steps of mixing and melting Ni metal and a high melting point method Nb metal, thereby reducing the melting temperature; in addition, except the impurities in the raw materials in the vacuum arc melting method, no other impurities are mixed, so that the purity of the alloy is ensured; a mother alloy obtained by using the vacuum arc melting method is further mixed with the rest materials for secondary melting, thereby obtaining a five-element alloy ingot with accurate proportion. The zirconium-based alloy ingot is die-cast in a vacuum environment, a cooling speed expected by over-cooling is met so as to prevent the materials from crystallization, and the zirconium-based amorphous alloy with the thickness of 0.5-3mm can be manufactured.
Description
Technical field
The present invention relates to alloy pig technical field is and in particular to zirconium-base alloy ingot and preparation method thereof and prepared zirconio are non-
Peritectic alloy.
Background technology
Non-crystaline amorphous metal is similar to liquid, is the alloy with irregular atomic structre, thus also referred to as non-crystaline amorphous metal or
amorphous alloy.The atom of metal all ordered arrangement form crystalline texture under normal circumstances, but the atom of non-crystaline amorphous metal
Irregular arrangement, and there is no crystalline texture, so there is higher intensity, preferably elasticity than general metal material, and
Relatively lighter, so causing a sensation effect in metal industry when developing originally.After non-crystaline amorphous metal adds suitable heat
The state of the imaging the same free forming of plastics can be become, so this non-crystaline amorphous metal manufacture method is just rising to as new after developing
Industrial materials.
The zirconium-base amorphous alloy (zriconium base amorphous alloy) of volume production is successfully imported at the beginning of the 2000's
It is the non-crystaline amorphous metal being fabricated by along with the metal such as copper, nickel, niobium, aluminum based on zirconium, its alloy surface unusual light, so
It is referred to as liquidmetal.Non-crystaline amorphous metal it product (the inside and outside component of mobile phone), medical apparatus and instruments (artificial femoral joint, knee joint,
Internal transplantation device, operation tool), military articles for use, the field such as sports goods very popular, non-crystaline amorphous metal product passes through new
Pressure casting method casting, so have the advantages that the easy molding of labyrinth, rear processing charges minimize.Zirconium-base amorphous alloy
The atomic number of the main atom-zirconium (zriconium) of (zriconium-based amorphous alloy) is 40, belongs to
The silver-gray transition metal of 4th race (with titanium (ti), hafnium (hf)) nominal is titanium family), its metal itself easily reacts formation two
Zirconium oxide protecting film, so corrosion resistance is very strong.In addition this metal surface intensity is strong, high mechanical strength, heat conductivity are good.Make
Metal for storing flow control more than nine on the earth widely uses in fields such as atomic energy, synthetic fibers, petrochemistry.Particularly in pottery
In porcelain products, atomic energy development field, demand increase is quickly.Zirconium is minimum in metal material to neutron absorption basal area, and
And its corrosion resistance is very strong, so demand is most in atomic energy material.In addition this metal not only mechanical performance and corrosion resistant
Outside corrosion is very good, also with the Uranous oxide (uo for nuclear fuel2) compatibility is very good, is suitable for being used as the pile core of reactor
Structural material.
In view of the application of zirconium-base amorphous alloy, occur in that zirconium-base alloy ingot material, such as in Application No. 97109961.8
State's application for a patent for invention quinary metallic glass alloys, only introduce the composition of zirconium-base alloy ingot in literary composition, have no and introduce the conjunction of this zirconio
Ingot preparation method；And for example the Chinese invention patent application zirconium-base alloy ingot part of Application No. 201110051331.4 and
Its manufacture method, because the defect of its preparation method can not obtain the zirconium-base alloy ingot with accurate atom ratio.
Content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide one kind can be had
Accurately zirconium-base alloy ingot of atom ratio and preparation method thereof and the zirconium-base amorphous alloy being obtained.
The purpose of the present invention is achieved through the following technical solutions:
A kind of zirconium-base alloy ingot, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 45-70%
cu 10-20%
ni 8-18%
al 5-15%
nb 2-8%.
Preferably, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 55-70%
cu 12-18%
ni 10-16%
al 8-12%
nb 2-6%.
It is more highly preferred to, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 57%
cu 15.4%
ni 12.6%
al 10%
nb 5%.
A kind of preparation method of zirconium-base alloy ingot, it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are melted by vacuum arc
The method of melting carries out melting, obtains foundry alloy, and can be made using vacuum arc fusion method will not in addition to impurity contained in raw material
It is mixed into other impurities it is ensured that the purity of alloy；
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu
Metal, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot.
Preferably, the preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: in order to maintain the purity of alloy, anti-oxidation, the melter of vacuum arc melting furnace is taken out
To 10-4The vacuum of torr, then pours into high-purity argon gas to melter, and the amount of high-purity argon gas is the 60%-80% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight,
Melt under the conditions of temperature is for 2500-3500 DEG C；The fusing point of nb element is about 2470 DEG C, belongs to materials with high melting point, ni element
Fusing point is about 1453 DEG C, nb element is carried out mixed melting according to weight than for 51:49 with ni element, fusing point can be reduced to
1200℃；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy.
Preferably, the preparation of described step b secondary alloy specifically includes following steps:
Before step b1, melting: in order to maintain the purity of alloy, anti-oxidation, melter is evacuated to 10-4The vacuum of torr
Degree, pours into high-purity argon gas to melting interior, the volume of high-purity argon gas accounts for the 20%-30% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining
Ni metal is melted in the melter of vacuum high frequency smelting furnace, and melting adopts diffusion melting method, in order to reach zirconium carbide
Yield minimizes, and melt temperature not can exceed that 1200 DEG C, preferably controls melt temperature at 1100 DEG C -1200 DEG C, melting
Time is 60-90min；
Step b3, melting terminate: in order to keep glass forming ability and protection ingot mould, cool down molten soup in 20-30min
To 900 DEG C -950 DEG C, in order to keep high-purity and dispel smog, then with air pump, melter is pumped to 10-1The vacuum of torr
Degree；
Step b4, the soup that falls: in the cooling chamber of ingot mould, in order to rapidly cool down, pour into the 60-80% argon of whole cooling chamber volume
Gas, starts circulation hot switch, then pours molten soup in ingot mould into and cools down 30-60min through circulation hot switch, obtains
Zirconium-base alloy ingot.Carry out die casting using the zirconium-base alloy ingot manufacturing by vacuum induction fusion method under vacuum conditions, full
The supercool required rate of cooling of foot, to suppress material crystalline, can produce the sample of minimum thickness 0.5- maximum gauge 3mm.
It is more highly preferred to, when molten soup is poured in ingot mould in step b4, need to enter according to the speed pouring 50kg within 3min into
OK.
A kind of zirconium-base amorphous alloy, zirconium-base alloy ingot as claimed in claim 4 is carried out die casting, and obtaining thickness is
The zirconium-base amorphous alloy of 0.5mm-3mm.It should be noted that described zirconium-base alloy ingot is not completely amorphous, zirconium-base alloy ingot
Top layer is amorphous, and the portion of zirconium-base alloy ingot is crystallization, is only using the product that zirconium-base alloy ingot goes out as die casting raw material die casting
Zirconium-base amorphous alloy.
Preferably, described zr metal, cu metal, ni metal, al metal, nb metal all using purity be 99.9% with
On raw material.
The beneficial effects of the present invention is: the preparation method of the zirconium-base alloy ingot of the present invention divides vacuum arc fusion method and true
Two steps of outage cycle fusion method are carried out.Vacuum arc fusion method is melted ni metal with materials with high melting point nb metal mixed,
Reduce melt temperature, in addition, vacuum arc fusion method will not to be mixed into other in addition to impurity contained in raw material impure
Thing is it is ensured that the purity of alloy；The foundry alloy that vacuum arc fusion method obtains is carried out second again and melts with remaining material mixing
Melt, thus obtaining five kinds of mischmetal ingots with accurate proportioning.Described zirconium-base alloy ingot carries out die casting under vacuum conditions, full
The supercool required rate of cooling of foot, to suppress material crystalline, can produce the zirconium-base amorphous alloy that thickness is 0.5- 3mm.
Specific embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not limitation of the invention.
Embodiment 1.
A kind of zirconium-base alloy ingot, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 65%
cu 15%
ni 8%
al 9%
nb 3%.
A kind of preparation method of zirconium-base alloy ingot, it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are melted by vacuum arc
The method of melting carries out melting, obtains foundry alloy, and the preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: the melter of vacuum arc melting furnace is evacuated to 10-4The vacuum of torr, then to melting
Room pours into high-purity argon gas, and the amount of high-purity argon gas is the 60% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight,
Melt under the conditions of temperature is 2500 DEG C；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy.
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu
Metal, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot.Described step
The preparation of rapid b secondary alloy specifically includes following steps:
Before step b1, melting: melter is evacuated to 10-4The vacuum of torr, pours into high-purity argon gas to melting interior, high-purity
The volume of argon accounts for the 20% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining
Ni metal is melted in the melter of vacuum high frequency smelting furnace, and melt temperature is controlled at 1100 DEG C, and the melting time is
80min；
Step b3, melting terminate: in 30min, molten soup is cooled to 900 DEG C, is then pumped to melter with air pump
10-1The vacuum of torr；
Step b4, the soup that falls: pour into 60% argon of whole cooling chamber volume in the cooling chamber of ingot mould, start circulation hot
Switch, then pours molten soup in ingot mould into and cools down 30min through circulation hot switch, obtain zirconium-base alloy ingot, wherein, melts
The speed of ingot mould poured into by soup, needs to carry out according to the speed pouring 50kg within 3min into.
Wherein, the zr metal in this preparation method, cu metal, ni metal, al metal, nb metal using purity are all
More than 99.9% raw material.
A kind of zirconium-base amorphous alloy, above-mentioned zirconium-base alloy ingot is carried out die casting, obtains the zirconium-base amorphous conjunction that thickness is 3mm
Gold.
Embodiment 2.
A kind of zirconium-base alloy ingot, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 50%
cu 20%
ni 17%
al 5%
nb 8%.
A kind of preparation method of zirconium-base alloy ingot, it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are melted by vacuum arc
The method of melting carries out melting, obtains foundry alloy, and the preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: the melter of vacuum arc melting furnace is evacuated to 10-4The vacuum of torr, then to melting
Room pours into high-purity argon gas, and the amount of high-purity argon gas is the 80% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight,
Melt under the conditions of temperature is 3000 DEG C；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy.
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu
Metal, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot.Described step
The preparation of rapid b secondary alloy specifically includes following steps:
Before step b1, melting: melter is evacuated to 10-4The vacuum of torr, pours into high-purity argon gas to melting interior, high-purity
The volume of argon accounts for the 30% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining
Ni metal is melted in the melter of vacuum high frequency smelting furnace, and melt temperature is controlled at 1200 DEG C, and the melting time is
60min；
Step b3, melting terminate: in 20min, molten soup is cooled to 900 DEG C, is then pumped to melter with air pump
10-1The vacuum of torr；
Step b4, the soup that falls: pour into 80% argon of whole cooling chamber volume in the cooling chamber of ingot mould, start circulation hot
Switch, then pours molten soup in ingot mould into and cools down 60min through circulation hot switch, obtain zirconium-base alloy ingot, wherein, melts
The speed of ingot mould poured into by soup, needs to carry out according to the speed pouring 50kg within 3min into.
Wherein, the zr metal in this preparation method, cu metal, ni metal, al metal, nb metal using purity are all
More than 99.9% raw material.
A kind of zirconium-base amorphous alloy, above-mentioned zirconium-base alloy ingot is carried out die casting, obtains the zirconium-base amorphous conjunction that thickness is 3mm
Gold.
Embodiment 3.
A kind of zirconium-base alloy ingot, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 57%
cu 15.4%
ni 12.6%
al 10%
nb 5%.
A kind of preparation method of zirconium-base alloy ingot, it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are melted by vacuum arc
The method of melting carries out melting, obtains foundry alloy, and the preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: the melter of vacuum arc melting furnace is evacuated to 10-4The vacuum of torr, then to melting
Room pours into high-purity argon gas, and the amount of high-purity argon gas is the 70% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight,
Melt under the conditions of temperature is 3000 DEG C；The zirconium-base alloy ingot of above-mentioned composition accounts for 6.03%, ni according to nb for percentage by weight
Account for 9.65%.For nb, it is that in composition, 51% weight includes all 100% (6.03%) contents at its 2 yuan, for ni,
After weighing 49% (5.75%) weight, remaining ni (3.9%) waits until second to place into melting when melting.The reality of nb
Fusing point is 2400 degree about, but when percentage by weight is nb:ni=51:49, its fusing point can be reduced to 1200 DEG C；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy, the fusing point of foundry alloy is 1200 DEG C.
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu
Metal, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot.Described step
The preparation of rapid b secondary alloy specifically includes following steps:
Before step b1, melting: melter is evacuated to 10-4The vacuum of torr, pours into high-purity argon gas to melting interior, high-purity
The volume of argon accounts for the 25% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining
Ni metal is melted in the melter of vacuum high frequency smelting furnace, and melt temperature is controlled at 1150 DEG C, and the melting time is
80min；
Step b3, melting terminate: in 25min, molten soup is cooled to 930 DEG C, is then pumped to melter with air pump
10-1The vacuum of torr；
Step b4, the soup that falls: pour into 70% argon of whole cooling chamber volume in the cooling chamber of ingot mould, start circulation hot
Switch, then pours molten soup in ingot mould into and cools down 50min through circulation hot switch, obtain zirconium-base alloy ingot, wherein, melts
The speed of ingot mould poured into by soup, needs to carry out according to the speed pouring 50kg within 3min into.
Wherein, the zr metal in this preparation method, cu metal, ni metal, al metal, nb metal using purity are all
More than 99.9% raw material.
A kind of zirconium-base amorphous alloy, above-mentioned zirconium-base alloy ingot is carried out die casting, obtains the zirconium-base amorphous conjunction that thickness is 2mm
Gold.
Embodiment 4.
A kind of zirconium-base alloy ingot, described zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 70%
cu 10%
ni 8%
al 10%
nb 2%.
A kind of preparation method of zirconium-base alloy ingot, it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are melted by vacuum arc
The method of melting carries out melting, obtains foundry alloy, and the preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: the melter of vacuum arc melting furnace is evacuated to 10-4The vacuum of torr, then to melting
Room pours into high-purity argon gas, and the amount of high-purity argon gas is the 80% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight,
Melt under the conditions of temperature is 3500 DEG C；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy.
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu
Metal, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot.Described step
The preparation of rapid b secondary alloy specifically includes following steps:
Before step b1, melting: melter is evacuated to 10-4The vacuum of torr, pours into high-purity argon gas to melting interior, high-purity
The volume of argon accounts for the 30% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining
Ni metal is melted in the melter of vacuum high frequency smelting furnace, and melt temperature is controlled at 1200 DEG C, and the melting time is
80min；
Step b3, melting terminate: in 30min, molten soup is cooled to 950 DEG C, is then pumped to melter with air pump
10-1The vacuum of torr；
Step b4, the soup that falls: pour into 80% argon of whole cooling chamber volume in the cooling chamber of ingot mould, start circulation hot
Switch, then pours molten soup in ingot mould into and cools down 60min through circulation hot switch, obtain zirconium-base alloy ingot, wherein, melts
The speed of ingot mould poured into by soup, needs to carry out according to the speed pouring 50kg within 3min into.
Wherein, the zr metal in this preparation method, cu metal, ni metal, al metal, nb metal using purity are all
More than 99.9% raw material.
A kind of zirconium-base amorphous alloy, above-mentioned zirconium-base alloy ingot is carried out die casting, obtains the zirconium-base amorphous conjunction that thickness is 0.5mm
Gold.
Embodiment 1-4 is obtained with the physical and mechanical propertiess such as yield strength, the consistency and elasticity deformation of zirconium-base amorphous alloy enter
Row test, refers to table 1.
.
It can be seen from Table 1 that, the yield strength of the zirconium-base amorphous alloy that embodiment of the present invention 1-4 obtains, hardness and bullet
Property deformation etc. physical and mechanical propertiess good.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can be realized with alternate manner,
Without departing from obvious replacement any on the premise of present inventive concept all within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of zirconium-base alloy ingot it is characterised in that: it comprises the following steps:
Step a, the preparation of foundry alloy: the nb metal needed for zirconium-base alloy ingot and part ni metal are passed through vacuum arc fusion method
Carry out melting, obtain foundry alloy；
Step b, the preparation of zirconium-base alloy ingot: the zr metal needed for the foundry alloy that obtain step a and zirconium-base alloy ingot, cu gold
Genus, al metal and remaining ni metal, carry out melting by vacuum high frequency fusion method, obtain zirconium-base alloy ingot,
The preparation of described step a foundry alloy specifically includes following steps:
Before step a1, melting: the melter of vacuum arc melting furnace is evacuated to 10-4The vacuum of torr, then fills to melter
Enter high-purity argon gas, the amount of high-purity argon gas is the 60%-80% of melter's volume；
When step a2, melting: the nb metal needed for zirconium-base alloy ingot and ni metal are mixed than for 51:49 according to weight, in temperature
Spend for melting under the conditions of 2500-3500 DEG C；
Step a3, melting terminate: after melting terminates, cooled down, obtain foundry alloy；
The preparation of described step b secondary alloy specifically includes following steps:
Before step b1, melting: melter is evacuated to 10-4The vacuum of torr, pours into high-purity argon gas, high-purity argon gas to melting interior
Volume account for the 20%-30% of whole melter volume；
When step b2, melting: by the zr metal needed for foundry alloy and zirconium-base alloy ingot, cu metal, al metal and remaining ni gold
Belong to and being melted in the melter of vacuum high frequency smelting furnace, melt temperature is controlled at 1100 DEG C -1200 DEG C, the melting time is
60-90min；
Step b3, melting terminate: in 20-30min, molten soup is cooled to 900 DEG C -950 DEG C, then with air pump by melter
It is pumped to 10-1The vacuum of torr；
Step b4, the soup that falls: pour into the 60-80% argon of whole cooling chamber volume in the cooling chamber of ingot mould, start circulation hot and hand over
Change planes, then pour molten soup in ingot mould into and cool down 30-60min through circulation hot switch, obtain zirconium-base alloy ingot,
Above-mentioned zirconium-base alloy ingot is made up of the atom of following atomic percent:
zr 45-70%
cu 10-20%
ni 8-18%
al 5-15%
nb 2-8%.
2. zirconium-base alloy ingot according to claim 1 preparation method it is characterised in that: in step b4, ingot mould poured into by molten soup
When middle, need to carry out according to the speed pouring 50kg within 3min into.
3. zirconium-base alloy ingot according to claim 1 preparation method it is characterised in that: described zr metal, cu metal, ni
The raw material that metal, al metal, nb metal are all more than 99.9% using purity.
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| CN104195476A (en) * | 2014-09-26 | 2014-12-10 | 东莞台一盈拓科技股份有限公司 | Method for manufacturing zirconium-based amorphous alloy with cold crucible smelting furnace device |
| CN104190896B (en) * | 2014-09-26 | 2016-07-06 | 东莞帕姆蒂昊宇液态金属有限公司 | The electric arc melting pressure casting method of non-crystaline amorphous metal |
| CN104313514B (en) * | 2014-10-27 | 2017-01-25 | 东莞帕姆蒂昊宇液态金属有限公司 | Application of amorphous alloy to preparation of razor blade and razor |
| CN104451471B (en) * | 2014-12-29 | 2017-11-03 | 东莞帕姆蒂昊宇液态金属有限公司 | A kind of non-crystaline amorphous metal spectacle frame and glasses and preparation method |
| CN104451472B (en) * | 2014-12-29 | 2017-04-05 | 东莞帕姆蒂昊宇液态金属有限公司 | A kind of non-crystaline amorphous metal spectacle frame and glasses and preparation method |
| CN104645423B (en) * | 2015-02-11 | 2017-11-14 | 东莞帕姆蒂昊宇液态金属有限公司 | A kind of non-crystaline amorphous metal scalpel and its manufacture method |
| CN106591743A (en) * | 2017-01-23 | 2017-04-26 | 苏州大学 | High-plasticity zirconium base amorphous alloy and preparation method thereof |
| CN108330413B (en) * | 2018-05-04 | 2020-04-21 | 深圳市锆安材料科技有限公司 | High-compression-resistance zirconium-based amorphous alloy and preparation method thereof |
| CN110157996B (en) * | 2019-05-10 | 2021-11-09 | 河北工业大学 | Novel corrosion-resistant zirconium-based alloy and preparation method thereof |
| CN113930695B (en) * | 2021-10-14 | 2022-12-20 | 盘星新型合金材料(常州)有限公司 | Al-containing low-density block amorphous alloy and preparation method and application thereof |
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| JP3852805B2 (en) * | 1998-07-08 | 2006-12-06 | 独立行政法人科学技術振興機構 | Zr-based amorphous alloy excellent in bending strength and impact strength and its production method |
| CN101440465B (en) * | 2007-11-20 | 2010-11-17 | 比亚迪股份有限公司 | Zirconium based amorphous alloy and manufacture method thereof |
| CN101440464B (en) * | 2007-11-24 | 2011-01-26 | 比亚迪股份有限公司 | Zirconium based amorphous alloy and manufacture method thereof |
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