EP3045557B1 - Alliage amorphe à base de zircone et son procédé de préparation - Google Patents

Alliage amorphe à base de zircone et son procédé de préparation Download PDF

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Publication number
EP3045557B1
EP3045557B1 EP14843474.9A EP14843474A EP3045557B1 EP 3045557 B1 EP3045557 B1 EP 3045557B1 EP 14843474 A EP14843474 A EP 14843474A EP 3045557 B1 EP3045557 B1 EP 3045557B1
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Prior art keywords
zirconium
amorphous alloy
based amorphous
raw materials
alloy
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German (de)
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EP3045557A4 (fr
EP3045557A1 (fr
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Limin Huang
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Dongguan Zhian Intellectual Property Service Co Ltd
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Dongguan Zhian Intellectual Property Service Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/022—Casting heavy metals, with exceedingly high melting points, i.e. more than 1600 degrees C, e.g. W 3380 degrees C, Ta 3000 degrees C, Mo 2620 degrees C, Zr 1860 degrees C, Cr 1765 degrees C, V 1715 degrees C
    • 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
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • 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

Definitions

  • the invention belongs to the field of metal material and metallurgical technology, and relates to an amorphous alloy, more particularly to a zirconium-based amorphous alloy and a method for preparing the same.
  • Amorphous alloy has the special structure of disorderly long-range and orderly short-range, thereby featuring high intensity, high rigidity, abrasive resistance, corrosion resistance, wide range of elastic limits, high resistivity, brilliant superconductivity, and low magnetic loss. For these reasons, the amorphous alloy is considered as the most promising new structural material, and has a wide application in the fields of machinery, medical treatment, IT electronics, and military, etc.
  • WO 2011/047591 A1 discloses a zirconium-based amorphous alloy having a general formula of (Zr x Al y Cu z Ni 1-x-y-z ) 100-a-b Sc a Y b , wherein x, y, z are atomic percentages, and a and b are atomic molar ratios, 0.45 ⁇ x ⁇ 0.60, 0.08 ⁇ y ⁇ 0.12, 0.25 ⁇ z ⁇ 0.35, 0 ⁇ a ⁇ 5, and 0 ⁇ b ⁇ 0.1.
  • amorphous alloy For the sake of integrity of amorphous structure, conventional preparation methods of amorphous alloy pose high requirements for the purity of the raw material and the production conditions. For instance, purity of raw material is required to be above 99.9% (mass ratio), and the environment is required to have a rather high vacuum degree in the production process, for example 10 -4 -10 -3 Pa under melting atmosphere, because even small amount of oxygen or other impurity could greatly influence the formation of amorphous alloy.
  • zirconium-based amorphous alloy is brilliant at amorphous formation, and that the requirements for the purity of raw material and the production conditions could be slightly lowered by controlling the components in the amorphous alloy.
  • a zirconium-based amorphous alloy By adding at least one element of Y and Sc and at least one element of Si and C and controlling the content proportions thereof, the requirements for the purity of the raw material, the vacuum degree of the melting, the oxygen content in the melting atmosphere, and the cooling rate are greatly decreased, and in the meanwhile, the comprehensive performance and the stability of the zirconium-based amorphous alloy are improved.
  • a zirconium-based amorphous alloy having the following formula: (Zr 1-x-y Ti x Hf y ) a (Cu m Ni n ) b Al c M d N e , in which, a, b, c, d, and e represent numbers of atoms, 30 ⁇ a ⁇ 75 15 ⁇ b ⁇ 60, 5 ⁇ c ⁇ 35, 0.1 ⁇ d ⁇ 20, 0.1 ⁇ e ⁇ 5, and a sum of a, b, c, d, and e is 100; x, y, m, and n represent atomic fractions of Ti, Hf, Cu, and Ni, respectively, and 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.05, 0.2 ⁇ m/n ⁇ 5.
  • M is at least one selected from Y and Sc
  • N is Si or a mixture of C and Si.
  • the alloy consists of a crystalline phase and an amorphous phase, the crystalline phase accounts for between 5 and 50 v. % of a total volume of the zirconium-based amorphous alloy, and an amorphous phase accounts for between 50 and 95 v. % of the total volume of the zirconium-based amorphous alloy.
  • a, b, c, d, and e represent the numbers of the atoms, 50 ⁇ a ⁇ 75, 20 ⁇ b ⁇ 55, 5 ⁇ c ⁇ 20, 0.1 ⁇ d ⁇ 10, and 0.1 ⁇ e ⁇ 2, and the sum of a, b, c, d, and e is 100.
  • x, y, m, and n represent atomic fractions of Ti, Hf, Cu, and Ni, respectively, and 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.03, and 0.4 ⁇ m/n ⁇ 4.5.
  • the crystalline phase accounts for between 10 and 25 v. % of the zirconium-based amorphous alloy, and the amorphous phase accounts for between 75 and 90 v. % of the zirconium-based amorphous alloy.
  • a method for preparing the zirconium-based amorphous alloy comprises: melting raw materials of the zirconium-based amorphous alloy in the presence of an inert gas or in vacuum, and then cooling and shaping the raw materials.
  • the raw materials of the zirconium-based amorphous alloy comprise: Zr, Ti, Hf, Cu, Ni, Al, M, and N, and an addition of each component enable the formula of the zirconium-based amorphous alloy to satisfy (Zr 1-x-y Ti x Hf y ) a (Cu m Ni n ) b Al c M d N e .
  • the inert gas is at least one selected from the group consisting of helium, neon, argon, krypton, xenon, and radon gas, and a purity of the inert gas is higher than or equal to 94 v. %.
  • the vacuum condition is at a pressure of lower than 1000 pascal which is presented by an absolute pressure.
  • a melting temperature is between 1000 and 3000°C.
  • a melting time is between 0.5 and 10 min.
  • the vacuum condition is smaller than 100 pascal.
  • the melting temperature is between 1200 and 2700°C.
  • the melting time is between 2 and 5 min.
  • the vacuum condition is between 0.1 and 50 pascal.
  • the zirconium-based amorphous alloy and the method for preparing the same are summarized as follows:
  • the preparation requirements of the amorphous alloy can be decreased.
  • the original high requirement on the purity of the raw material is greatly decreased, and a certain amount of impurity elements are allowed to exist in the raw materials.
  • the comprehensive performance of the zirconium-based amorphous alloy cannot be affected; on the contrary, the production cost on the raw materials during the industrialized batch production can be reduced.
  • the preparation method of the invention is able to produce the zirconium-based amorphous alloy having a critical size of larger than 3 mm.
  • the produced zirconium-based amorphous alloy not only possesses excellent mechanical performance, but also imposes low requirement on the purity of the raw material and the content of the impurity elements. Specifically, it permits existence of less than or equal to 5 % (atomic percentage) of metallic impurity elements and less than or equal to 1% (atomic percentage) of non-metallic impurity elements.
  • a zirconium-based amorphous alloy provided in the invention is having the following formula: (Zr 1-x-y Ti x Hf y ) a (Cu m Ni n ) b Al c M d N e , in which, a, b, c, d, and e represent numbers of atoms, 30 ⁇ a ⁇ 75, 15 ⁇ b ⁇ 60, 5 ⁇ c ⁇ 35, 0.1 ⁇ d ⁇ 20, 0.1 ⁇ e ⁇ 5, and a sum of a, b, c, d, and e is 100; x, y, m, and n represent atomic fractions of Ti, Hf, Cu, and Ni, respectively, and 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.05, 0.2 ⁇ m/n ⁇ 5.
  • M is at least one selected from Y and Sc, and N is Si or a mixture of C and Si.
  • a crystalline phase accounts for between 5 and 50 v. % of a total volume of the zirconium-based amorphous alloy, and an amorphous phase accounts for between 50 and 95 v. % of the total volume of the zirconium-based amorphous alloy.
  • a, b, c, d, and e represent the numbers of the atoms, 50 ⁇ a ⁇ 75, 20 ⁇ b ⁇ 55, 5 ⁇ c ⁇ 20, 0.1 ⁇ d ⁇ 10, and 0.1 ⁇ e ⁇ 2, and the sum of a, b, c, d, and e is 100.
  • x, y, m, and n represent atomic fractions of Ti, Hf, Cu, and Ni, respectively, and 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.03, and 0.4 ⁇ m/n ⁇ 4.5.
  • the crystalline phase accounts for between 10 and 25 v. % of the zirconium-based amorphous alloy, and the amorphous phase accounts for between 75 and 90 v. % of the zirconium-based amorphous alloy.
  • the produced zirconium-based amorphous alloy always contains some metallic impurity elements, such as Mg, Ca, and Co, and several non-metallic impurity elements, such as C, O, N, B, and P. But for the zirconium-based amorphous alloy of the invention, existence of a certain amount of impurity elements will not affect the performance of the produced zirconium-based amorphous alloy.
  • the zirconium-based amorphous alloy is allowed to contain less than or equal to 5% (atomic percentage) of the metallic impurity elements and less than or equal to 1 % (atomic percentage) of the non-metallic impurity elements.
  • the contents of the impurities are within the above range, the melting and the preparation of the zirconium-based amorphous alloy will not be affected.
  • the purities of the raw materials of the zirconium-based amorphous alloy are operable as long as it satisfies the common requirements, and preferable purities thereof are high than 98 wt. %.
  • the proportion between the crystalline phase and the amorphous phase therein can be adjusted by controlling the composition of the zirconium-based amorphous alloy and controlling the condition for the cooling and shaping according to the common method in the technical field.
  • the condition for the cooling and shaping includes: the cooling rate, the pressure, the material of the die, and the thermal conductivity of the die.
  • the cooling rate is one of the important factors to control proportion of the crystalline phase to the amorphous phase of the zirconium-based amorphous alloy, while the pressure, the material of the die, and the thermal conductivity of the die have a relatively wide selection range, and the cooperative selection thereof can satisfy the condition for the cooling and shaping as along as a proper cooling rate is obtained.
  • the volume percentage of the crystalline phase is generally negatively proportional to the cooling rate.
  • the cooling rate can be selected within the common range, such as higher than 10 K/s, and preferable between 10 and 10 4 K/s.
  • the inert gas is at least one selected from the group consisting of helium, neon, argon, krypton, xenon, and radon gas, and a purity of the inert gas is higher than or equal to 94 v. %.
  • the vacuum condition is at a pressure of lower than 1000 pascal which is presented by an absolute pressure.
  • a melting temperature is between 1000 and 3000°C.
  • a melting time is between 0.5 and 10 min.
  • the melting time is between 2 and 5 min.
  • a melting device can be the common melting devices, such as the vacuum arc melting furnace, a vacuum induction furnace, or a vacuum resistance furnace.
  • the zirconium-based amorphous alloy has excellent shaping performance.
  • the cooling and shaping can adopt the common die-casting methods and the stainless steel and copper alloy materials in the technical filed.
  • the cooling of the die can adopt the water cooling and oil cooling methods.
  • Raw materials having purities of 99 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 10 pascal. After that, argon gas having a purity of 99.9 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1500°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 50% of Zr, 2% of Ti, 15% of Cu, 10% of Ni, 15% of Al, 4% of Y, 2% of Sc, and 2% of Si.
  • a melted sample was finally casted into a copper alloy die by a die-casting method for cooling and shaping so as to obtain the zirconium-based amorphous alloy.
  • Raw materials having purities of 99 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 10 -1 pascal. After that, argon gas having a purity of 99.9 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1650°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 60% of Zr, 3% of Ti, 2% of Hf, 12.5% of Cu, 7.5% of Ni, 5% of Al, 5% of Y, 3% of Sc, 1.5% of Si, and 0.5% of C.
  • a melted sample was finally casted into a copper alloy die by a die-casting method for cooling and shaping so as to obtain the zirconium-based amorphous alloy.
  • Raw materials having purities of 99 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 10 -1 pascal. After that, argon gas having a purity of 99.9 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1600°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 60% of Zr, 1.5% of Ti, 0.5% of Hf, 10.5% of Cu, 9.5% of Ni, 8% of Al, 0.5% of Y, 1.2% of Sc, and 0.3% of Si.
  • a melted sample was finally casted into a copper alloy die by a die-casting method for cooling and shaping so as to obtain the zirconium-based amorphous alloy.
  • Raw materials having purities of 98 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 200 pascal. After that, argon gas having a purity of 99 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1500°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 50.5% of Zr, 0.5% of Hf, 30% of Cu, 7.5% of Ni, 10% of Al, 0.8% of Y, and 0.8% of Si.
  • a melted sample was finally casted into a copper alloy die by a die-casting method for cooling and shaping so as to obtain the zirconium-based amorphous alloy.
  • Raw materials having purities of 98 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 50 pascal. After that, argon gas having a purity of 99 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1600°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 57.5% of Zr, 2.3% of Ti, 1.2% of Hf, 23% of Cu, 6.3% of Ni, 9.2% of Al, 0.2% of Y, and 0.3% of Si.
  • a melted sample was finally casted into a copper alloy die by a die-casting method for cooling and shaping so as to obtain the zirconium-based amorphous alloy.
  • the preparation of the zirconium-based amorphous alloy is the same as that of Example 1 except that the raw materials for the zirconium-based amorphous alloy have purities of 99.8 wt. %.
  • Raw materials having purities of 99.8 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 10 pascal. After that, argon gas having a purity of 99.9 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1500°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 50.9% of Zr, 29.9% of Cu, 7.4% of Ni, 9.8% of Al, and 2% of Y.
  • Raw materials having purities of 99.7 wt. % for the zirconium-based amorphous alloy were added into a vacuum arc melting furnace, the vacuum arc melting furnace was then deaerated until a pressure therein was 10 pascal. After that, argon gas having a purity of 99.9 v. % was introduced into the vacuum arc melting furnace as a protective gas, and the melting was performed at a temperature of 1800°C for 3 min to make the raw materials for the zirconium-based amorphous alloy fully melted.
  • Components and contents (atomic percentages) of the raw materials for the zirconium-based amorphous alloy were as follows: 55% of Zr, 2% of Ti, 16.5% of Cu, 13.5% of Ni, 9.6% of Al, 0.4% of Y, and 3% of Nb.
  • the amorphous alloy that has excellent performance can be acquired under low purity of the raw materials and loosened preparation condition.
  • the amorphous alloy produced in the invention has the proportion of the crystalline phase of between 10 and 25% and the oxygen content of between 600 and 1200 ppm, and has much better mechanical performance compared with the conventional zirconium-based amorphous alloy prepared in the comparison example.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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  • Powder Metallurgy (AREA)

Claims (5)

  1. Alliage à base de zirconium, ayant la formule suivante:

            (Zr1-x-yTixHfy)a(CumNin)bAlcMdNe

    où 30≤a≤75,
    15≤b≤60, 5≤c≤35, 0,1≤d≤20, 0,1≤e≤5, 0≤x≤0,2,
    0 ≤ y ≤ 0,05, 0,2 ≤ m/n ≤ 5, a + b + c + d + e = 100, a, b, c, d et e sont des nombres atomiques, x, y, m et n sont des fractions atomiques, M est au moins un élément choisi parmi Y et Sc, N est Si ou un mélange de C et Si; l'alliage est constitué d'une phase cristalline et d'une phase amorphe, la phase cristalline représente entre 5 et 50 % en volume du volume total de l'alliage à base de zirconium et la phase amorphe représente entre 50 et 95 % en volume du volume total de l'alliage à base de zirconium.
  2. Alliage selon la revendication 1, dans lequel 30 ≤ a ≤ 75, 20 ≤ b ≤ 55, 5 ≤ c ≤ 20, 0,1 ≤ d ≤ 10, 0,1 ≤ e ≤ 2, a + b + c + d + e = 100, 0 ≤ x ≤ 0,15, 0 ≤ y ≤ 0,03, 0,4 ≤ m/n ≤ 4,5; la phase cristalline représente entre 10 et 25 % en volume de l'alliage à base de zirconium, et la phase amorphe représente entre 75 et 90 % en volume de l'alliage à base de zirconium.
  3. Procédé de fabrication de l'alliage selon la revendication 1, comprenant: la fusion de matières premières de l'alliage à base de zirconium en présence d'un gaz inerte ou sous vide, puis le refroidissement et la mise en forme des matières premières; où
    le gaz inerte est de l'hélium, du néon, de l'argon, du krypton, du xénon, du radon ou un mélange de ceux-ci, et la pureté du gaz inerte est supérieure ou égale à 94 % en volume;
    le vide est inférieur à 1000 Pa de pression absolue;
    la température de fusion est comprise entre 1000 et 3000°C;
    le temps de fusion est compris entre 0,5 et 10 min;
    les matières premières de l'alliage à base de zirconium comprennent: Zr, Ti, Hf, Cu, Ni.Al, M et N, et
    une addition de chaque composant permet à la formule de l'alliage à base de zirconium de satisfaire à (Zr1-x-yTixHfy)a(CumNin)bAlcMdNe.
  4. Procédé selon la revendication 3, dans lequel la condition de vide est inférieure à 100 Pascals; la température de fusion est comprise entre 1200 et 2700°C; et le temps de fusion est compris entre 2 et 5 min.
  5. Procédé selon la revendication 3, dans lequel le vide est compris entre 0,1 et 50 Pa de pression absolue.
EP14843474.9A 2013-09-10 2014-08-15 Alliage amorphe à base de zircone et son procédé de préparation Not-in-force EP3045557B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310410770.9A CN103484800B (zh) 2013-09-10 2013-09-10 一种锆基非晶合金及其制备方法
PCT/CN2014/084500 WO2015035845A1 (fr) 2013-09-10 2014-08-15 Alliage amorphe à base de zircone et son procédé de préparation

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EP3045557A1 EP3045557A1 (fr) 2016-07-20
EP3045557A4 EP3045557A4 (fr) 2016-08-31
EP3045557B1 true EP3045557B1 (fr) 2019-04-17

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US (1) US20160186293A1 (fr)
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WO (1) WO2015035845A1 (fr)

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EP3045557A1 (fr) 2016-07-20
CN103484800B (zh) 2015-12-09
WO2015035845A1 (fr) 2015-03-19
US20160186293A1 (en) 2016-06-30
CN103484800A (zh) 2014-01-01

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