WO2015096479A1 - Zirconium-based amorphous alloy and preparation method therefor - Google Patents

Zirconium-based amorphous alloy and preparation method therefor Download PDF

Info

Publication number
WO2015096479A1
WO2015096479A1 PCT/CN2014/083461 CN2014083461W WO2015096479A1 WO 2015096479 A1 WO2015096479 A1 WO 2015096479A1 CN 2014083461 W CN2014083461 W CN 2014083461W WO 2015096479 A1 WO2015096479 A1 WO 2015096479A1
Authority
WO
WIPO (PCT)
Prior art keywords
zirconium
alloy
amorphous alloy
based amorphous
purity
Prior art date
Application number
PCT/CN2014/083461
Other languages
French (fr)
Chinese (zh)
Inventor
张法亮
Original Assignee
深圳市比亚迪汽车研发有限公司
比亚迪股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳市比亚迪汽车研发有限公司, 比亚迪股份有限公司 filed Critical 深圳市比亚迪汽车研发有限公司
Publication of WO2015096479A1 publication Critical patent/WO2015096479A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

Definitions

  • the present invention relates to the field of materials, and more particularly, to a zirconium-based amorphous alloy and a method of preparing the same. Background technique
  • Amorphous alloys have attracted a lot of research by researchers because of their high strength, high hardness, corrosion resistance and excellent high temperature fluidity. Their critical dimensions have gradually evolved from micron to millimeters and even to centimeters. . Generally, an amorphous alloy having a critical cooling rate of less than 500 ° C / s and a critical dimension of more than 1 mm is called a bulk amorphous alloy. The emergence of bulk amorphous alloys has made it possible to industrialize production.
  • amorphous forming ability of amorphous alloys is easily affected by non-metallic elements or impurity elements, resulting in a significant reduction in the critical dimensions of amorphous alloys or even in the formation of amorphous, especially non-metallic gas elements such as oxygen and nitrogen.
  • the critical dimension of the alloy Therefore, in the manufacture of amorphous alloys, the purity of raw materials is usually very demanding, and the environment for smelting is also very strict, even under high vacuum preparation conditions. Not only greatly increases the cost of actual production of amorphous alloys, but also makes it difficult to promote industrial production.
  • an object of the present invention is to provide a zirconium-based amorphous alloy which has a low purity requirement, a large critical dimension, and a good mechanical property, and a preparation method thereof.
  • the invention provides a zirconium-based amorphous alloy.
  • the invention also provides a method of preparing a zirconium-based amorphous alloy.
  • the method comprises: melting and cooling a raw material of a zirconium-based amorphous alloy under inert gas protection or under vacuum, wherein the raw material of the zirconium-based amorphous alloy comprises Zr, Cu , Al, Er, Y and ⁇ , and the amounts of Zr, Cu, Al, Er, Y and M can be effectively formed
  • ⁇ is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy
  • the Er element is added to the composition of the zirconium-based amorphous alloy provided by the present invention, and the combination of Er and Y in a specific ratio can not only improve the amorphous forming ability of the amorphous alloy, but also obtain a critical dimension larger, and The mechanical properties of crystalline alloys are less affected.
  • the zirconium-based amorphous alloy provided by the invention is more favorable for the industrial production of the amorphous alloy, for example, can allow higher content of the magazine gas element, greatly reduce the requirements for the smelting vacuum environment; can reduce the requirement for material purity, The use of industrial grade zirconium material can greatly reduce the material cost of amorphous alloys.
  • the invention provides a zirconium-based amorphous alloy.
  • the inventors have found that the introduction of rare earth elements into zirconium-based amorphous alloys can reduce the purity requirements of raw materials and improve the amorphous forming ability of zirconium-based amorphous alloys, but the amorphous forming ability of zirconium-based amorphous alloys is amorphous.
  • the type and amount of rare earth elements added to the alloy are very sensitive, and the type and amount of rare earth elements added may have an important influence on the mechanical properties of the amorphous alloy.
  • the inventors have found that the addition of the rare earth element Y can significantly improve the amorphous forming ability of the amorphous alloy and can increase the critical size of the amorphous alloy, but the addition of the rare earth element Y can significantly reduce the obtained zirconium-based non- The mechanical properties of crystalline alloys are not conducive to the engineering application of amorphous alloys.
  • the rare earth element Er is introduced, and Er and Y are combined in a specific ratio, which can not only effectively improve the amorphous forming ability of the zirconium-based amorphous alloy, but also the zirconium-based amorphous alloy.
  • the effect of mechanical properties can be much less than the addition of rare earth element Y alone.
  • the zirconium-based amorphous alloy of this composition has a better amorphous forming ability, and industrial grade raw materials can be used, thereby reducing the cost of producing an amorphous alloy. Moreover, the zirconium-based amorphous alloy having the above composition has good bending strength even if it has a high oxygen content, reduces the manufacturing requirements for producing an amorphous alloy, and has a better industrial production application prospect.
  • the composition of the zirconium-based amorphous alloy is: Zr 5 i.9Cu3oAlioNi 7 (Ero.9iYo.o9)ii, Zr 5 iCu3oAlioNi 7 Hfi(Ero.8Yo.2)i ,
  • d represents a corresponding atomic percentage of the element in the zirconium-based amorphous alloy, such as Where M is Ni.
  • the rare earth element Er is added to the composition of the zirconium-based amorphous alloy provided by the present invention, and the rare earth elements Er and Y are combined in a specific amount, which can improve the amorphous forming ability of the zirconium-based amorphous alloy, and can allow impurities, especially impurities, to be contained.
  • the content of gas elements is higher than when the rare earth element Y is added alone, which greatly reduces the requirements for the smelting vacuum environment.
  • the zirconium-based amorphous alloy has an oxygen element content of 100 ppm or less.
  • rare earth elements Er and Y which are combined in a specific amount are added to the composition of the zirconium-based amorphous alloy of the present invention, and an impurity element may be present in the zirconium-based amorphous alloy.
  • the atomic percentage of the metal impurity element in the zirconium-based amorphous alloy is 2% or less based on the total amount of the zirconium-based amorphous alloy.
  • the amorphous forming ability of the zirconium-based amorphous alloy is remarkably improved.
  • the zirconium-based amorphous alloy has a critical dimension of 3 mm or more.
  • the invention also provides a method of preparing a zirconium-based amorphous alloy.
  • the method comprises: melting and cooling a raw material of a zirconium-based amorphous alloy under inert gas protection or under vacuum, wherein the raw material of the zirconium-based amorphous alloy comprises Zr, Cu , Al, Er, Y and ⁇ , and the amounts of Zr, Cu, Al, Er, Y and M can be effectively formed
  • ⁇ is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy
  • the raw materials of the zirconium-based amorphous alloy described above include Zr, Cu, Al, Er, Y, and M.
  • the raw materials of the zirconium-based amorphous alloy include Zr, Cu, Al, Er, Y, and M elements. While the form of the Zr, Cu, Al, Er, Y, and M elements is not particularly limited in the process of preparing the zirconium-based amorphous alloy, including but not limited to, it is provided in the form of a simple substance, an alloy, or a compound.
  • the production of the zirconium-based amorphous alloy may be carried out using a raw material of a low-purity amorphous alloy.
  • the purity of the raw material of the zirconium-based amorphous alloy is industrial grade, wherein the purity of the Zr, Cu, Al, and M metals is 99% by weight or more.
  • industrial grade HZr-1 can be used for the zirconium material
  • industrial grade metal raw materials with a purity of 99% by weight or more can be used for the metal raw materials Cu, A1 and M.
  • the zirconium-based amorphous alloy does not need to add an expensive element Sc, thereby greatly reducing the raw material cost of the alloy.
  • the rare earth metal may also be selected from low purity raw materials. According to some embodiments of the present invention, the purity of Er and Y is 98% by weight or more. In view of the fact that the rare earth element is an easily oxidizable element, and in order to facilitate smelting and mixing with the master alloy, it is preferred to add the rare earth element in the form of an intermediate alloy.
  • the Er and Y are provided in the form of an AIRE alloy, wherein RE represents a combination of Er and Y.
  • the preparation of a zirconium-based amorphous alloy by adding a rare earth element Er can improve the forming ability of the amorphous alloy, and the obtained zirconium-based amorphous alloy is allowed to have an oxygen content of less than 1000 ppm, which can reduce the vacuum environment during smelting.
  • the requirement for vacuum conditions during the smelting is less than 500 Pa. According to a preferred embodiment of the invention, the requirement for vacuum conditions during said smelting is less than 100 Pa.
  • the inert gas protection or vacuum conditions are such that the zirconium-based amorphous alloy material is protected from oxidation during the smelting process.
  • the zirconium-based amorphous alloy material of the present invention has a good oxidation resistance, and therefore requires less inert gas protection or vacuum conditions.
  • the inert gas is one or more of a group of elemental gases in the periodic table.
  • the inert gas may have a purity of not less than 95% by volume, and may be, for example, 95 to 99.99% by volume.
  • the method of smelting may be various conventional smelting methods in the art as long as the zirconium-based amorphous alloy material is sufficiently melted.
  • the smelting may be vacuum induction melting, vacuum arc melting or vacuum consumable electrode melting.
  • the smelting may be carried out in a smelting apparatus, and the smelting temperature and the smelting time may vary depending on the amorphous alloy raw material.
  • the smelting temperature may be 1000-1500 ° C; the smelting time may be 10-50 minutes, preferably 10-30 minutes.
  • the smelting apparatus may be a conventional smelting apparatus such as a vacuum arc melting furnace, a vacuum induction melting furnace or a vacuum resistance furnace.
  • the zirconium-based amorphous alloy of the present invention has a strong amorphous forming ability, and the cooling molding can employ various conventional pressure casting molding methods in the art, for example, pressure casting a molten alloy material (melt) into a mold. Then cool down.
  • the pressure casting method may be any one of gravity casting, negative pressure casting, positive pressure casting, and high pressure casting, and casting conditions such as casting pressure are known to those skilled in the art, for example, high pressure.
  • the casting pressure can be 2-20 MPa.
  • the gravity casting refers to casting into a mold by the gravity of the melt itself. The specific method of operation of the casting is well known to those skilled in the art.
  • the mold material may be a copper alloy, stainless steel, and various mold steel materials having a thermal conductivity of 30-400 W/m*K (preferably 50-200 W/m*K).
  • the mold can be water cooled and oil cooled. There is no special requirement for the degree of cooling, as long as it can be formed into the amorphous alloy of the present invention, the cooling rate can be 500. K/S or above.
  • the alloys prepared in the following examples and comparative examples were analyzed for whether they were amorphous by an XRD diffractometer (Japanese Science D/Max 2200PC).
  • the critical dimension of the amorphous alloy prepared by XRD diffractometer (Japanese Science D/Max 2500PC) was analyzed.
  • the diffraction angle was 2 ⁇ between 20 ° - 60 °
  • the scanning speed was 4 ° / min
  • the scanning voltage was 40 kV
  • the current was 200 mA. .
  • the oxygen content in the prepared amorphous alloy was measured by an oxygen-nitrogen content tester (Beijing Nike IRO-II infrared oxygen meter) with an instrument accuracy of 0.5% by weight of RSD and a high purity Ar of protective gas.
  • composition of the prepared amorphous alloy was analyzed by inductively coupled plasma optical emission spectroscopy using a full spectrum direct reading inductively coupled plasma optical emission spectrometer (ICP-AES) (American Thermo Electron Corporation, model TEVA).
  • ICP-AES inductively coupled plasma optical emission spectrometer
  • the flexural strength of the prepared amorphous alloy was measured in accordance with the method of ISO 6892.1-2009 using a universal testing machine (INSTRON).
  • This embodiment illustrates the preparation method of the zirconium-based amorphous alloy ZrswCu ⁇ A ⁇ N Er wYo.u provided by the present invention.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is an elemental metal having a metal purity of more than 99% by weight, and Al, Cu, Ni, Er, Y are elemental metals having a purity of more than 99% by weight.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a circle having a diameter of 2-20 mm and a height of 20 mm.
  • the alloy sample A1 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A1 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample A1 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A1 are shown in Table 1.
  • Example 2 This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi ⁇ Cu ⁇ AhoNi Hf ⁇ Ei ⁇ Y ⁇ provided by the present invention.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y. .
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • Metal casting recorded as alloy sample A2.
  • the alloy sample A2 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A2 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample A2 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A2 are shown in Table 1.
  • This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi ⁇ Cu ⁇ A oMwHfiTio ⁇ Er ⁇ Y ⁇ provided by the present invention.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y.
  • Ti is made of AlTi master alloy.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • the metal casting was recorded as alloy sample A3.
  • the alloy sample A3 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A3 was an amorphous alloy.
  • the critical dimensions of the alloy sample A3 were measured, and the results are shown in Table 1.
  • the oxygen content and composition of the alloy sample A3 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A3 are shown in Table 1.
  • This embodiment illustrates the preparation of a zirconium-based amorphous alloy Zr 51 Cu 27 Al 8 Ni 7 Co 3 Hf 0 . 8 Fe 2 . 5 Ti 0 . 49 (Er 0 . 52 Y 0 . 48 ) 0 . 21 provided by the present invention. method.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y.
  • Fe and Ti are respectively made of an intermediate alloy containing aluminum.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • the metal casting was recorded as alloy sample A4.
  • the alloy sample A4 was subjected to XRD powder diffraction analysis, and the XRD spectrum obtained was a diffraction peak having a peak shape of a taro peak, indicating that the alloy sample A4 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample A4 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A4 are shown in Table 1.
  • This example illustrates the Zr-based amorphous alloy of the present invention provides Zr 51. 5 C U29 Al 1Q Ni 7 (E r 8 Y Q. 2) Preparation Method 2. 5.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, and the purity of Al, Cu, Ni, Er, Y is more than 99. Amount of elemental metal, Er and Y use AlErY master alloy.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • the metal casting was recorded as alloy sample A5.
  • the alloy sample A5 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A5 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample A5 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A5 are shown in Table 1.
  • This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi ⁇ Cu AlsM ⁇ Ei ⁇ Yo ⁇ provided by the present invention.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, Ni, Er, and Y are elemental metals having a purity of more than 99% by weight, and Er and yttrium are made of an AlErY master alloy.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • the metal casting was recorded as alloy sample A6.
  • the alloy sample A6 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample A1 was an amorphous alloy.
  • the alloy sample A6 oxygen content and composition were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample A6 are shown in Table 1.
  • This comparative example illustrates the preparation of a zirconium-based amorphous alloy ZrswCu ⁇ AhoNi Eru.
  • the raw materials of each component were put into a vacuum melting furnace, and the vacuum was 50 Pa, and the purity was 99.99% by volume.
  • the specific argon gas was used as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes to sufficiently melt the alloy raw material. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, M, and Er are elemental metals having a purity of more than 99% by weight, and Er is an AlEr master alloy.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • Metal casting recorded as alloy sample Dl.
  • the alloy sample D1 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D1 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample D1 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample D1 are shown in Table 1.
  • This comparative example illustrates the preparation method of zirconium-based amorphous alloy Zi ⁇ .sCu ⁇ AhoNi HftEi ⁇ .
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of industrial grade HZr-1 zirconium having a metal purity of more than 99% by weight, Al, Cu, Ni, Hf, Er are elemental metals having a purity of more than 99% by weight, and Er is an AlEr master alloy.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • Metal casting denoted alloy sample D2.
  • the alloy sample D2 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D2 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample D2 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample D2 are shown in Table 1.
  • This comparative example illustrates the preparation of a zirconium-based amorphous alloy Zi ⁇ O ⁇ AhoHftNi Yz.
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of industrial grade HZr-1 zirconium having a metal purity of more than 99% by weight, Al, Cu, M, Hf, Y are elemental metals having a purity of more than 99% by weight, and the A1Y master alloy is used.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • Metal casting recorded as alloy sample D3.
  • the alloy sample D3 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D3 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample D3 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample D3 are shown in Table 1.
  • This comparative example illustrates the preparation method of zirconium-based amorphous alloy Zr 52 . 9 Cu 3Q Al 1Q Ni 7 (Er Q . 67 Y Q . 33 u 5 .
  • the raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, Ni, Er, and Y are elemental metals having a purity of more than 99% by weight, and Er and yttrium are made of an AlErY master alloy.
  • the proportioned metal was put into a vacuum melting furnace and filled with 99.99% of argon gas for atmosphere protection to carry out alloying and smelting, the smelting temperature was 1100 ° C, and the smelting time was 15 min.
  • the smelting temperature during the smelting process is obtained by infrared temperature measurement.
  • the molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm.
  • Metal casting denoted alloy sample D4.
  • the alloy sample D4 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D4 was an amorphous alloy.
  • the oxygen content and composition of the alloy sample D4 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage.
  • the results of the amorphous alloy composition of the alloy sample D4 are shown in Table 1.
  • metal zirconium adopts elemental metal with metal purity greater than 99.9% by weight
  • Al, Cu, Ni, Er, Y adopts elemental metal with purity greater than 99.9% by weight
  • Elemental metals having a metal purity greater than 99% by weight, Al, Cu, Ni, Er, Y are elemental metals having a purity greater than 99% by weight.
  • the alloy sample D5 was obtained.
  • the critical dimensions, oxygen content, composition and flexural strength of the alloy are shown in Table 1.
  • the zirconium-based amorphous alloy provided by the present invention can improve the amorphous forming ability and can obtain a larger critical size in the case of using industrial grade raw materials. Moreover, it still has a high bending strength in the case of a high oxygen content, indicating that the amorphous alloy provided by the present invention has a small severity required for the manufacturing process, and the oxygen content has little influence on the mechanical properties.
  • a rare earth element Er and Y a molar ratio of atoms between Er and Y satisfying 0 ⁇ x ⁇ 0.5
  • a combination of ErY are contained in a specific ratio composition.
  • Comparative Examples 1-3 did not employ a specific combination of Er and Y. Comparative Example 1 Compared with Example 1 and Comparative Example 2, Example 2, the composition of the amorphous alloy in the comparative example was only Er, and the critical dimensions of the alloy samples D1 and D2 obtained when using the industrial grade raw material were smaller than the implementation. Alloy samples A1 and A2 of Examples 1 and 2.
  • Comparative Example 3 Compared with Example 1, the composition of the amorphous alloy was only Y, and the alloy sample D3 obtained when the industrial grade raw material was used had a bending strength which was not as good as that of the alloy sample A1 of Example 1 even though the oxygen content was low. In the amorphous alloy of Comparative Example 4, although Er and Y were also present, the atomic percentage of the ErY combination was not within the range specified by the present invention, so the alloy sample D4 obtained when the industrial grade raw material was used had a small critical dimension and poor bending strength.
  • Comparative Example 5 requires the use of a higher purity raw material than Comparative Example 4 to obtain both a large critical dimension and a high bending strength, but in the actual industrial production, the manufacturing cost of the amorphous alloy will be greatly increased, and there is no practical industrial production significance. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
  • Powder Metallurgy (AREA)

Abstract

A zirconium-based amorphous alloy and a preparation method therefor. The composition of the amorphous alloy is ZraCubAlcMd(Er1-xYx)e, wherein M is at least one selected from Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, 40≤a≤70, 15≤b≤35, 5≤c≤15, 3≤d≤15, 0.2＜e≤2.5, and 0＜x＜0.5, and the amorphous alloy is obtained by smelting and cooling molding under the protection of an inert gas or a vacuum condition.

Description

锆基非晶合金及其制备方法  Zirconium-based amorphous alloy and preparation method thereof
技术领域 Technical field
本发明涉及材料领域， 更具体的， 本发明涉及锆基非晶合金及其制备方法。 背景技术  The present invention relates to the field of materials, and more particularly, to a zirconium-based amorphous alloy and a method of preparing the same. Background technique
非晶合金因具有高强度、 高硬度、 耐腐蚀和优异的高温流动性等材料性能吸引了广大 科研工作者进行不断的研究， 其临界尺寸逐渐从微米级发展到毫米级甚者可达到厘米级。 通常情况下把临界冷却速率小于 500°C/s， 临界尺寸大于 1mm的非晶合金称为大块非晶合 金。 大块非晶合金的出现为工业化生产提供了可能。  Amorphous alloys have attracted a lot of research by researchers because of their high strength, high hardness, corrosion resistance and excellent high temperature fluidity. Their critical dimensions have gradually evolved from micron to millimeters and even to centimeters. . Generally, an amorphous alloy having a critical cooling rate of less than 500 ° C / s and a critical dimension of more than 1 mm is called a bulk amorphous alloy. The emergence of bulk amorphous alloys has made it possible to industrialize production.
但是， 非晶合金的非晶形成能力很容易受到非金属元素或杂质元素的影响， 导致非晶 合金临界尺寸的大幅减小甚至无法形成非晶， 尤其氧氮等非金属气体元素会大幅恶化非经 合金的临界尺寸。 因而， 在制造非晶合金时， 通常对原材料的纯度有非常苛刻的要求， 并 且对冶炼的环境也要求非常严格， 甚至需要在高真空的制备条件下。 不仅大大增加了非晶 合金实际生产的成本， 且难于推广进行工业化生产。  However, the amorphous forming ability of amorphous alloys is easily affected by non-metallic elements or impurity elements, resulting in a significant reduction in the critical dimensions of amorphous alloys or even in the formation of amorphous, especially non-metallic gas elements such as oxygen and nitrogen. The critical dimension of the alloy. Therefore, in the manufacture of amorphous alloys, the purity of raw materials is usually very demanding, and the environment for smelting is also very strict, even under high vacuum preparation conditions. Not only greatly increases the cost of actual production of amorphous alloys, but also makes it difficult to promote industrial production.
因而， 目前关于非晶合金的研究仍有待深入。 发明内容  Therefore, the current research on amorphous alloys remains to be deepened. Summary of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。 为此， 本发明的一个 目的在于提出一种对原料纯度要求较低， 临界尺寸较大， 且机械性能较好的锆基非晶合金 及其制备方法。  The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to provide a zirconium-based amorphous alloy which has a low purity requirement, a large critical dimension, and a good mechanical property, and a preparation method thereof.
在本发明的一个方面， 本发明提供一种锆基非晶合金。 根据本发明的实施例， 该锆基 非晶合金的组成为：
Figure imgf000002_0001
其中， M为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf和 Ta中的至少一种， a、 b、 c、 d和 e为各元素在该锆基非晶合金中对应的原子百分数， 分别为： 40 a 70， 15^b=¾35, 5^c=¾ 15, 3^d=¾ 15, 0.2<e=¾2.5, 0<x<0.5。 In one aspect of the invention, the invention provides a zirconium-based amorphous alloy. According to an embodiment of the invention, the composition of the zirconium-based amorphous alloy is:
Figure imgf000002_0001
Wherein M is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy The percentages are: 40 a 70, 15^b=3⁄435, 5^c=3⁄4 15, 3^d=3⁄4 15, 0.2<e=3⁄42.5, 0<x<0.5.
在本发明的另一方面， 本发明还提供了一种制备锆基非晶合金的方法。 根据本发明的 实施例， 该方法包括： 在惰性气体保护下或真空条件下， 将锆基非晶合金的原料进行熔炼 并冷却成型， 其中， 所述锆基非晶合金的原料包括 Zr、 Cu、 Al、 Er、 Y和 Μ， 并且所述 Zr、 Cu、 Al、 Er、 Y和 M的量能有效形成
Figure imgf000002_0002
其中， Μ为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf和 Ta中的至少一种， a、 b、 c、 d和 e为各元素在该锆基非晶合金中 对应的原子百分数， 分别为： 40 a 70， 15^b=¾35, 5^c=¾ 15, 3^d=¾ 15, 0.2<e=¾2.5, 0<x<0.5。 本发明提供的锆基非晶合金的组成中加入了 Er元素， 并且 Er和 Y以特定比例组合， 不仅可以提高该非晶合金的非晶形成能力， 获得的临界尺寸更大， 而且对该非晶合金的机 械性能影响更小。 另外本发明提供的锆基非晶合金更有利于非晶合金的工业化生产制造， 例如可以允许更高的杂志气体元素含量， 大大降低对冶炼真空环境的要求； 可以降低对材 料纯度的要求， 可以选用工业级的锆材， 可以大大降低非晶合金的材料成本。 In another aspect of the invention, the invention also provides a method of preparing a zirconium-based amorphous alloy. According to an embodiment of the present invention, the method comprises: melting and cooling a raw material of a zirconium-based amorphous alloy under inert gas protection or under vacuum, wherein the raw material of the zirconium-based amorphous alloy comprises Zr, Cu , Al, Er, Y and Μ, and the amounts of Zr, Cu, Al, Er, Y and M can be effectively formed
Figure imgf000002_0002
Wherein Μ is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy The percentages are: 40 a 70, 15^b=3⁄435, 5^c=3⁄4 15, 3^d=3⁄4 15, 0.2<e=3⁄42.5, 0<x<0.5. The Er element is added to the composition of the zirconium-based amorphous alloy provided by the present invention, and the combination of Er and Y in a specific ratio can not only improve the amorphous forming ability of the amorphous alloy, but also obtain a critical dimension larger, and The mechanical properties of crystalline alloys are less affected. In addition, the zirconium-based amorphous alloy provided by the invention is more favorable for the industrial production of the amorphous alloy, for example, can allow higher content of the magazine gas element, greatly reduce the requirements for the smelting vacuum environment; can reduce the requirement for material purity, The use of industrial grade zirconium material can greatly reduce the material cost of amorphous alloys.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。 具体实施方式  Other features and advantages of the invention will be described in detail in the detailed description which follows. detailed description
以下对本发明的具体实施方式进行详细说明。 应当理解的是， 此处所描述的具体实施 方式仅用于说明和解释本发明，并不用于限制本发明。实施例中未注明具体技术或条件的， 按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。 所用试剂或仪器未注 明生产厂商者， 均为可以通过市购获得的常规产品。  Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are intended to be illustrative and not restrictive. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that are commercially available.
在本发明的一个方面， 本发明提供一种锆基非晶合金。 根据本发明的实施例， 该锆基 非晶合金的组成为：
Figure imgf000003_0001
其中， M为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf和 Ta中的至少一种， a、 b、 c、 d和 e为各元素在该锆基非晶合金中对应的原子百分数， 分别为： 40 a 70， 15^b=¾35 , 5^c=¾ 15 , 3 ^d=¾ 15 , 0.2<e=¾2.5 , 0<x<0.5。 In one aspect of the invention, the invention provides a zirconium-based amorphous alloy. According to an embodiment of the invention, the composition of the zirconium-based amorphous alloy is:
Figure imgf000003_0001
Wherein M is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy The percentages are: 40 a 70, 15^b=3⁄435 , 5^c=3⁄4 15 , 3 ^d=3⁄4 15 , 0.2<e=3⁄42.5 , 0<x<0.5.
发明人发现， 在锆基非晶合金中引入稀土元素虽然可以降低对原材料的纯度的要求， 提高锆基非晶合金的非晶形成能力， 但是锆基非晶合金的非晶形成能力对非晶合金中添加 的稀土元素的种类和数量非常敏感， 而且添加的稀土元素的种类和数量会对非晶合金的机 械性能产生重要影响。 另外， 发明人发现， 加入稀土元素 Y虽然可以显著地提高非晶合金 的非晶形成能力， 并且可以提高非晶合金的临界尺寸， 但是添加过量的稀土元素 Y， 会显 著降低得到的锆基非晶合金的机械性能， 而不利于非晶合金的工程应用。  The inventors have found that the introduction of rare earth elements into zirconium-based amorphous alloys can reduce the purity requirements of raw materials and improve the amorphous forming ability of zirconium-based amorphous alloys, but the amorphous forming ability of zirconium-based amorphous alloys is amorphous. The type and amount of rare earth elements added to the alloy are very sensitive, and the type and amount of rare earth elements added may have an important influence on the mechanical properties of the amorphous alloy. In addition, the inventors have found that the addition of the rare earth element Y can significantly improve the amorphous forming ability of the amorphous alloy and can increase the critical size of the amorphous alloy, but the addition of the rare earth element Y can significantly reduce the obtained zirconium-based non- The mechanical properties of crystalline alloys are not conducive to the engineering application of amorphous alloys.
本发明提供的锆基非晶合金中， 引入稀土元素 Er， 并且 Er和 Y以特定比例组合， 不 仅可以有效地提高该锆基非晶合金的非晶形成能力， 而且对该锆基非晶合金的机械性能的 影响可以远小于单独加入稀土元素 Y。  In the zirconium-based amorphous alloy provided by the present invention, the rare earth element Er is introduced, and Er and Y are combined in a specific ratio, which can not only effectively improve the amorphous forming ability of the zirconium-based amorphous alloy, but also the zirconium-based amorphous alloy. The effect of mechanical properties can be much less than the addition of rare earth element Y alone.
根据本发明的实施例，本发明的锆基非晶合金的组成为： ZraCubAlcMd(Er1-xYx)e,其中， M为选自 Ni、 Fe、 Co、 Ti和 Hf中的至少一种， a、 b、 c、 d和 e为各元素在该锆基非晶合 金中对应的原子百分数， 分别为： 40 a 70， 15 ^b=¾35 , 5 ^c=¾ 15 , 3 ^d=¾ 15 , 0.2<e ^2.5 , 0<x<0.5。 此组成的锆基非晶合金具有更好的非晶形成能力， 可以使用工业级原材 料， 从而降低生产非晶合金的成本。 并且具有上述组成的锆基非晶合金即使含氧量高， 仍 然具有好的弯曲强度， 降低了生产非晶合金的制造要求， 有更好的工业生产应用前景。 According to an embodiment of the present invention, the composition of the zirconium-based amorphous alloy of the present invention is: Zr a Cu b Al c M d (Er 1-x Y x ) e , wherein M is selected from the group consisting of Ni, Fe, Co, Ti And at least one of Hf, a, b, c, d and e are the corresponding atomic percentages of the respective elements in the zirconium-based amorphous alloy, respectively: 40 a 70, 15 ^ b = 3⁄435 , 5 ^ c = 3⁄4 15 , 3 ^d=3⁄4 15 , 0.2<e ^2.5 , 0<x<0.5. The zirconium-based amorphous alloy of this composition has a better amorphous forming ability, and industrial grade raw materials can be used, thereby reducing the cost of producing an amorphous alloy. Moreover, the zirconium-based amorphous alloy having the above composition has good bending strength even if it has a high oxygen content, reduces the manufacturing requirements for producing an amorphous alloy, and has a better industrial production application prospect.
根据本发 明 的一些优选实施例 ， 所述锆基非 晶合金的组成为 ： Zr5i.9Cu3oAlioNi7(Ero.9iYo.o9)i.i 、 Zr5iCu3oAlioNi7Hfi(Ero.8Yo.2)i 、According to some preferred embodiments of the present invention, the composition of the zirconium-based amorphous alloy is: Zr 5 i.9Cu3oAlioNi 7 (Ero.9iYo.o9)ii, Zr 5 iCu3oAlioNi 7 Hfi(Ero.8Yo.2)i ,
Ζι·50Οι30Α110Νί6·5Ηί Τί0·5(Ει·0·75Υ0·25)2 、 Zr51Cu27Al8Ni7Co3Hf0.8Fe2.5Ti0.49(Er0.52Y0.48) 21 或者 Zr51+5Cu29Al10Ni7(Er0+8Y0+2)2+5或 Zr65Cu21Al8Ni5(Er0+6Y 4)l o Ζι· 50 Οι 30 Α1 10 Νί 6 · 5 Ηί Τί 0 · 5 (Ει· 0 · 75 Υ 0 · 25 ) 2 , Zr 51 Cu 27 Al 8 Ni 7 Co 3 Hf 0 . 8 Fe 2 . 5 Ti 0 . 49 (Er 0 . 52 Y 0 . 48 ) 21 or Zr 51 + 5 Cu 29 Al 10 Ni 7 (Er 0 + 8 Y 0 + 2 )2+ 5 or Zr 65 Cu 21 Al 8 Ni 5 (Er 0 + 6 Y 4 ) lo
本发明的锆基非晶合金的组成中， 当 M为一种元素时， d表示该元素在所述锆基非晶 合金中对应的原子百分数， 如
Figure imgf000004_0001
其中 M为 Ni。 当 M为 2种 或两种以上的元素时， d表示 M选择的每种元素在该锆基非晶合金中对应的原子百分数之 和， 如 Zr5oCu3oAlioNi6.5HfiTio.5(Ero.75Yo.25)2, 其中 M为 Ni、 Hf和 Ti， d则为 Ni、 Hf和 Ti 在锆基非晶合金中分别对应的原子百分数 6.5、 1和 0.5的和， 即 d=6.5+l+0.5=8。 In the composition of the zirconium-based amorphous alloy of the present invention, when M is an element, d represents a corresponding atomic percentage of the element in the zirconium-based amorphous alloy, such as
Figure imgf000004_0001
Where M is Ni. When M is two or more two kinds of elements, d represents element M selected corresponding to each of the Zr-based amorphous alloy and the atomic percent, such as Zr5oCu3oAlioNi 6 .5HfiTio.5 (Ero.75Yo.25) 2, wherein M is Ni, Hf and Ti, and d is the sum of atomic percentages of 6.5, 1 and 0.5 of Ni, Hf and Ti in the zirconium-based amorphous alloy, that is, d = 6.5 + l + 0.5 = 8.
本发明提供的锆基非晶合金的组成中加入稀土元素 Er， 并且稀土元素 Er和 Y以特定 量组合， 可以改善该锆基非晶合金的非晶形成能力， 可以允许含有杂质元素尤其是杂质气 体元素的含量比单独加入稀土元素 Y时更高， 大大降低了对冶炼真空环境的要求。 根据本 发明的实施例， 所述锆基非晶合金中氧元素含量为 lOOOppm以下。  The rare earth element Er is added to the composition of the zirconium-based amorphous alloy provided by the present invention, and the rare earth elements Er and Y are combined in a specific amount, which can improve the amorphous forming ability of the zirconium-based amorphous alloy, and can allow impurities, especially impurities, to be contained. The content of gas elements is higher than when the rare earth element Y is added alone, which greatly reduces the requirements for the smelting vacuum environment. According to an embodiment of the present invention, the zirconium-based amorphous alloy has an oxygen element content of 100 ppm or less.
根据本发明的实施例， 本发明的锆基非晶合金的组成中加入以特定量组合的稀土元素 Er和 Y， 该锆基非晶合金中可以存在杂质元素。 根据本发明的实施例， 以所述锆基非晶合 金的总量为基准， 所述锆基非晶合金中金属杂质元素的原子百分数为 2%以下。  According to an embodiment of the present invention, rare earth elements Er and Y which are combined in a specific amount are added to the composition of the zirconium-based amorphous alloy of the present invention, and an impurity element may be present in the zirconium-based amorphous alloy. According to an embodiment of the present invention, the atomic percentage of the metal impurity element in the zirconium-based amorphous alloy is 2% or less based on the total amount of the zirconium-based amorphous alloy.
根据本发明的实施例， 所述锆基非晶合金的非晶形成能力明显改善。 根据本发明的一 些实施例， 所述锆基非晶合金的临界尺寸为 3mm以上。  According to an embodiment of the present invention, the amorphous forming ability of the zirconium-based amorphous alloy is remarkably improved. According to some embodiments of the present invention, the zirconium-based amorphous alloy has a critical dimension of 3 mm or more.
在本发明的另一方面， 本发明还提供了一种制备锆基非晶合金的方法。 根据本发明的 实施例， 该方法包括： 在惰性气体保护下或真空条件下， 将锆基非晶合金的原料进行熔炼 并冷却成型， 其中， 所述锆基非晶合金的原料包括 Zr、 Cu、 Al、 Er、 Y和 Μ， 并且所述 Zr、 Cu、 Al、 Er、 Y和 M的量能有效形成
Figure imgf000004_0002
其中， Μ为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf和 Ta中的至少一种， a、 b、 c、 d和 e为各元素在该锆基非晶合金中 对应的原子百分数， 分别为： 40 a 70， 15^b=¾35, 5^c=¾ 15, 3^d=¾ 15, 0.2<e=¾2.5, 0<x<0.5。 In another aspect of the invention, the invention also provides a method of preparing a zirconium-based amorphous alloy. According to an embodiment of the present invention, the method comprises: melting and cooling a raw material of a zirconium-based amorphous alloy under inert gas protection or under vacuum, wherein the raw material of the zirconium-based amorphous alloy comprises Zr, Cu , Al, Er, Y and Μ, and the amounts of Zr, Cu, Al, Er, Y and M can be effectively formed
Figure imgf000004_0002
Wherein Μ is at least one selected from the group consisting of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and a, b, c, d and e are the corresponding atoms of the respective elements in the zirconium-based amorphous alloy The percentages are: 40 a 70, 15^b=3⁄435, 5^c=3⁄4 15, 3^d=3⁄4 15, 0.2<e=3⁄42.5, 0<x<0.5.
需要说明的是， 前面所述的锆基非晶合金的原料包括 Zr、 Cu、 Al、 Er、 Y和 M是指锆 基非晶合金的原料包括 Zr、 Cu、 Al、 Er、 Y和 M元素， 而在制备所述锆基非晶合金的过程 中， Zr、 Cu、 Al、 Er、 Y和 M元素的提供形式不受特别限制， 包括但不限于以单质、 合金 或化合物的形式提供。  It should be noted that the raw materials of the zirconium-based amorphous alloy described above include Zr, Cu, Al, Er, Y, and M. The raw materials of the zirconium-based amorphous alloy include Zr, Cu, Al, Er, Y, and M elements. While the form of the Zr, Cu, Al, Er, Y, and M elements is not particularly limited in the process of preparing the zirconium-based amorphous alloy, including but not limited to, it is provided in the form of a simple substance, an alloy, or a compound.
根据本发明的实施例， 由所述锆基非晶合金的原料形成的锆基非晶合金的组成为： ZraCubAlcMd(Eri-xYx)e, 其中， M为选自 Ni、 Fe、 Co、 Ti和 Hf中的至少一种， a、 b、 c、 d 和 e为各元素在该锆基非晶合金中对应的原子百分数， 分别为： 40 a 70， 15^b^35, 5 ^c=¾ 15, 3^d=¾ 15, 0.2<e=¾2.5, 0<x<0.5。 根据本发明的实施例， 可以选用低纯度的非晶合金的原材料进行所述锆基非晶合金的 生产制造。 根据本发明的一些实施例， 所述锆基非晶合金的原料的纯度为工业级， 其中， Zr、 Cu、 A1和 M金属的纯度为 99重量％以上。 如锆材可以选用工业级的 HZr-l， 而金属 原材料 Cu、 A1和 M可以采用纯度为 99重量％以上的工业级金属原材料。 另外， 所述锆基 非晶合金不需添加昂贵的元素 Sc， 从而大大降低了合金的原材料成本。 此外， 稀土金属也 可以选取低纯度的原料， 根据本发明的一些实施例， Er和 Y的纯度为 98重量％以上。 考 虑到稀土元素为易氧化元素， 同时为了易于与母合金进行冶炼混合， 优选以中间合金的形 式加入稀土元素。根据本发明的实施例，所述 Er和 Y是以 AIRE合金的形式提供的，其中， RE表示 Er和 Y的组合。 According to an embodiment of the present invention, the composition of the zirconium-based amorphous alloy formed from the raw material of the zirconium-based amorphous alloy is: Zr a Cu b Al c M d (Eri - x Y x ) e , wherein M is selected From at least one of Ni, Fe, Co, Ti and Hf, a, b, c, d and e are the corresponding atomic percentages of the respective elements in the zirconium-based amorphous alloy, respectively: 40 a 70, 15^ b^35, 5 ^c=3⁄4 15, 3^d=3⁄4 15, 0.2<e=3⁄42.5, 0<x<0.5. According to an embodiment of the present invention, the production of the zirconium-based amorphous alloy may be carried out using a raw material of a low-purity amorphous alloy. According to some embodiments of the present invention, the purity of the raw material of the zirconium-based amorphous alloy is industrial grade, wherein the purity of the Zr, Cu, Al, and M metals is 99% by weight or more. For example, industrial grade HZr-1 can be used for the zirconium material, and industrial grade metal raw materials with a purity of 99% by weight or more can be used for the metal raw materials Cu, A1 and M. In addition, the zirconium-based amorphous alloy does not need to add an expensive element Sc, thereby greatly reducing the raw material cost of the alloy. Further, the rare earth metal may also be selected from low purity raw materials. According to some embodiments of the present invention, the purity of Er and Y is 98% by weight or more. In view of the fact that the rare earth element is an easily oxidizable element, and in order to facilitate smelting and mixing with the master alloy, it is preferred to add the rare earth element in the form of an intermediate alloy. According to an embodiment of the invention, the Er and Y are provided in the form of an AIRE alloy, wherein RE represents a combination of Er and Y.
根据本发明的实施例，制备锆基非晶合金加入稀土元素 Er可以改善非晶合金形成能力， 制备获得的锆基非晶合金中允许存在 lOOOppm以下的氧含量， 可以降低进行熔炼时对真空 环境的要求，根据本发明的一些实施例，进行所述熔炼时对真空条件的要求为小于 500 Pa。 根据本发明的优选实施例， 进行所述熔炼时对真空条件的要求为小于 100 Pa。  According to an embodiment of the present invention, the preparation of a zirconium-based amorphous alloy by adding a rare earth element Er can improve the forming ability of the amorphous alloy, and the obtained zirconium-based amorphous alloy is allowed to have an oxygen content of less than 1000 ppm, which can reduce the vacuum environment during smelting. Requirements, according to some embodiments of the invention, the requirement for vacuum conditions during the smelting is less than 500 Pa. According to a preferred embodiment of the invention, the requirement for vacuum conditions during said smelting is less than 100 Pa.
根据本发明的实施例， 所述惰性气体保护或真空条件是为了使锆基非晶合金原料在熔 炼过程中获得保护， 避免被氧化。 本发明的锆基非晶合金原料的抗氧化性能较好， 因此对 惰性气体保护或真空条件的要求比较低。 根据本发明的实施例， 所述惰性气体为元素周期 表中零族元素气体中的一种或几种。根据本发明的实施例，所述惰性气体的纯度不低于 95% 体积百分比即可， 例如可以为 95-99.99%体积百分比。  According to an embodiment of the invention, the inert gas protection or vacuum conditions are such that the zirconium-based amorphous alloy material is protected from oxidation during the smelting process. The zirconium-based amorphous alloy material of the present invention has a good oxidation resistance, and therefore requires less inert gas protection or vacuum conditions. According to an embodiment of the present invention, the inert gas is one or more of a group of elemental gases in the periodic table. According to an embodiment of the present invention, the inert gas may have a purity of not less than 95% by volume, and may be, for example, 95 to 99.99% by volume.
根据本发明的实施例， 所述熔炼的方法可以为本领域中各种常规的熔炼方法， 只要将 锆基非晶合金原料充分熔融即可。 根据本发明的实施例， 所述熔炼可以为真空感应熔炼、 真空电弧熔炼或真空自耗式电极熔炼。 所述熔炼可以在熔炼设备内进行， 熔炼温度和熔炼 时间随非晶合金原材料的不同会有一些变化， 在本发明的一些实施例中， 熔炼温度可以为 1000-1500 °C ; 熔炼时间可以为 10-50分钟， 优选为 10-30分钟。 所述熔炼设备可以为常规 的熔炼设备， 例如真空电弧熔炼炉、 真空感应熔炼炉或真空电阻炉。  According to an embodiment of the present invention, the method of smelting may be various conventional smelting methods in the art as long as the zirconium-based amorphous alloy material is sufficiently melted. According to an embodiment of the invention, the smelting may be vacuum induction melting, vacuum arc melting or vacuum consumable electrode melting. The smelting may be carried out in a smelting apparatus, and the smelting temperature and the smelting time may vary depending on the amorphous alloy raw material. In some embodiments of the present invention, the smelting temperature may be 1000-1500 ° C; the smelting time may be 10-50 minutes, preferably 10-30 minutes. The smelting apparatus may be a conventional smelting apparatus such as a vacuum arc melting furnace, a vacuum induction melting furnace or a vacuum resistance furnace.
本发明的锆基非晶合金的非晶成形能力强， 所述冷却成型可以采用本领域中各种常规 的压力铸造成型方法， 例如， 将熔融的合金材料 （熔体） 压力铸造到模具中， 然后冷却。 根据本发明的实施例， 所述压力铸造方法可以为重力铸造、 负压铸造、 正压铸造、 高压铸 造中的任意一种， 铸造条件， 如铸造压力为本领域技术人员所公知， 例如， 高压铸造的压 力可以为 2-20 MPa。 所述重力浇铸是指利用熔体本身的重力作用浇铸到模具中。 所述铸造 的具体操作方法为本领域技术人员所公知。 例如， 模具材料可以为铜合金、 不锈钢及导热 系数为 30-400W/m*K (优选为 50-200W/m*K)的各种模具钢材料。模具可进行水冷、油冷。 对冷却的程度没有特别要求， 只要能成型为本发明的非晶合金即可， 冷却速率可以为 500 K/S以上。 The zirconium-based amorphous alloy of the present invention has a strong amorphous forming ability, and the cooling molding can employ various conventional pressure casting molding methods in the art, for example, pressure casting a molten alloy material (melt) into a mold. Then cool down. According to an embodiment of the present invention, the pressure casting method may be any one of gravity casting, negative pressure casting, positive pressure casting, and high pressure casting, and casting conditions such as casting pressure are known to those skilled in the art, for example, high pressure. The casting pressure can be 2-20 MPa. The gravity casting refers to casting into a mold by the gravity of the melt itself. The specific method of operation of the casting is well known to those skilled in the art. For example, the mold material may be a copper alloy, stainless steel, and various mold steel materials having a thermal conductivity of 30-400 W/m*K (preferably 50-200 W/m*K). The mold can be water cooled and oil cooled. There is no special requirement for the degree of cooling, as long as it can be formed into the amorphous alloy of the present invention, the cooling rate can be 500. K/S or above.
以下将通过实施例对本发明进行详细描述。  The invention will be described in detail below by way of examples.
采用 XRD衍射仪 （日本理学 D/Max2200PC) 分析以下实施例和对比例中制备的合金 是否为非晶。分析条件为铜靶， 入射波长 λ=1.54060Α，加速电压为 40 kV， 电流为 20 mA， 采用步进扫描， 扫描步长为 0.04°。  The alloys prepared in the following examples and comparative examples were analyzed for whether they were amorphous by an XRD diffractometer (Japanese Science D/Max 2200PC). The analysis conditions were a copper target with an incident wavelength of λ=1.54060 Α, an accelerating voltage of 40 kV, a current of 20 mA, and a step scan with a scan step of 0.04°.
采用 XRD衍射仪 （日本理学 D/Max2500PC) 分析制备的非晶合金的临界尺寸， 衍射 角度 2Θ介于 20° - 60° ， 扫描速度为 4° /min, 扫描电压为 40 kV， 电流为 200 mA。  The critical dimension of the amorphous alloy prepared by XRD diffractometer (Japanese Science D/Max 2500PC) was analyzed. The diffraction angle was 2 Θ between 20 ° - 60 °, the scanning speed was 4 ° / min, the scanning voltage was 40 kV, and the current was 200 mA. .
采用氧氮含量测试仪 （北京纳克公司 IRO-II红外测氧仪） 测量制备的非晶合金中的氧 含量， 仪器精度为 RSD 0.5重量％， 保护气体为高纯 Ar。  The oxygen content in the prepared amorphous alloy was measured by an oxygen-nitrogen content tester (Beijing Nike IRO-II infrared oxygen meter) with an instrument accuracy of 0.5% by weight of RSD and a high purity Ar of protective gas.
按照电感耦合等离子体发射光谱法， 采用全谱直读电感耦合等离子体发射光谱仪 (ICP-AES) (美国热电子公司， 型号 TEVA) 分析制备的非晶合金中的组成。  The composition of the prepared amorphous alloy was analyzed by inductively coupled plasma optical emission spectroscopy using a full spectrum direct reading inductively coupled plasma optical emission spectrometer (ICP-AES) (American Thermo Electron Corporation, model TEVA).
按照 ISO 6892.1-2009方法， 采用万能力学实验机 （INSTRON公司） 测定制备的非晶 合金的弯曲强度。  The flexural strength of the prepared amorphous alloy was measured in accordance with the method of ISO 6892.1-2009 using a universal testing machine (INSTRON).
实施例 1  Example 1
本实施例说明本发明提供的锆基非晶合金 ZrswCu^A^N Er wYo. u的制备方法。 将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  This embodiment illustrates the preparation method of the zirconium-based amorphous alloy ZrswCu^A^N Er wYo.u provided by the present invention. The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的单质金属， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99 重量％的单质金属。  The metal zirconium is an elemental metal having a metal purity of more than 99% by weight, and Al, Cu, Ni, Er, Y are elemental metals having a purity of more than 99% by weight.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20 MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 Al。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a circle having a diameter of 2-20 mm and a height of 20 mm. A table metal casting, denoted as an alloy sample Al.
将合金样品 A1进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 A1为非晶合金。  The alloy sample A1 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A1 was an amorphous alloy.
测定合金样品 A1的临界尺寸， 结果见表 1。  The critical dimension of the alloy sample A1 was measured, and the results are shown in Table 1.
测试合金样品 A1 的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 A1的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample A1 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A1 are shown in Table 1.
取部分合金样品 Al， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample Al was taken and injected into a mold in a vacuum pressure casting apparatus, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
实施例 2 本实施例说明本发明提供的锆基非晶合金 Zi^Cu^AhoNi Hf^Ei^Y ^的制备方法。 将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。 Example 2 This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi^Cu^AhoNi Hf^Ei^Y^ provided by the present invention. The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属（Zr+ Hf)纯度大于 99重量％的工业级 HZr-1锆材， Al、 Cu、 Ni、 Hf、 Er、 Y采用纯度大于 99重量％的单质金属， Er和 Y采用 AlErY中间合金。  Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y. .
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 A2。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. Metal casting, recorded as alloy sample A2.
将合金样品 A2进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 A2为非晶合金。  The alloy sample A2 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A2 was an amorphous alloy.
测定合金样品 A2的临界尺寸， 结果见表 1。  The critical dimension of the alloy sample A2 was measured, and the results are shown in Table 1.
测试合金样品 A2的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 A2的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample A2 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A2 are shown in Table 1.
取部分合金样品 A2， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample A2 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
实施例 3  Example 3
本实施例说明本发明提供的锆基非晶合金 Zi^Cu^A oMwHfiTio^Er^Y^ 的制备方 法。  This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi^Cu^A oMwHfiTio^Er^Y^ provided by the present invention.
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属（Zr+ Hf)纯度大于 99重量％的工业级 HZr-1锆材， Al、 Cu、 Ni、 Hf、 Er、 Y采用纯度大于 99重量％的单质金属， Er和 Y采用 AlErY中间合金， Ti采用 AlTi中 间合金。  Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y. Ti is made of AlTi master alloy.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件记为合金样品 A3。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. The metal casting was recorded as alloy sample A3.
将合金样品 A3进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 A3为非晶合金。 测定合金样品 A3的临界尺寸， 结果见表 1。 The alloy sample A3 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A3 was an amorphous alloy. The critical dimensions of the alloy sample A3 were measured, and the results are shown in Table 1.
测试合金样品 A3的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 A3的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample A3 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A3 are shown in Table 1.
取部分合金样品 A3， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample A3 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
实施例 4  Example 4
本 实 施 例 说 明 本 发 明 提 供 的 锆 基 非 晶 合 金 Zr51Cu27Al8Ni7Co3Hf0.8Fe2.5Ti0.49(Er0.52Y0.48)0.21的制备方法。 This embodiment illustrates the preparation of a zirconium-based amorphous alloy Zr 51 Cu 27 Al 8 Ni 7 Co 3 Hf 0 . 8 Fe 2 . 5 Ti 0 . 49 (Er 0 . 52 Y 0 . 48 ) 0 . 21 provided by the present invention. method.
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属（Zr+ Hf)纯度大于 99重量％的工业级 HZr-1锆材， Al、 Cu、 Ni、 Hf、 Er、 Y采用纯度大于 99重量％的单质金属， Er和 Y采用 AlErY中间合金， Fe和 Ti分别采 用含铝的中间合金。  Metal zirconium is made of industrial grade HZr-1 zirconium with a purity of more than 99% by weight of metal (Zr+Hf), elemental metal with a purity of more than 99% by weight for Al, Cu, Ni, Hf, Er, Y, and AlErY master alloy for Er and Y. Fe and Ti are respectively made of an intermediate alloy containing aluminum.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件记为合金样品 A4。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. The metal casting was recorded as alloy sample A4.
将合金样品 A4进行 XRD粉末衍射分析， 得到的 XRD谱图中为出现峰型为馒头峰的 衍射峰， 说明合金样品 A4为非晶合金。  The alloy sample A4 was subjected to XRD powder diffraction analysis, and the XRD spectrum obtained was a diffraction peak having a peak shape of a taro peak, indicating that the alloy sample A4 was an amorphous alloy.
测定合金样品 A4的临界尺寸， 结果见表 1。  The critical dimensions of the alloy sample A4 were measured and the results are shown in Table 1.
测试合金样品 A4的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 A4的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample A4 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A4 are shown in Table 1.
取部分合金样品 A4， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample A4 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
实施例 5  Example 5
本实施例说明本发明提供的锆基非晶合金 Zr51.5CU29Al1QNi7(Er 8YQ.2)2.5的制备方法。 将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。 This example illustrates the Zr-based amorphous alloy of the present invention provides Zr 51. 5 C U29 Al 1Q Ni 7 (E r 8 Y Q. 2) Preparation Method 2. 5. The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的锆材， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99重 量％的单质金属， Er和 Y采用 AlErY中间合金。 The metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, and the purity of Al, Cu, Ni, Er, Y is more than 99. Amount of elemental metal, Er and Y use AlErY master alloy.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件记为合金样品 A5。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. The metal casting was recorded as alloy sample A5.
将合金样品 A5进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 A5为非晶合金。  The alloy sample A5 was subjected to XRD powder diffraction analysis, and a diffraction peak having a peak shape of a taro peak appeared in the XRD spectrum, indicating that the alloy sample A5 was an amorphous alloy.
测定合金样品 A5的临界尺寸， 结果见表 1。  The critical dimensions of alloy sample A5 were determined and the results are shown in Table 1.
测试合金样品 A5的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 A5的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample A5 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A5 are shown in Table 1.
取部分合金样品 A5， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample A5 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
实施例 6  Example 6
本实施例说明本发明提供的锆基非晶合金 Zi^Cu AlsM^Ei^Yo^的制备方法。 将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  This embodiment illustrates the preparation method of the zirconium-based amorphous alloy Zi^Cu AlsM^Ei^Yo^ provided by the present invention. The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的锆材， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99重 量％的单质金属， Er和 Υ采用 AlErY中间合金。  The metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, Ni, Er, and Y are elemental metals having a purity of more than 99% by weight, and Er and yttrium are made of an AlErY master alloy.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件记为合金样品 A6。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. The metal casting was recorded as alloy sample A6.
将合金样品 A6进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 A1为非晶合金。  The alloy sample A6 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample A1 was an amorphous alloy.
测定合金样品 A6的临界尺寸， 结果见表 1。  The critical dimensions of the alloy sample A6 were measured and the results are shown in Table 1.
测试合金样品 A6氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元素 的质量分数换算成原子百分数， 合金样品 A6的非晶合金成分结果列于表 1中。  The alloy sample A6 oxygen content and composition were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample A6 are shown in Table 1.
取部分合金样品 A6， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample A6 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
对比例 1  Comparative example 1
本对比例说明锆基非晶合金 ZrswCu^AhoNi Eru的制备方法。  This comparative example illustrates the preparation of a zirconium-based amorphous alloy ZrswCu^AhoNi Eru.
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。 The raw materials of each component were put into a vacuum melting furnace, and the vacuum was 50 Pa, and the purity was 99.99% by volume. The specific argon gas was used as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes to sufficiently melt the alloy raw material. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的锆材， Al、 Cu、 M、 Er采用纯度大于 99重量％ 的单质金属， Er采用 AlEr中间合金。  The metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, M, and Er are elemental metals having a purity of more than 99% by weight, and Er is an AlEr master alloy.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 Dl。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. Metal casting, recorded as alloy sample Dl.
将合金样品 D1进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 D1为非晶合金。  The alloy sample D1 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D1 was an amorphous alloy.
测定合金样品 D1的临界尺寸， 结果见表 1。  The critical dimension of the alloy sample D1 was measured, and the results are shown in Table 1.
测试合金样品 D1 的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 D1的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample D1 were measured, and the mass fraction of the metal element contained in the alloy obtained by the ICP-AES analysis was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample D1 are shown in Table 1.
取部分合金样品 Dl， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample D1 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
对比例 2  Comparative example 2
本对比例说明锆基非晶合金 Zi^.sCu^AhoNi HftEi^的制备方法。  This comparative example illustrates the preparation method of zirconium-based amorphous alloy Zi^.sCu^AhoNi HftEi^.
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的工业级 HZr-1锆材， Al、 Cu、 Ni、 Hf、 Er采用纯 度大于 99重量％的单质金属， Er采用 AlEr中间合金。  The metal zirconium is made of industrial grade HZr-1 zirconium having a metal purity of more than 99% by weight, Al, Cu, Ni, Hf, Er are elemental metals having a purity of more than 99% by weight, and Er is an AlEr master alloy.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ), 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 D2。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. Metal casting, denoted alloy sample D2.
将合金样品 D2进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 D2为非晶合金。  The alloy sample D2 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D2 was an amorphous alloy.
测定合金样品 D2的临界尺寸， 结果见表 1。  The critical dimension of the alloy sample D2 was measured, and the results are shown in Table 1.
测试合金样品 D2的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 D2的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample D2 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample D2 are shown in Table 1.
取部分合金样品 D2， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。 对比例 3 Part of the alloy sample D2 was taken into a vacuum pressure casting equipment and injected into the mold at a cooling rate of 500 K/s. The rate was cooled, and a sheet of 1.5 mm X 6 mm X 12 mm was obtained, and the bending strength was measured. The results are shown in Table 1. Comparative example 3
本对比例说明锆基非晶合金 Zi^O^AhoHftNi Yz的制备方法。  This comparative example illustrates the preparation of a zirconium-based amorphous alloy Zi^O^AhoHftNi Yz.
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的工业级 HZr-1锆材， Al、 Cu、 M、 Hf、 Y采用纯 度大于 99重量％的单质金属， Υ采用 A1Y中间合金。  The metal zirconium is made of industrial grade HZr-1 zirconium having a metal purity of more than 99% by weight, Al, Cu, M, Hf, Y are elemental metals having a purity of more than 99% by weight, and the A1Y master alloy is used.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ) , 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 D3。  The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. Metal casting, recorded as alloy sample D3.
将合金样品 D3进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 D3为非晶合金。  The alloy sample D3 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D3 was an amorphous alloy.
测定合金样品 D3的临界尺寸， 结果见表 1。  The critical dimensions of the alloy sample D3 were measured and the results are shown in Table 1.
测试合金样品 D3的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 D3的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample D3 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample D3 are shown in Table 1.
取部分合金样品 D3， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample D3 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
对比例 4  Comparative example 4
本对比例说明锆基非晶合金 Zr52.9Cu3QAl1QNi7(ErQ.67YQ.33 u5的制备方法。 This comparative example illustrates the preparation method of zirconium-based amorphous alloy Zr 52 . 9 Cu 3Q Al 1Q Ni 7 (Er Q . 67 Y Q . 33 u 5 .
将各组分原料投入真空熔炼炉内， 并抽真空为 50 Pa, 再通入纯度为 99.99%体积百分 比的氩气作为保护气体， 进行合金熔炼， 熔炼温度为 1100°C， 熔炼时间为 15分钟， 使合 金原料充分熔融。 然后翻熔 3次， 使其充分合金化。 熔炼过程中的冶炼温度采用红外测温 测试获得。  The raw materials of each component were put into a vacuum melting furnace, vacuumed to 50 Pa, and argon gas having a purity of 99.99% by volume was introduced as a shielding gas to carry out alloy melting, the melting temperature was 1100 ° C, and the melting time was 15 minutes. , the alloy raw material is fully melted. It is then melted 3 times to fully alloy it. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
金属锆采用金属纯度大于 99重量％的锆材， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99重 量％的单质金属， Er和 Υ采用 AlErY中间合金。  The metal zirconium is made of a zirconium material having a metal purity of more than 99% by weight, Al, Cu, Ni, Er, and Y are elemental metals having a purity of more than 99% by weight, and Er and yttrium are made of an AlErY master alloy.
将配比后的金属投入真空熔炼炉中， 并充入 99.99%的氩气进行气氛保护， 进行合金化 冶炼， 冶炼温度为 1100°C， 冶炼时间为 15Min。 冶炼过程中的冶炼温度采用红外测温测试 获得。  The proportioned metal was put into a vacuum melting furnace and filled with 99.99% of argon gas for atmosphere protection to carry out alloying and smelting, the smelting temperature was 1100 ° C, and the smelting time was 15 min. The smelting temperature during the smelting process is obtained by infrared temperature measurement.
将熔融的合金样品通过高压铸造的方法铸造到金属模具中 （其中， 压力 20MPa， 模具 材料 SKD61 ) , 并以 1000 K/s的冷却速率冷却， 获得直径为 2-20mm， 高为 20mm的圆台形 金属铸件， 记为合金样品 D4。 The molten alloy sample was cast into a metal mold by a high pressure casting method (pressure 20 MPa, mold material SKD61), and cooled at a cooling rate of 1000 K/s to obtain a truncated cone shape having a diameter of 2-20 mm and a height of 20 mm. Metal casting, denoted alloy sample D4.
将合金样品 D4进行 XRD粉末衍射分析， 得到的 XRD谱图中出现峰型为馒头峰的衍 射峰， 说明合金样品 D4为非晶合金。  The alloy sample D4 was subjected to XRD powder diffraction analysis, and the XRD spectrum showed a diffraction peak with a peak shape of the taro peak, indicating that the alloy sample D4 was an amorphous alloy.
测定合金样品 D4的临界尺寸， 结果见表 1。  The critical dimensions of the alloy sample D4 were measured and the results are shown in Table 1.
测试合金样品 D4的氧含量和组成成分， 将由 ICP-AES分析得到的合金中所含金属元 素的质量分数换算成原子百分数， 合金样品 D4的非晶合金成分结果列于表 1中。  The oxygen content and composition of the alloy sample D4 were measured, and the mass fraction of the metal element contained in the alloy analyzed by ICP-AES was converted into atomic percentage. The results of the amorphous alloy composition of the alloy sample D4 are shown in Table 1.
取部分合金样品 D4， 放入真空压力铸造设备中注射到模具中， 并以 500 K/s的冷却速 率冷却， 获得 1.5mm X 6mm X 12mm的板材， 测定其弯曲强度， 结果见表 1。  A part of the alloy sample D4 was placed in a vacuum pressure casting apparatus and injected into a mold, and cooled at a cooling rate of 500 K/s to obtain a sheet of 1.5 mm X 6 mm X 12 mm, and the bending strength was measured. The results are shown in Table 1.
对比例 5  Comparative example 5
按照对比例 4的方法， 不同的是， 用 "金属锆采用金属纯度大于 99.9重量％的单质金 属， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99.9重量％的单质金属"替代 "金属锆采用金属纯 度大于 99重量％的单质金属， Al、 Cu、 Ni、 Er、 Y采用纯度大于 99重量％的单质金属"。  According to the method of Comparative Example 4, the difference is that "metal zirconium adopts elemental metal with metal purity greater than 99.9% by weight, and Al, Cu, Ni, Er, Y adopts elemental metal with purity greater than 99.9% by weight" instead of "metal zirconium". Elemental metals having a metal purity greater than 99% by weight, Al, Cu, Ni, Er, Y are elemental metals having a purity greater than 99% by weight.
得到合金样品 D5， 合金的临界尺寸、 氧含量、 组成成分和弯曲强度结果见表 1 。  The alloy sample D5 was obtained. The critical dimensions, oxygen content, composition and flexural strength of the alloy are shown in Table 1.
表 1  Table 1
从上述实施例、 对比例和表 1 的数据结果可以看出， 采用本发明提供的锆基非晶合金 可以提高非晶形成能力， 可以在使用工业级原材料的情况下获得更大的临界尺寸， 而且在 氧含量高的情况下仍然具有高度弯曲强度， 说明本发明提供的非晶合金对生产制造过程要 求的苛刻度小， 氧含量对机械性能影响小。 特别是在所述锆基非晶合金的组成中含有特定 比例组合的稀土元素 Er和 Y (Er与 Y间的原子摩尔比满足 0<x<0.5 )且 ErY组合的原子 百分数满足 0.3 <e 2时可以有更好的效果，即更大的临界尺寸，且同时弯曲强度数值也高。 对比例 1-3没有采用 Er和 Y的特定组合。其中对比例 1相比实施例 1以及对比例 2相 比实施例 2， 对比例中的非晶合金的组成中只有 Er， 使用工业级原料时得到的合金样品 D1 和 D2的临界尺寸均小于实施例 1和 2的合金样品 A1和 A2。对比例 3相比实施例 1，非晶 合金的组成中只有 Y，使用工业级原料时得到的合金样品 D3即使氧含量低，弯曲强度也不 如实施例 1的合金样品 A1。 对比例 4的非晶合金中虽然也有 Er和 Y， 但是 ErY组合的原 子百分数不在本发明所特定的范围内， 因此使用工业级原料时得到的合金样品 D4 的临界 尺寸小且弯曲强度差。 对比例 5需要使用比对比例 4纯度更高的原材料， 才可以同时获得 大临界尺寸和高弯曲强度，但是这样在实际工业化生产中非晶合金的制造成本将大幅增加， 没有实际的工业化生产意义。 It can be seen from the data of the above examples, comparative examples and Table 1 that the zirconium-based amorphous alloy provided by the present invention can improve the amorphous forming ability and can obtain a larger critical size in the case of using industrial grade raw materials. Moreover, it still has a high bending strength in the case of a high oxygen content, indicating that the amorphous alloy provided by the present invention has a small severity required for the manufacturing process, and the oxygen content has little influence on the mechanical properties. In particular, in the composition of the zirconium-based amorphous alloy, a rare earth element Er and Y (a molar ratio of atoms between Er and Y satisfying 0<x<0.5) and a combination of ErY are contained in a specific ratio composition. When the percentage satisfies 0.3 <e 2 , there is a better effect, that is, a larger critical dimension, and at the same time, the bending strength value is also high. Comparative Examples 1-3 did not employ a specific combination of Er and Y. Comparative Example 1 Compared with Example 1 and Comparative Example 2, Example 2, the composition of the amorphous alloy in the comparative example was only Er, and the critical dimensions of the alloy samples D1 and D2 obtained when using the industrial grade raw material were smaller than the implementation. Alloy samples A1 and A2 of Examples 1 and 2. Comparative Example 3 Compared with Example 1, the composition of the amorphous alloy was only Y, and the alloy sample D3 obtained when the industrial grade raw material was used had a bending strength which was not as good as that of the alloy sample A1 of Example 1 even though the oxygen content was low. In the amorphous alloy of Comparative Example 4, although Er and Y were also present, the atomic percentage of the ErY combination was not within the range specified by the present invention, so the alloy sample D4 obtained when the industrial grade raw material was used had a small critical dimension and poor bending strength. Comparative Example 5 requires the use of a higher purity raw material than Comparative Example 4 to obtain both a large critical dimension and a high bending strength, but in the actual industrial production, the manufacturing cost of the amorphous alloy will be greatly increased, and there is no practical industrial production significance. .
实施例 1-6 中使用本发明提供的锆基非晶合金时可以采用工业级原材料， 可以降低对 制备时熔炼的真空条件的要求， 可以有利于工业化生产制备和产品的商品化应用。 在本说明书的描述中，参考术语"一个实施例"、 "一些实施例"、 "示例"、 "具体示例"、 或 "一些示例"等的描述意指结合该实施例或示例描述的具体特征、 结构、 材料或者特点 包含于本发明的至少一个实施例或示例中。 在本说明书中， 对上述术语的示意性表述不必 须针对的是相同的实施例或示例。 而且， 描述的具体特征、 结构、 材料或者特点可以在任 一个或多个实施例或示例中以合适的方式结合。 此外， 在不相互矛盾的情况下， 本领域的 技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结 合和组合。  In the use of the zirconium-based amorphous alloy provided by the present invention in Examples 1-6, industrial grade raw materials can be used, which can reduce the vacuum conditions for smelting at the time of preparation, and can be favored for industrial production preparation and commercial application of products. In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms is not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. Further, those skilled in the art can combine and combine the various embodiments or examples described in the specification and the features of the different embodiments or examples without departing from the scope of the invention.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的， 不能理解为对本发明的限制， 本领域的普通技术人员在本发明的范围内可以对上述实施例 进行变化、 修改、 替换和变型。  Although the embodiments of the present invention have been shown and described, it is understood that the above-described embodiments are illustrative and are not to be construed as limiting the scope of the invention. The embodiments are subject to variations, modifications, substitutions and variations.

Claims

权利要求书 claims
1、一种锆基非晶合金，其特征在于，该锆基非晶合金的组成为： ZraCubAlcMd(Er1-xYx)e, 其中， M为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf禾 P Ta中的至少一种， 40 a 70， 15^b ^35 , 5^c=¾ 15 , 3 ^d=¾ 15 , 0.2<e=¾2.5 , 0<x<0.5。 1. A zirconium-based amorphous alloy, characterized in that the composition of the zirconium-based amorphous alloy is: Zr a Cu b Al c M d (Er 1-x Y x ) e , where M is selected from Ni, At least one of Fe, Co, Mn, Cr, Ti, Hf and Ta, 40a70, 15^b^35, 5^c=¾15, 3^d=¾15, 0.2<e=¾2. 5, 0<x<0.5.
2、 根据权利要求 1所述的锆基非晶合金， 其中， M为选自 Ni、 Fe、 Co、 Ti和 Hf中的 至少一种。 2. The zirconium-based amorphous alloy according to claim 1, wherein M is at least one selected from Ni, Fe, Co, Ti and Hf.
3、 根据权利要求 1 或 2所述的锆基非晶合金， 其中， 所述锆基非晶合金的组成为： Zr5i.9Cu3oAlioNi7(Ero.9iYo.o9)i.i 、 Zr5iCu3oAlioNi7Hfi(Ero.8Yo.2)i 、 Zr5oCu3oAlioNi6.5HfiTio.5(Ero.75Yo.25)2 、 Zr51Cu27Al8Ni7Co3Hf0.8Fe2.5Ti0.49(Er0.52Y0.48)0.21 、 Zr51+5Cu29Al10Ni7(Er0+8Y0+2)2+5或 Zr65Cu21Al8Ni5(Er0+6Y0+4)l o 3. The zirconium-based amorphous alloy according to claim 1 or 2, wherein the composition of the zirconium-based amorphous alloy is: Zr 5 i.9Cu3oAlioNi 7 (Ero.9iYo.o9)ii, Zr 5 iCu3oAlioNi 7 Hfi (Ero.8Yo.2)i, Zr5oCu3oAlioNi6.5HfiTio.5(Ero.7 5 Yo.25)2, Zr 51 Cu2 7 Al 8 Ni7Co3Hf 0 . 8 Fe2. 5 Ti 0 . 49 (Er 0 . 52 Y 0 . 48 ) 0 . 21 , Zr 51 + 5 Cu 29 Al 10 Ni 7 (Er 0 + 8 Y 0 + 2 )2+ 5 or Zr 65 Cu 21 Al 8 Ni 5 (Er 0 + 6 Y 0 + 4 ) lo
4、 根据权利要求 1-3中任意一项所述的锆基非晶合金， 其中， 以所述锆基非晶合金的 总量为基准， 所述锆基非晶合金中金属杂质元素的原子百分数为 2%以下。 4. The zirconium-based amorphous alloy according to any one of claims 1 to 3, wherein, based on the total amount of the zirconium-based amorphous alloy, the atoms of metal impurity elements in the zirconium-based amorphous alloy The percentage is less than 2%.
5、 根据权利要求 1-4中任意一项所述的锆基非晶合金， 其中， 所述锆基非晶合金的临 界尺寸为 3mm以上。 5. The zirconium-based amorphous alloy according to any one of claims 1 to 4, wherein the critical size of the zirconium-based amorphous alloy is 3 mm or more.
6、 根据权利要求 1-5中任意一项所述的锆基非晶合金， 其中， 所述锆基非晶合金中氧 元素含量为 lOOOppm以下。 6. The zirconium-based amorphous alloy according to any one of claims 1 to 5, wherein the oxygen element content in the zirconium-based amorphous alloy is less than 1000 ppm.
7、 一种制备锆基非晶合金的方法， 其特征在于， 包括： 7. A method for preparing zirconium-based amorphous alloy, which is characterized by including:
在惰性气体保护下或真空条件下， 将锆基非晶合金的原料进行熔炼并冷却成型， 以便 获得所述锆基非晶合金， Under the protection of inert gas or under vacuum conditions, the raw materials of the zirconium-based amorphous alloy are smelted and cooled to form, so as to obtain the zirconium-based amorphous alloy,
其中， in,
所述锆基非晶合金的原料包括 Zr、 Cu、 Al、 Er、 Y和 M， 并且所述 Zr、 Cu、 Al、 Er、 Y和 M的量能有效形成
Figure imgf000014_0001
 The raw materials of the zirconium-based amorphous alloy include Zr, Cu, Al, Er, Y and M, and the amounts of Zr, Cu, Al, Er, Y and M can effectively form
Figure imgf000014_0001
M为选自 Ni、 Fe、 Co、 Mn、 Cr、 Ti、 Hf和 Ta中的至少一种， M is at least one selected from Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta,
40^a=¾70, 15^b=¾35 , 5^c=¾ 15 , 3 ^d=¾ 15 , 0.2<e=¾2.5 , 0<x<0.5。 40^a=¾70, 15^b=¾35, 5^c=¾ 15, 3^d=¾ 15, 0.2<e=¾2.5, 0<x<0.5.
8、根据权利要求 7所述的方法， 其中， M为选自 Ni、 Fe、 Co、 Ti和 Hf中的至少一种。 8. The method according to claim 7, wherein M is at least one selected from Ni, Fe, Co, Ti and Hf.
9、根据权利要求 7或 8所述的方法，其中，所述锆基非晶合金的原料的纯度为工业级， 其中， Zr、 Cu、 Al和 M金属的纯度为 99重量％以上， Er和 Y的纯度为 98重量％以上。 9. The method according to claim 7 or 8, wherein the purity of the raw material of the zirconium-based amorphous alloy is industrial grade, wherein the purity of Zr, Cu, Al and M metals is above 99% by weight, Er and The purity of Y is 98% by weight or more.
10、 根据权利要求 7-9中任一项所述的方法， 其中， 所述 Er和 Y是以 AIRE合金的形 式提供的， 其中， RE表示 Er和 Y的组合。 10. The method according to any one of claims 7-9, wherein the Er and Y are provided in the form of an AIRE alloy, where RE represents a combination of Er and Y.
PCT/CN2014/083461 2013-12-26 2014-07-31 Zirconium-based amorphous alloy and preparation method therefor WO2015096479A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310731855.7 2013-12-26
CN201310731855.7A CN104745973A (en) 2013-12-26 2013-12-26 Zr-based amorphous alloy and manufacturing method thereof

Publications (1)

Publication Number Publication Date
WO2015096479A1 true WO2015096479A1 (en) 2015-07-02

Family

ID=53477478

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/083461 WO2015096479A1 (en) 2013-12-26 2014-07-31 Zirconium-based amorphous alloy and preparation method therefor

Country Status (2)

Country Link
CN (1) CN104745973A (en)
WO (1) WO2015096479A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105239024A (en) * 2015-11-13 2016-01-13 东莞宜安科技股份有限公司 High-hardness amorphous composite as well as preparation method and application thereof
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

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105132837B (en) * 2015-08-27 2017-04-12 常州世竟液态金属有限公司 Low-cost bulk amorphous alloy
CN106567015B (en) * 2016-11-21 2019-02-26 中国科学院金属研究所 A kind of CuZr base lump non-crystalline alloy and its preparation method and application
CN106756647B (en) * 2016-12-12 2019-06-11 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel
CN108193147B (en) * 2018-02-07 2020-11-27 瑞声精密制造科技(常州)有限公司 High-toughness zirconium-based amorphous alloy material and preparation method thereof
CN109355602B (en) * 2018-11-15 2020-12-29 北京科技大学 Nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability and preparation and application thereof
CN109468548B (en) * 2019-01-04 2020-01-14 盘星新型合金材料(常州)有限公司 Wide supercooled liquid region zirconium-based amorphous alloy
CN109957732B (en) * 2019-04-08 2020-11-27 东北大学 Method for continuously preparing zirconium-based amorphous thin strip
CN110004325B (en) * 2019-04-13 2020-10-20 常州世竟液态金属有限公司 High-biocompatibility zirconium alloy
CN113528986B (en) * 2021-07-15 2022-09-27 深圳大学 Ultrahigh-toughness large-size zirconium-based amorphous alloy and preparation method and application thereof
CN113913710A (en) * 2021-10-14 2022-01-11 盘星新型合金材料(常州)有限公司 Be-free low-density bulk amorphous alloy and preparation method and application thereof
CN114032479A (en) * 2021-11-11 2022-02-11 盘星新型合金材料(常州)有限公司 Zr-based bulk amorphous alloy suitable for small electronic equipment and preparation method thereof
CN115041659B (en) * 2022-06-11 2023-08-18 安徽昊方机电股份有限公司 Grooved needle for warp knitting machine and method for manufacturing grooved needle by amorphous alloy injection molding process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03158446A (en) * 1989-11-17 1991-07-08 Takeshi Masumoto Amorphous alloy excellent in workability
JPH1171661A (en) * 1997-08-29 1999-03-16 Akihisa Inoue High strength amorphous alloy and its production
CN1948543A (en) * 2006-11-03 2007-04-18 北京航空航天大学 Copper base large non crystal alloy and its preparation method
CN101161851A (en) * 2007-11-30 2008-04-16 北京航空航天大学 Zr-Al-Co-RE-Cu amorphous alloy
CN101235472A (en) * 2007-11-15 2008-08-06 北京航空航天大学 Zirconium-base amorphous-crystal multiple phase material and preparation method thereof
CN102965599A (en) * 2012-11-26 2013-03-13 华为技术有限公司 Zirconium-based amorphous alloy

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03158446A (en) * 1989-11-17 1991-07-08 Takeshi Masumoto Amorphous alloy excellent in workability
JPH1171661A (en) * 1997-08-29 1999-03-16 Akihisa Inoue High strength amorphous alloy and its production
CN1948543A (en) * 2006-11-03 2007-04-18 北京航空航天大学 Copper base large non crystal alloy and its preparation method
CN101235472A (en) * 2007-11-15 2008-08-06 北京航空航天大学 Zirconium-base amorphous-crystal multiple phase material and preparation method thereof
CN101161851A (en) * 2007-11-30 2008-04-16 北京航空航天大学 Zr-Al-Co-RE-Cu amorphous alloy
CN102965599A (en) * 2012-11-26 2013-03-13 华为技术有限公司 Zirconium-based amorphous alloy

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105239024A (en) * 2015-11-13 2016-01-13 东莞宜安科技股份有限公司 High-hardness amorphous composite as well as preparation method and application thereof
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

Also Published As

Publication number Publication date
CN104745973A (en) 2015-07-01

Similar Documents

Publication Publication Date Title
WO2015096479A1 (en) Zirconium-based amorphous alloy and preparation method therefor
Lu et al. Role of yttrium in glass formation of Fe-based bulk metallic glasses
US11359265B2 (en) 1 GPA high-strength high-modulus aluminum-based light medium-entropy alloy and preparation method thereof
Guo et al. Ductile titanium-based glassy alloy ingots
EP2494084B1 (en) Zr-BASED AMORPHOUS ALLOY AND PREPARING METHOD THEREOF
US9616495B2 (en) Amorphous alloy and method for manufacturing the same
WO2014079188A1 (en) Zirconium-based amorphous alloy
US20110308671A1 (en) Zr-BASED AMORPHOUS ALLOY AND METHOD OF PREPARING THE SAME
Park et al. Formation of Mg–Cu–Ni–Ag–Zn–Y–Gd bulk glassy alloy by casting into cone-shaped copper mold in air atmosphere
WO2014059769A1 (en) Zirconium-based amorphous alloy
WO2015035845A1 (en) Zirconium-based amorphous alloy and preparation method therefor
EP2499270B1 (en) Zirconium-based amorphous alloy, preparing method and recycling method thereof
EP2455503B1 (en) Grain refiner for magnesium and magnesium alloy and preparation method thereof
CN102080196B (en) Zirconium-based amorphous alloy and preparation method thereof
US11655529B2 (en) Zr-based amorphous alloy and manufacturing method thereof
JP2004353053A (en) Titanium based amorphous alloy
Park et al. Effect of Y addition on thermal stability and the glass forming ability in Fe–Nb–B–Si bulk glassy alloy
CN111636026B (en) High-niobium low-density refractory multi-principal-element alloy and vacuum drop casting method thereof
Zhao et al. Synthesis and elastic properties of amorphous steels with high Fe content
Hao et al. Bulk metallic glass formation of Ti-based alloys from low purity elements
CN109722559B (en) Oxygen-alloying-containing copper-zirconium/hafnium-based amorphous alloy and preparation method thereof
CN102952969B (en) Large-size Zr standard crystal material and preparation method thereof
CN101195874A (en) Method for improving amorphous alloy forming ability
Wu et al. Effects of La microalloying on microstructure evolution of pure copper
CN104911513A (en) Large size ZrTi quasicrystal material and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14874200

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14874200

Country of ref document: EP

Kind code of ref document: A1