CN103866210A - Low-price Zr-based alloy ingot and preparation method thereof and prepared low-price Zr-based amorphous alloy - Google Patents
Low-price Zr-based alloy ingot and preparation method thereof and prepared low-price Zr-based amorphous alloy Download PDFInfo
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- CN103866210A CN103866210A CN201410133028.2A CN201410133028A CN103866210A CN 103866210 A CN103866210 A CN 103866210A CN 201410133028 A CN201410133028 A CN 201410133028A CN 103866210 A CN103866210 A CN 103866210A
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Abstract
The invention relates to the technical field of alloy ingots, and particularly relates to a low-price Zr-based alloy ingot and a preparation method thereof and a prepared low-price Zr-based amorphous alloy. According to the invention, high-purity Zr is replaced with Zr-2 and Zr-4, and then a low-price Zr-based alloy ingot is prepared by using a vacuum arc melting method and a vacuum high-frequency melting method. Because high-purity Zr is replaced with Zr-2 and Zr-4, the price of the Zr-based alloy ingot is greatly reduced. Meanwhile, Zr2 and Zr4 contain 1.4% of Sn in percentage by weight, so that the replaceable Nb maximum range can reach 50% of the Nb content of the low-price Zr-based alloy ingot. The low-price Zr-based alloy ingot is subjected to pressure casting in a vacuum environment for satisfying the cooling speed required for super-cooling so as to restrain the crystallization of materials, therefore, a low-price Zr-based amorphous alloy with a thickness of 0.5-3 mm can be manufactured.
Description
Technical field
The present invention relates to alloy pig technical field, be specifically related to zirconium base alloy ingot and preparation method thereof and the low price zirconium-base amorphous alloy making at a low price.
Background technology
Non-crystaline amorphous metal and liquid phase seemingly, are the alloys with irregular atomic structre, so be also referred to as non-crystaline amorphous metal or Amorphous alloy.All ordered arrangement formation crystalline texture of the atom of metal under normal circumstances, but the atomic arrangement of non-crystaline amorphous metal is irregular, and there is no crystalline texture, so there is higher intensity, better elasticity than general metallic substance, and low weight, so when developing originally in the metal industry effect that causes a sensation.Non-crystaline amorphous metal adds the state that can become free forming as plastics after suitable heat, so this non-crystaline amorphous metal manufacture method develops rear just rising to as new Industrial materials.
The zirconium-base amorphous alloy (Zriconium base Amorphous alloy) that successfully imports volume production at the beginning of the 2000's is added the non-crystaline amorphous metal that the metal manufactures such as copper, nickel, niobium, aluminium form take zirconium as basis, its alloy surface is very smooth, so be called as Liquidmetal.Non-crystaline amorphous metal is very welcome in fields such as IT product (the inside and outside member of mobile phone), medicine equipment (transplantation device, operation tool in artificial femoral joint, knee joint, body), military articles for use, sports goodss, non-crystaline amorphous metal product is by Novel pressure casting method casting, so have advantages of the easy moulding of complex construction, post-treatment cost minimization.
The ordination number of the main atom-zirconium (Zriconium) of zirconium-base amorphous alloy (Zriconium-based Amorphous alloy) is 40; belonging to the 4th silver-gray transition metal of family (with titanium (Ti), hafnium (Hf)) nominal is titanium family); its metal itself easily reacts and forms zirconium dioxide protective membrane, so erosion resistance is very strong.In addition this metallic surface intensity is strong, physical strength is high, heat conductivity good.Be widely used in fields such as nuclear power, synthon, petroleum chemistry as the metal of storing flow control more than nine on the earth.Particularly in ceramic product, nuclear power development field, demand increase is very fast.Zirconium amasss in metallic substance minimum to thermal neutron section of cross absorption, and its erosion resistance is very strong, so demand is maximum in nuclear power material.In addition this metal not only mechanical property and erosion resistance very good outside, also with uranium dioxide (UO for nuclear fuel
2) compatibility is very good, is applicable to being used as the core structural material of reactor.
But can not contain Hf (hafnium) in this material of main atom-zirconium of zirconium-base amorphous alloy, so the hafnium (Hf) that will separate is wherein smelted acquisition afterwards.What particularly point out is, chemical action and the character of Zr and Hf are almost identical, but the density of Zr only has the half left and right of Hf, so Hf isolation technique belongs to the most difficult technology in all elements isolation technique, so Hf isolation technique and metallurgical refining are played very large impact to the price of Zr.
Zirconium metal divides a variety of grade separations to produce.Grade 702 Zirconium, Grade 704 Zirconium (Zr-1.5Sn), Grade 705 Zirconium (Zr-2.5Nb), Grade 706 Zirconium (Zr-2.5Nb), Zircaloy-2 (Zr2),Zircaloy-4 (Zr4)。2013 time, crystal zirconium price is about USD120 ~ USD200.Although so its processability brilliance of zirconium-base amorphous alloy, can reduce post-treatment expense, be difficult to compete with techniques such as aluminium alloy casting, magnesium alloy cast, copper alloy casting, MIM in price.
Summary of the invention
In order to overcome the shortcoming and defect existing in prior art, the low price zirconium-base amorphous alloy that the object of the present invention is to provide low price zirconium base alloy ingot that a kind of cost is low and preparation method thereof and make.
Object of the present invention is achieved through the following technical solutions: a kind of zirconium base alloy ingot at a low price, and described low price 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%
Sn 0.5-4%。
Preferably, described low price 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%
Sn 0.5-3%。
More preferred, described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 56.8%
Cu 15.6%
Ni 12.9%
Al 10%
Nb 4.1%
Sn 0.7%。
A preparation method for low price zirconium base alloy ingot, it comprises the following steps:
The preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy, adopt vacuum arc scorification in starting material, contained impurity, can not sneak into other impurities except making, guaranteed the purity of alloy;
Step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price, wherein Zr metal employing model is the Zr metal of Zr2 or Zr4.
Preferably, the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: in order to maintain the purity of alloy, anti-oxidation, the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness 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 steps A 2, melting: being that 51:49 mixes by Nb metal required low price zirconium base alloy ingot and Ni metal according to weight ratio, is melting under 2500-3500 ℃ of condition in temperature; The fusing point of Nb element is about 2470 ℃, belongs to materials with high melting point, and the fusing point of Ni element is about 1453, and Nb element and Ni element are carried out to mixed melting according to above-mentioned weight ratio, can be melting point depression to 1200 ℃.
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy.
Preferably, the preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: in order to maintain the purity of alloy, anti-oxidation, melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for the 20%-30% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melting adopts diffusion melting method, minimize in order to reach zirconium carbide generation, melt temperature can not exceed 1200 ℃, preferably melt temperature is controlled to 1100 ℃-1200 ℃, the fusion time is 60-90min;
Step B3, melting finish: in order to keep glass forming ability and protection ingot mould, will melt soup and be cooled to 900 ℃-950 ℃ in 20-30min, and in order to keep high purity and to dispel smog, then melter will be pumped to 10 with off-gas pump
-1the vacuum tightness of torr;
Step B4, the soup that falls: for cooling rapidly, to the 60-80% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 30-60min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.
Utilize and under vacuum environment, carry out die casting by the produced low price zirconium base alloy of vacuum induction scorification ingot, met cold needed speed of cooling to suppress material crystallization, can produce the low price zirconium-base amorphous alloy of minimum thickness 0.5-maximum ga(u)ge 3mm.
More preferred, when in step B4, molten soup is poured in ingot mould, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
Preferably, all to use purity be more than 99.9% starting material for described Cu metal, Ni metal, Al metal, Nb metal.
A kind of zirconium-base amorphous alloy at a low price, carries out die casting by low price zirconium base alloy ingot, and obtaining thickness is the low price zirconium-base amorphous alloy of 0.5mm-3mm.It should be noted that, the low price zirconium base alloy ingot that step B4 obtains is not complete amorphous, the top layer of zirconium base alloy ingot is amorphous at a low price, and the Inner portion of zirconium base alloy ingot is crystallization at a low price, and the product going out as the die casting of die casting starting material using low price zirconium base alloy ingot is only zirconium-base amorphous alloy at a low price.
Beneficial effect of the present invention is: the present invention Zr-2, Zr-4 substitutes high purity zirconium, then adopts vacuum arc scorification and vacuum high frequency scorification to make zirconium base alloy ingot at a low price.The price of Zr-2 and Zr-4 is about 20-40USD, and high purity zirconium price is about USD120-USD200, and with Zr-2, Zr-4 substitutes high purity zirconium, greatly reduces the price of zirconium base alloy ingot at a low price.Meanwhile, contain the Sn of weight percent 1.4% in Zr2 and Zr4, the maximum range that can displace Nb can reach 50% of Nb content in zirconium base alloy ingot at a low price.Zirconium base alloy ingot carries out die casting under vacuum environment at a low price, meets cold needed speed of cooling to suppress material crystallization, and can produce thickness is the low price zirconium-base amorphous alloy of 0.5-3mm.
Accompanying drawing explanation
Fig. 1 is the broadwise out section after the low price zirconium-base amorphous alloy compression testing of the embodiment of the present invention 1;
Fig. 2 is the broadwise out section after the low price zirconium-base amorphous alloy compression testing of the embodiment of the present invention 4.
embodiment:
For the ease of those skilled in the art's understanding, below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1.
A kind of zirconium base alloy ingot at a low price, described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 65%
Cu 15%
Ni 8%
Al 9%
Nb 2%
Sn 4%。
A preparation method for low price zirconium base alloy ingot, it comprises the following steps:
the preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy, the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness of torr, then pours into high-purity argon gas to melter, and the amount of high-purity argon gas is 60% of melter's volume;
When steps A 2, melting: being that 51:49 mixes according to weight ratio, be 2500 ℃ conditions under melting in temperature by Nb metal required low price zirconium base alloy ingot and Ni metal;
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy.
step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price.The preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for 20% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melt temperature is controlled to 1100 ℃, the fusion time is 80min;
Step B3, melting finish: in 30min, will melt soup and be cooled to 900 ℃, and then with off-gas pump, melter will be pumped to 10
-1the vacuum tightness of torr;
Step B4, the soup that falls: to 60% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 30min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.Wherein, molten soup is poured the speed of ingot mould into, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
Wherein, all to use purity be more than 99.9% starting material for the Cu metal in this preparation method, Ni metal, Al metal, Nb metal.
A kind of zirconium-base amorphous alloy at a low price, carries out die casting by low price zirconium base alloy ingot, and obtaining thickness is the low price zirconium-base amorphous alloy of 3mm.
Embodiment 2.
A kind of zirconium base alloy ingot at a low price, described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 50%
Cu 20%
Ni 17%
Al 5%
Nb 6.5%
Sn 1.5%。
A preparation method for low price zirconium base alloy ingot, it comprises the following steps:
the preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy, the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness of torr, then pours into high-purity argon gas to melter, and the amount of high-purity argon gas is 80% of melter's volume;
When steps A 2, melting: being that 51:49 mixes by Nb metal required low price zirconium base alloy ingot and Ni metal according to weight ratio, is melting under 3000 ℃ of conditions in temperature;
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy, the fusing point of mother alloy is 1200 ℃.
step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price.The preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for 30% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melt temperature is controlled to 1200 ℃, the fusion time is 60min;
Step B3, melting finish: in 20min, will melt soup and be cooled to 900 ℃, and then with off-gas pump, melter will be pumped to 10
-1the vacuum tightness of torr;
Step B4, the soup that falls: to 80% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 60min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.Wherein, molten soup is poured the speed of ingot mould into, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
Wherein, all to use purity be more than 99.9% starting material for the Cu metal in this preparation method, Ni metal, Al metal, Nb metal.
A kind of zirconium-base amorphous alloy at a low price, carries out die casting by low price zirconium base alloy ingot, and obtaining thickness is the low price zirconium-base amorphous alloy of 3mm.
Embodiment 3.
A kind of zirconium base alloy ingot at a low price, described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 56.8%
Cu 15.6%
Ni 12.9%
Al 10%
Nb 4.1%
Sn 0.7%。
A preparation method for low price zirconium base alloy ingot, it comprises the following steps:
the preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy, the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness of torr, then pours into high-purity argon gas to melter, and the amount of high-purity argon gas is 70% of melter's volume;
When steps A 2, melting: be that 51:49 mixes by Nb metal required low price zirconium base alloy ingot and Ni metal according to weight ratio, be melting under 3000 ℃ of conditions in temperature, the low price zirconium base alloy ingot of above-mentioned composition recently says that according to weight percent Nb accounts for 6.03%, Ni and accounts for 9.65%.With regard to Nb, be that in composition, 51% weight comprises all content of 100% (6.03%) at its 2 yuan, with regard to Ni, weigh after 49% (5.75%) weight, when remaining Ni (3.9%) melting for the second time by the time, put into again melting.The actual fusing point of Nb is 2400 about degree, but weight percent is when being Nb:Ni=51:49, and its fusing point can be reduced to 1200 ℃;
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy, the fusing point of mother alloy is 1200 ℃.
step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price.The preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for 25% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melt temperature is controlled to 1150 ℃, the fusion time is 80min;
Step B3, melting finish: in 25min, will melt soup and be cooled to 930 ℃, and then with off-gas pump, melter will be pumped to 10
-1the vacuum tightness of torr;
Step B4, the soup that falls: to 70% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 50min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.Wherein, molten soup is poured the speed of ingot mould into, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
Wherein, all to use purity be more than 99.9% starting material for the Cu metal in this preparation method, Ni metal, Al metal, Nb metal.
A kind of zirconium-base amorphous alloy at a low price, carries out die casting by low price zirconium base alloy ingot, and obtaining thickness is the low price zirconium-base amorphous alloy of 2mm.
Embodiment 4.
A kind of zirconium base alloy ingot at a low price, described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 68%
Cu 10%
Ni 8%
Al 9%
Nb 2%
Sn 3%。
A preparation method for low price zirconium base alloy ingot, it comprises the following steps:
the preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy, the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness of torr, then pours into high-purity argon gas to melter, and the amount of high-purity argon gas is 80% of melter's volume;
When steps A 2, melting: being that 51:49 mixes by Nb metal required low price zirconium base alloy ingot and Ni metal according to weight ratio, is melting under 3500 ℃ of conditions in temperature;
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy.
step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price.The preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for 30% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melt temperature is controlled to 1200 ℃, the fusion time is 80min;
Step B3, melting finish: in 30min, will melt soup and be cooled to 950 ℃, and then with off-gas pump, melter will be pumped to 10
-1the vacuum tightness of torr;
Step B4, the soup that falls: to 80% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 60min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.Wherein, molten soup is poured the speed of ingot mould into, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
Wherein, all to use purity be more than 99.9% starting material for the Cu metal in this preparation method, Ni metal, Al metal, Nb metal.
A kind of zirconium-base amorphous alloy at a low price, carries out die casting by low price zirconium base alloy ingot, and obtaining thickness is the low price zirconium-base amorphous alloy of 1mm.
Test 1, the low price zirconium-base amorphous alloy differential scanning calorimeter that embodiment 1-4 is obtained are analyzed, and find non-existent Tg interval in xln structure, thereby have confirmed non-crystal structure.Meanwhile, in noncrystal, can see and not start there is clear and definite GTT (glassy transition phenomenon) before crystallization.
Test 2, see Fig. 1 and Fig. 2, the broadwise out section after the low price zirconium-base amorphous alloy compression testing that observation embodiment 1 and embodiment 4 obtain, can see non-crystalline state fine pulse-like tissue, does not see the frangible fracture form that xln just has.
The physical and mechanical properties such as yield strength, consistency and elasticity distortion of test 3, low price zirconium-base amorphous alloy that embodiment 1-4 is obtained is tested, and refers to table 1.
Can find out by table 1, the yield strength of the low price zirconium-base amorphous alloy that embodiment of the present invention 1-4 obtains, consistency and elasticity distortion etc. physical and mechanical properties is good.
Above-described embodiment is preferably implementation of the present invention, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (9)
1. a low price zirconium base alloy ingot, is characterized in that: described low price 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%
Sn 0.5-4%。
2. low price zirconium base alloy ingot according to claim 1, is characterized in that: described low price 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%
Sn 0.5-3%。
3. low price zirconium base alloy ingot according to claim 1, is characterized in that: described low price zirconium base alloy ingot is made up of the atom of following atomic percent:
Zr 56.8%
Cu 15.6%
Ni 12.9%
Al 10%
Nb 4.1%
Sn 0.7%。
4. a preparation method for low price zirconium base alloy ingot, is characterized in that: it comprises the following steps:
The preparation of steps A, mother alloy: Nb metal required low price zirconium base alloy ingot and part Ni metal are carried out to melting by vacuum arc scorification, obtain mother alloy;
Step B, the preparation of zirconium base alloy ingot at a low price: the mother alloy that steps A is obtained and at a low price required Zr metal, Cu metal, Al metal and the remaining Ni metal of zirconium base alloy ingot, carry out melting by vacuum high frequency scorification, obtain zirconium base alloy ingot at a low price, wherein Zr metal employing model is the Zr metal of Zr2 or Zr4.
5. the preparation method of low price zirconium base alloy ingot according to claim 4, is characterized in that: the preparation of described steps A mother alloy specifically comprises the following steps:
Before steps A 1, melting: the melter of vacuum arc melting furnace is evacuated to 10
-4the vacuum tightness 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 steps A 2, melting: being that 51:49 mixes by Nb metal required low price zirconium base alloy ingot and Ni metal according to weight ratio, is melting under 2500-3500 ℃ of condition in temperature;
Steps A 3, melting finish: after melting finishes, carry out coolingly, obtain mother alloy.
6. the preparation method of low price zirconium base alloy ingot according to claim 4, is characterized in that: the preparation of described step B secondary alloy specifically comprises the following steps:
Before step B1, melting: melter is evacuated to 10
-4the vacuum tightness of torr pours into high-purity argon gas in melter, and the volume of high-purity argon gas accounts for the 20%-30% of whole melter volume;
When step B2, melting: mother alloy and required Zr metal, Cu metal, Al metal and the remaining Ni metal of low price zirconium base alloy ingot are carried out to melting in the melter of vacuum high frequency smelting furnace, melt temperature is controlled to 1100 ℃-1200 ℃, and the fusion time is 60-90min;
Step B3, melting finish: in 20-30min, will melt soup and be cooled to 900 ℃-950 ℃, and then with off-gas pump, melter will be pumped to 10
-1the vacuum tightness of torr;
Step B4, the soup that falls: to the 60-80% argon gas that pours into whole cooling room volume in the cooling room of ingot mould, start circulation hot exchange board, then will melt soup and pour in ingot mould through the cooling 30-60min of circulation hot exchange board, obtain zirconium base alloy ingot at a low price.
7. the preparation method of low price zirconium base alloy ingot according to claim 6, is characterized in that: when in step B4, molten soup is poured in ingot mould, need to carry out with the speed of the interior 50kg of pouring into according to 3min.
8. the preparation method of low price zirconium base alloy ingot according to claim 4, is characterized in that: it is more than 99.9% starting material that described Cu metal, Ni metal, Al metal and Nb metal all use purity.
9. a low price zirconium-base amorphous alloy, is characterized in that: low price zirconium base alloy ingot as claimed in claim 4 is carried out to die casting, and obtaining thickness is the low price zirconium-base amorphous alloy of 0.5mm-3mm.
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| CN104190896A (en) * | 2014-09-26 | 2014-12-10 | 东莞台一盈拓科技股份有限公司 | Electric arc smelting pressure casting method for amorphous alloy |
| CN104451468A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451472A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451470A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451464A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104550823A (en) * | 2015-01-14 | 2015-04-29 | 东莞台一盈拓科技股份有限公司 | Application of amorphous alloy in preparation of electronic products |
| CN104668502A (en) * | 2015-02-11 | 2015-06-03 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy locating plate for repetitive locating fixture and manufacturing method of amorphous alloy locating plate |
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| CN114015953A (en) * | 2021-11-11 | 2022-02-08 | 盘星新型合金材料(常州)有限公司 | Non-toxic nickel-free Zr-based amorphous alloy and preparation method thereof |
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| CN104190896A (en) * | 2014-09-26 | 2014-12-10 | 东莞台一盈拓科技股份有限公司 | Electric arc smelting pressure casting method for amorphous alloy |
| 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 |
| CN104451464A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451468A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451472A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104451470A (en) * | 2014-12-29 | 2015-03-25 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy spectacle frame and glass and production method thereof |
| CN104550823A (en) * | 2015-01-14 | 2015-04-29 | 东莞台一盈拓科技股份有限公司 | Application of amorphous alloy in preparation of electronic products |
| WO2016112507A1 (en) * | 2015-01-14 | 2016-07-21 | 东莞帕姆蒂昊宇液态金属有限公司 | Watch case of amorphous alloy, watch and manufacturing method therefor |
| CN104668502A (en) * | 2015-02-11 | 2015-06-03 | 东莞台一盈拓科技股份有限公司 | Amorphous alloy locating plate for repetitive locating fixture and manufacturing method of amorphous alloy locating plate |
| CN105220085A (en) * | 2015-10-21 | 2016-01-06 | 东莞宜安科技股份有限公司 | A kind of high strength non-crystaline amorphous metal and its preparation method and application |
| 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 |
| CN110157996A (en) * | 2019-05-10 | 2019-08-23 | 河北工业大学 | A kind of new type corrosion resistant zirconium-base 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 |
| CN113802072A (en) * | 2020-06-17 | 2021-12-17 | 株式会社Bmg | Deformation induced zirconium based alloy |
| CN114015953A (en) * | 2021-11-11 | 2022-02-08 | 盘星新型合金材料(常州)有限公司 | Non-toxic nickel-free Zr-based amorphous alloy and preparation method thereof |
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