CN109355602B - Nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability and preparation and application thereof - Google Patents
Nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to a block amorphous alloy, and particularly relates to a nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability, preparation and application thereof, wherein the atomic percentage expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 2 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100. The preferred components of the zirconium-based bulk amorphous alloy have>7 percent of plastic deformation capacity, yield strength over 1600MPa, higher glass transition temperature and initial crystallization temperature, wider supercooling liquid phase region, no Ni, Be and other biocompatible elements, and wide application prospect in the fields of sports equipment, medical instruments, high-end micro-mechanical parts and the like.
Description
Technical Field
The invention belongs to a block amorphous alloy, and particularly relates to a nickel-free beryllium-free zirconium-based amorphous alloy which does not contain metal elements Ni and Be and has high glass forming capability, and preparation and application thereof.
Technical Field
The amorphous alloy is an alloy with short-range order and long-range disorder obtained by melt quenching, so that the amorphous alloy has incomparable functional characteristics of common crystalline metal materials, such as high strength, large elastic limit, high breaking strength, high hardness, corrosion resistance and the like, and has wide application prospects in the aspects of structural materials, miniature precision devices, sports equipment and the like.
Since the end of the last ninety years, researchers around the world have obtained bulk amorphous materials in many systems such as Pd-based, La-based, Mg-based, Fe-based, Ni-based, Zr-based, rare earth-based, and the like. Among them, Zr-based bulk amorphous is attracting attention because of its excellent amorphous forming ability and excellent mechanical properties, and is particularly favored in biomedical materials such as artificial joints, femoral head supports, etc. because of its biocompatibility and low elastic modulus and elastic limit closer to those of natural bones than those of medical stainless steel materials. In addition, compared with other system amorphous, the zirconium-based amorphous alloy has better mechanical properties such as high strength, high hardness, wear resistance, corrosion resistance, oxidation resistance and the like, and also has relatively lower material cost, so that the zirconium-based amorphous alloy has a larger application prospect in the fields of engineering materials, aerospace, sports equipment and the like. However, almost all of the currently developed zirconium-based amorphous alloys having strong glass-forming ability contain metallic nickel or beryllium. Nickel and beryllium are biocompatible elements with high cytotoxicity, and particularly, the removal of Be and Ni elements from amorphous alloy components with high glass forming capability can greatly reduce the amorphous forming capability of the system, so that large-size amorphous alloys cannot Be prepared. On the other hand, the room temperature brittleness of the Zr-based amorphous alloy containing Be can cause sudden and catastrophic fracture of the material, so that the practical application of the Zr-based amorphous alloy is limited.
Disclosure of Invention
The invention develops a nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability, aims to remove Be and Ni elements with toxic and side effects on cells, has strong glass forming capability, and can prepare centimeter-level bulk amorphous alloy and biocompatible amorphous alloy with larger room-temperature plastic deformation capability by a conventional electric arc melting copper mold suction casting method.
The technical scheme of the invention is as follows: a nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability comprises the following components in percentage by atom: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 2 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
Further, the nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability comprises the following components in percentage by atom: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 3 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
Further, when M is Nb element, a =56, b =26.7, c =7.5, d =6.8, and e =3, the atomic percentage of the nickel-free beryllium-free zirconium-based amorphous alloy component is expressed as: zr56Cu26.7Al7.5Co6.8Nb3Alloys capable of formingThe critical dimension of the bulk amorphous alloy is not less than 10mm, and the plastic deformation is not less than 5%.
Further, M is Si element, a =58, b =23, c =9, d =9, e =1, and the atomic percentage of the nickel-free beryllium-free zirconium-based amorphous alloy component is expressed as follows: zr58Cu23Al9Co9Si1The alloy can form bulk amorphous with critical dimension not less than 10 mm.
Further, M is Y element, a =57.3, b =25.7, c =6, d =9, e =2, Zr of the nickel-free beryllium-free zirconium-based amorphous alloy component57.3Cu25.7Al6Co9Y2The critical dimension of the alloy capable of forming bulk amorphous is 10mm, and the plastic deformation is not less than 4%.
The invention also aims to provide the preparation method of the nickel-free beryllium-free zirconium-based amorphous alloy by adopting an arc melting copper mold suction casting method, which comprises the following specific steps:
1) cutting high-purity metals Zr, Cu, Al, Co, Ag, Hf, Nb, Ge and Si according to the mass converted by the atomic ratio of the expression, wherein the purity of each element is more than 99.0wt%, removing oxide skin on the surface of the metal raw material, performing ultrasonic cleaning by using absolute ethyl alcohol, and weighing according to the required mass of each element.
2) Stacking the raw materials treated in the step 1 in a water-cooled copper crucible of a non-consumable vacuum arc furnace according to the sequence of high and low melting points, closing a furnace door, and vacuumizing the furnace chamber to 3 x 10-3Introducing argon under Pa, consuming oxygen by using pure titanium, and repeatedly smelting the raw materials for at least 5 times to obtain a uniformly smelted master alloy ingot;
3) and (4) carrying out suction casting on the smelted cast ingot into a cylindrical amorphous material by using a copper mold suction casting method.
The zirconium-based bulk amorphous material prepared by the preparation method is applied to the technical field of preparation of sports equipment, medical instruments and high-end micromechanical parts.
The invention has the beneficial effects that:
1) the alloy system does not contain Be and Ni elements harmful to organisms, and has excellent biocompatibility.
2) The alloy system has strong glass forming capability, the critical dimension of the amorphous alloy with preferred components prepared by the copper mold suction casting method is not less than 10mm, and the size requirement in the field of amorphous alloy processing can be met.
3) The alloy has better room-temperature plastic deformation capacity, and the plastic strain is more than 7% when the preferred components are broken.
FIG. 1 Zr prepared according to examples 1, 2 and 3 of the present invention57Cu26.7Al7.5Co5.8Hf3、Zr57Cu26.7Al7.5Co5.8Nb3Bulk amorphous alloy sample with diameter of 10mm and Zr57Cu26.7Al7.5Co5.8Ag3XRD pattern of 5mm sample.
FIG. 2 Zr prepared in example 1 of the present invention57Cu26.7Al7.5Co5.8Hf3DSC curve (temperature rising rate of 20K/min) of the bulk amorphous alloy.
FIG. 3 Zr prepared in example 1 of the present invention57Cu26.7Al7.5Co5.8Hf3The compressive stress strain curve of the bulk amorphous alloy is shown schematically.
FIG. 4 Zr prepared in example 2 of the present invention57Cu26.7Al7.5Co5.8Nb3DSC curve (temperature rising rate of 20K/min) of the bulk amorphous alloy.
FIG. 5 Zr prepared in example 2 of the present invention57Cu26.7Al7.5Co5.8Nb3The compressive stress strain curve of the bulk amorphous alloy is shown schematically.
FIG. 6 Zr prepared in example 2 of the present invention57Cu26.7Al7.5Co5.8Ag3DSC curve (temperature rising rate of 20K/min) of the bulk amorphous alloy.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
The invention relates to a nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capacity, which comprises the following components in atomic percentageThe ratio expression is: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 2 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
The invention relates to a nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capacity, which is characterized in that the atomic percentage expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 3 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
A method for preparing the nickel-free and beryllium-free zirconium-based amorphous alloy by adopting electric arc melting copper mold suction casting comprises the following specific steps:
step 1: designing components, cutting high-purity metals of Zr, Cu, Al, Co, Ag, Hf, Nb, Ge and Si according to the mass converted by the atomic ratio of the expression, wherein the purity of each element is more than 99.0wt%, removing oxide skin on the surface of a metal raw material, performing ultrasonic cleaning by using absolute ethyl alcohol, and weighing according to the required mass;
step 2: stacking the raw materials treated in the step 1 in a water-cooled copper crucible of a non-consumable vacuum arc furnace according to the sequence of high and low melting points, closing a furnace door, and vacuumizing the furnace chamber to 3 x 10-3Introducing argon under Pa, consuming oxygen by using pure titanium, and repeatedly smelting the raw materials for at least 5 times to obtain a uniformly smelted master alloy ingot;
and step 3: and (3) carrying out suction casting on the smelted cast ingot by using a copper mold suction casting method to obtain the cylindrical nickel-free beryllium-free zirconium-based amorphous alloy material.
The critical dimension of the nickel-free and beryllium-free zirconium-based amorphous alloy prepared by the method is not less than 10mm, and the plastic deformation capacity is not less than 7%.
The zirconium-based bulk amorphous material prepared by the preparation method is applied to the technical field of preparation of sports equipment, medical instruments and high-end micromechanical parts.
Example 1:
in zirconium-based bulk amorphous alloysThe atomic percentage of each component is as follows: zr 57%, Cu 26.7%, Al7.5%, Co5.8%, Hf3%57Cu26.7Al7.5Co5.8Hf3Has strong glass forming ability, and can obtain the bulk amorphous alloy with the critical dimension not less than 10mm under the condition of electric arc melting copper mold suction casting.
As shown in FIG. 1, Zr57Cu26.7Al7.5Co5.8Hf3The XRD pattern of the 10mm sample only has typical amorphous diffuse scattering peaks, which indicates that the alloy with the thickness of 10mm is an amorphous phase and has strong amorphous forming capability.
FIG. 2 shows Zr57Cu26.7Al7.5Co5.8Hf3The DSC curve of the sample shows a temperature rise rate of 20K/min, from which the glass transition temperature (T) can be seeng) Initial crystallization temperature (T)x) And supercooled liquid region width (T)x-Tg) 653K, 730K and 77K, respectively.
The room temperature compressive stress strain curve of the amorphous alloy is shown in fig. 3, 1.0 x 10-4s-1. It can be seen that the alloy does not immediately undergo catastrophic fracture after the yield strength is reached, but undergoes a period of plastic deformation: (>6 percent), which shows that the amorphous alloy has good plastic deformation capability.
Example 2:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 57%, Cu 26.7%, Al7.5%, Co5.8%, and Nb 3%57Cu26.7Al7.5Co5.8Nb3Has strong amorphous forming ability, and can obtain the bulk amorphous alloy with the critical dimension of 10mm at most under the condition of arc melting copper mold suction casting.
As shown in FIG. 1, Zr57Cu26.7Al7.5Co5.8Nb3The XRD pattern of the 10mm sample has the typical amorphous diffuse scattering peak, although a small peak appears at the first scattering peak, indicating that the 10mm alloy is mostly amorphous and still has a relatively strong glass forming ability.
FIG. 4 shows Zr57Cu26.7Al7.5Co5.8Nb3The DSC curve of the sample shows a temperature rise rate of 20K/min, from which the glass transition temperature (T) can be seeng) Initial crystallization temperature (T)x) And supercooled liquid region width (T)x-Tg) 668K, 747K and 79K, respectively.
The room temperature compressive stress strain curve of the amorphous alloy is shown in fig. 5, and the strain rate is 1.0 x 10-4s-1. It can be seen that the alloy does not immediately undergo catastrophic fracture after the yield strength is reached, but undergoes a period of plastic deformation: (>7 percent), which shows that the amorphous alloy has good plastic deformation capability.
Example 3:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 57%, Cu 26.7%, Al7.5%, Co5.8%, Ag3%57Cu26.7Al7.5Co5.8Ag3Has strong amorphous forming ability, and can obtain the block amorphous alloy with the critical dimension not less than 5mm under the condition of arc melting copper mold suction casting.
As shown in FIG. 1, Zr57Cu26.7Al7.5Co5.8Ag3The XRD pattern of the 5mm sample only has typical amorphous diffuse scattering peaks, which indicates that the alloy with the thickness of 5mm is an amorphous phase and has stronger glass forming capability.
FIG. 6 shows Zr57Cu26.7Al7.5Co5.8Ag3The DSC curve of the sample shows a temperature rise rate of 20K/min, from which the glass transition temperature (T) can be seeng) Initial crystallization temperature (T)x) And supercooled liquid region width (T)x-Tg) 653K, 720K, and 67K, respectively.
Example 4:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 56%, Cu 26.7%, Al7.5%, Co6.8%, Hf3% formed Zr56Cu26.7Al7.5Co6.8Hf3Has strong glass forming ability, and can obtain blocks with critical dimension not less than 10mm under the condition of arc melting copper mold suction castingBulk amorphous alloys.
Example 5:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 56%, Cu 26.7%, Al7.5%, Co6.8%, Y3%56Cu26.7Al7.5Co6.8Y3Has strong glass forming ability, and can obtain the bulk amorphous alloy with the critical dimension not less than 10mm under the condition of electric arc melting copper mold suction casting.
Example 6:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 58%, Cu 23%, Al 9%, Co9%, Si1%58Cu23Al9Co9Si1Has strong glass forming ability, and can obtain the bulk amorphous alloy with the critical dimension not less than 10mm under the condition of electric arc melting copper mold suction casting.
Example 7:
the zirconium-based bulk amorphous alloy comprises the following components in atomic percentage: zr 58%, Cu 27%, Al 9%, Co3%, Ge3% formed Zr58Cu27Al9Co3Ge3Has strong glass forming ability, and can obtain the bulk amorphous alloy with the critical dimension not less than 10mm under the condition of electric arc melting copper mold suction casting.
The invention has the beneficial effects that:
4) the alloy system does not contain Be and Ni elements harmful to organisms, and has excellent biocompatibility.
5) The alloy system has strong glass forming capability, the critical dimension of the amorphous alloy with preferred components prepared by the copper mold suction casting method is not less than 10mm, and the size requirement in the field of amorphous alloy processing can be met.
6) The alloy has better room-temperature plastic deformation capacity, and the plastic strain is more than 7% when the preferred components are broken.
The above detailed description of the preferred embodiments of the present invention is not intended to limit the scope of the present invention, but is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability is characterized in that the atomic percent expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 2 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
2. The nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability is characterized in that the atomic percent expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zraCubAlcCodMeWherein a is more than or equal to 56 and less than or equal to 58, b is more than or equal to 23 and less than or equal to 27, c is more than or equal to 5 and less than or equal to 9, d is more than or equal to 3 and less than or equal to 9, e is more than or equal to 1 and less than or equal to 3, M is Nb, Hf, Ag, Y, Si or Ge, and a + b + c + d + e = 100.
3. The nickel-free beryllium-free zirconium-based amorphous alloy according to claim 1 or 2, wherein when M is Nb element, a =56, b =26.7, c =7.5, d =6.8, and e =3, the atomic percentage expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zr56Cu26.7Al7.5Co6.8Nb3The alloy can form bulk amorphous alloy with the critical dimension not less than 10mm and the plastic deformation not less than 5%.
4. The nickel-free beryllium-free zirconium-based amorphous alloy according to claim 1 or 2, wherein M is Si element, a =58, b =23, c =9, d =9, e =1, and the composition of the nickel-free beryllium-free zirconium-based amorphous alloy in atomic percent is expressed as follows: zr58Cu23Al9Co9Si1The alloy can form bulk amorphous with critical dimension not less than 10 mm.
5. The nickel-free and beryllium-free zirconium-based amorphous alloy according to claim 1 or 2, which isCharacterized in that M is Y element, a =57.3, b =25.7, c =6, d =9, e =2, and the atomic percentage expression of the nickel-free beryllium-free zirconium-based amorphous alloy component is as follows: zr57.3Cu25.7Al6Co9Y2The critical dimension of the alloy capable of forming bulk amorphous is 10mm, and the plastic deformation is not less than 4%.
6. The nickel-free beryllium-free zirconium-based amorphous alloy according to claim 1 or 2, wherein M is Ag element, a =58, b =27, c =9, d =3, e =3, and the composition of the nickel-free beryllium-free zirconium-based amorphous alloy in atomic percent is expressed as follows: zr58Cu27Al9Co3Ag3The alloy can form bulk amorphous with a critical dimension not less than 10 mm.
7. The nickel-free beryllium-free zirconium-based amorphous alloy according to claim 1, wherein when M is Si, a =58%, b =23%, c =9%, d =9%, e =1%, and the atomic percentage expression of the components of the nickel-free beryllium-free zirconium-based amorphous alloy is as follows: zr58Cu23Al9Co9Si1Bulk amorphous alloy with critical dimension not less than 10 mm.
8. A method for preparing the nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability according to any one of claims 1 to 7 by adopting an electric arc melting copper mold suction casting method, which is characterized by comprising the following specific steps:
step 1) cutting high-purity metals of Zr, Cu, Al, Co, Ag, Hf, Nb, Ge and Si according to the mass converted by the atomic ratio of the expression of the design components, wherein the purity of each element is more than 99.0wt%, removing oxide skin on the surface of the metal raw material, and performing ultrasonic cleaning by using absolute ethyl alcohol for later use;
step 2) stacking the raw materials processed in the step 1 in a water-cooled copper crucible of a non-consumable vacuum arc furnace according to the sequence of high and low melting points, closing a furnace door, and pumping high vacuum to 3 x 10 to the furnace chamber-3Below Pa, introducing argon, consuming oxygen with pure titanium, and repeatedly smelting the raw materials for at least 5 timesObtaining a master alloy ingot which is uniformly smelted;
and 3) carrying out suction casting on the smelted cast ingot into a cylindrical nickel-free beryllium-free zirconium-based amorphous alloy by using a copper mold suction casting method.
9. The method as claimed in claim 8, wherein the critical dimension of the nickel-free beryllium-free zirconium-based amorphous alloy prepared by the method is not less than 10mm, and the plastic deformability is not less than 7%.
10. The nickel-free beryllium-free zirconium-based amorphous alloy prepared by the preparation method of claim 8 is applied to the technical field of preparation of sports equipment, medical instruments and high-end micromechanical parts.
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