US20180044770A1 - (ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof - Google Patents

(ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof Download PDF

Info

Publication number
US20180044770A1
US20180044770A1 US15/550,895 US201515550895A US2018044770A1 US 20180044770 A1 US20180044770 A1 US 20180044770A1 US 201515550895 A US201515550895 A US 201515550895A US 2018044770 A1 US2018044770 A1 US 2018044770A1
Authority
US
United States
Prior art keywords
amorphous alloy
zrm
cun
alloy
amorphous
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US15/550,895
Inventor
Haifeng Zhang
Zhengkun LI
Dechuan YU
Huameng FU
Zhengwang ZHU
Aimin Wang
Hong Li
Hongwei Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
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 Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Assigned to INSTITUTE OF METAL RESEARCH, CHINESE ACADEMY OF SCIENCES reassignment INSTITUTE OF METAL RESEARCH, CHINESE ACADEMY OF SCIENCES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FU, Huameng, LI, HONG, LI, Zhengkun, WANG, AIMIN, YU, Dechuan, ZHANG, HAIFENG, ZHANG, HONGWEI, ZHU, Zhengwang
Publication of US20180044770A1 publication Critical patent/US20180044770A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/10Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C22C1/002
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/11Making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys

Definitions

  • the present invention relates to a Zr-based amorphous alloy preparation technology, and more particularly to a (ZrM)-(CuN)—Ni—Al-RE amorphous alloy having a high glass froming ability and preparation and application thereof.
  • Zr-based amorphous alloys have many excellent properties due to their structural specificities, such as high strength (1500-2000 MPa), high hardness (about HRC 50), high elasticity limit (about 2%), excellent corrosion resistance and liquid near-net formability, etc., they have important application prospects in the fields of consumer electronics, medical and health, aerospace and transportation and other fields.
  • Zr-based amorphous alloy For the Zr-based amorphous alloy, a variety of alloy compositions have been developed, such as the Zr—Ti—Cu—Ni—Be system alloy developed in the United States, having a critical cooling rate of 1K/s, and with a strong glass froming ability and a high manufacturability. However, the application range of the alloy system is limited by its toxicBe element. Zr—Ti—Cu—Ni—Al and Zr—Nb—Cu—Ni—Al amorphous alloy have an amorphous size of ⁇ 15 mm and a relatively weak glass froming ability. Japan developed a Zr—Al—Ni—Cu alloy system, has an amorphous size of ⁇ 30 mm. However, the alloy system requires more strict preparation conditions, high-purity raw materials and high vacuum preparation technology, which restrict its application.
  • the manufacturability (ie, the manufacturability of the amorphous alloy by employing industrial grade raw materials, low vacuum preparation and multiple cyclic utilization) of the Zr—Cu—Ni—Al alloy in the application process determines its application feasibility. Aiming at this, the present invention has developed a (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy having excellent glass froming ability and manufacturability, excellent mechanical properties and more excellent antibacterial and bacteriostatic function, have broad application prospects in the consumer electronics, health care, transportation and other fields.
  • the present invention provides a Zr—Cu—Ni—Al alloy having the composition of M, N and RE elements, wherein the (ZrM)-(CuN)—Ni—Al-(RE) alloy has a high glass froming ability and manufacturability, excellent mechanical properties and antibacterial and bacteriostatic functions, which laid the application foundation of the alloy.
  • the conventional Zr—Cu—Ni—Al amorphous alloy has excellent mechanical properties and forming ability, but its manufacturing ability is relatively poor, that is, in the practical application of the preparation process, the forming, defect control, production efficiency and cost and other factors have to be considered together: the purity of raw materials and the preparation vacuum are relatively low, which result in its decreased glass froming ability, decreased manufacturability and limited practical application.
  • the present invention comprehensively considers the glass froming ability and manufacturability of Zr—Cu—Ni—Al type amorphous alloy, and aims to solve the bottleneck problem that restricts its application. It is found that the Zr—Cu—Ni—Al alloy can easily precipitate CuZr compound during the solidification process. If the precipitation of CuZr compound is effectively inhibited, the manufacturability of Zr—Cu—Ni—Al can be improved.
  • Cu-like element N (Ag), Zr-like element M (Hf, Ti), so during the precipitate process, Cu and N elements compete with each other to form the compounds (CuZr and AgCu compounds) with Zr element, and Zr and M (Hf, Ti) elements compete with each other to form the compounds (such as CuZr, CuHf).
  • N Ag
  • Zr-like element M Hf, Ti
  • Cu and N elements compete with each other to form the compounds (CuZr and AgCu compounds) with Zr element
  • Zr and M (Hf, Ti) elements compete with each other to form the compounds (such as CuZr, CuHf).
  • the result of competing with each other is that the solidification process is complicated, the precipitation of CuZr is inhibited, and the glass froming ability and manufacturability of Zr—Cu—Ni—Al are improved.
  • the addition of rare earth element RE can effectively reduce the effect of the increase of the oxygen content on the glass froming ability due to the low degree of vacuum.
  • the rare earth element RE is combined with oxygen to form oxide, floating on its surface, thus inhibiting the combination of oxygen and other elements
  • the addition of RE increases the complexity of alloying elements, to enhance the glass froming ability thereof.
  • the simultaneous addition of M, N and RE in the Zr—Cu—Ni—Al alloy significantly increases the forming ability and manufacturability of the alloy. Adding separately M, N or RE have a certain role, but simultaneously adding these elements will generate a best result.
  • a (ZrM)-(CuN)—Ni—Al-RE amorphous alloy for manufacturing a mechanical component which containing:
  • a rare earth element RE 40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti, and N is Ag, the rare earth element RE is Y, Gd, Er, Sc or a combination thereof.
  • the present invention is characterized in that a small amount of M, N and RE elements are simultaneously added into the basis alloy of Zr—Cu—Ni—Al. In practical applications, the factors such as cost, mechanical properties and surface quality of samples are taken into account.
  • the atomic percentages of Hf, Ag and RE elements are controlled at 1%, and the atomic percentage of Ti is controlled at ⁇ 2%.
  • the method for preparing (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to the present invention is characterized in that, preparing a mother alloy ingot by an arc melting process or an induction melting process, by using Zr, Cu, Ni, Al, M, N and RE as raw materials; heating the mother alloy ingot by arc heating or induction heating process; and then preparing the amorphous alloy by casting or die casting process, wherein the process parameter is: vacuum degree is 1 ⁇ 10 1 ⁇ 10 ⁇ 3 , or being filled with argon, the melting temperature is 860 ⁇ 1200° C., and the cooling rate is 10 ⁇ 10 3 K/s.
  • the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy of the present invention can be used in the fields of consumer electronics, medical and health, aerospace or transportation, for manufacturing complex components.
  • the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy described in the present invention has the following characteristics:
  • the amorphous alloy has a high forming ability, in particular, has a good manufacturability, and its optimal glass froming ability is greater than 20 mm. Utilizing industrial manufacturing technology, the alloy repeated melting-casting preparation samples more than 4 times, still able to form amorphous, so as to ensure the quality and meet the actual production needs.
  • the mechanical properties of the amorphous alloy are as follows: the compressive fracture strength is greater than 1500 Pa, and the amorphous alloy has a more excellent antibacterial and bacteriostatic function, for the presence of Ag element is in the alloy.
  • the preparation raw materials can be industrial grade of metal Zr, Cu, Ni, Al, M, N and RE, and the vacuum is not demanding.
  • the amorphous alloy can be widely used in consumer electronics, health care, transportation and other fields, and is an ideal material for manufacturing complex, thin-walled parts, which has a broad application prospect.
  • FIG. 1 is a schematic diagram of an amorphous alloy component.
  • All raw materials (Zr, Hf, Ti, Cu, Ni, Al, Ag, Y, Gd, Sc) used in this embodiment are industrial grade metals
  • Zr and Ti metals are sponge zirconium
  • sponge titanium
  • Hf can be sponge zirconium containing a certain amount of Hf, which are prepared according to the atomic percentage.
  • mother alloy ingot by arc melting or induction melting, under the protection of argon.
  • the refined alloy ingot need to be flipped 3 to 4 times during the arc melting process of the mother alloy ingot, and then obtaining the mother alloy ingot by Cu mold casting and induction heating, wherein the heating temperature is about 1000° C., the vacuum is 10 ⁇ 1 ⁇ 10 ⁇ 2 Pa.
  • the antimicrobial properties of the amorphous alloy can be measured by a coating method (see JIS Z 2801-2000) to detect its sterilization rate against common Escherichia coli ATCC25922, wherein the concentration of bacteria is 4.2 ⁇ 10 5 cfu/ml.
  • the results show that the bactericidal rate of the amorphous alloy against Escherichia coli is more than 99.9%.
  • the Zr55Cu30Ni5Al10 alloy is one of the Zr—Cu—Ni—Al quaternary amorphous alloys having strongest forming capacity, reported in the literature, and its forming capacity is ⁇ 30 mm.
  • the alloy system requires a very demanding on the purity of the composition and preparation conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention relates to a (ZrM)-(CuN)—Ni—Al-RE amorphous alloy, which containing, by atom percent, 40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti; and N is Ag, wherein the amorphous alloy further contains a small amount of Hf, Ti, Ag and Re on the basis of a Zr—Al—Ni—Cu amorphous alloy, to maintain the mechanical properties of the Zr—Al—Ni—Cu amorphous alloy, and has a relatively strong glass froming ability, manufacturability and antimicrobial property.

Description

    FIELD OF INVENTION
  • The present invention relates to a Zr-based amorphous alloy preparation technology, and more particularly to a (ZrM)-(CuN)—Ni—Al-RE amorphous alloy having a high glass froming ability and preparation and application thereof.
  • DESCRIPTION OF RELATED ARTS
  • Zr-based amorphous alloys have many excellent properties due to their structural specificities, such as high strength (1500-2000 MPa), high hardness (about HRC 50), high elasticity limit (about 2%), excellent corrosion resistance and liquid near-net formability, etc., they have important application prospects in the fields of consumer electronics, medical and health, aerospace and transportation and other fields.
  • For the Zr-based amorphous alloy, a variety of alloy compositions have been developed, such as the Zr—Ti—Cu—Ni—Be system alloy developed in the United States, having a critical cooling rate of 1K/s, and with a strong glass froming ability and a high manufacturability. However, the application range of the alloy system is limited by its toxicBe element. Zr—Ti—Cu—Ni—Al and Zr—Nb—Cu—Ni—Al amorphous alloy have an amorphous size of φ15 mm and a relatively weak glass froming ability. Japan developed a Zr—Al—Ni—Cu alloy system, has an amorphous size of φ30 mm. However, the alloy system requires more strict preparation conditions, high-purity raw materials and high vacuum preparation technology, which restrict its application.
  • In order to improve the glass froming ability of the Zr-based amorphous alloy, a large amount of research work has been done by adjusting the compositions of the Zr—Cu—Ni—Al alloy and adding alloying elements, which mainly focused on the forming ability of the Zr—Cu—Ni—Al amorphous alloy itself. Ag, Ti, Fe, Hf and rare earth RE elements are added separately to the Zr—Cu—Ni—Al alloy, or Ag and Re are added simultaneously, but the principle of addition is not clearly stated (or is not clear), so that the added element and its content is not targeted, and the amorphous manufacturability of the alloy is not significantly improved or unknown.
  • The manufacturability (ie, the manufacturability of the amorphous alloy by employing industrial grade raw materials, low vacuum preparation and multiple cyclic utilization) of the Zr—Cu—Ni—Al alloy in the application process determines its application feasibility. Aiming at this, the present invention has developed a (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy having excellent glass froming ability and manufacturability, excellent mechanical properties and more excellent antibacterial and bacteriostatic function, have broad application prospects in the consumer electronics, health care, transportation and other fields.
  • SUMMARY OF THE PRESENT INVENTION
  • The present invention provides a Zr—Cu—Ni—Al alloy having the composition of M, N and RE elements, wherein the (ZrM)-(CuN)—Ni—Al-(RE) alloy has a high glass froming ability and manufacturability, excellent mechanical properties and antibacterial and bacteriostatic functions, which laid the application foundation of the alloy.
  • The conventional Zr—Cu—Ni—Al amorphous alloy has excellent mechanical properties and forming ability, but its manufacturing ability is relatively poor, that is, in the practical application of the preparation process, the forming, defect control, production efficiency and cost and other factors have to be considered together: the purity of raw materials and the preparation vacuum are relatively low, which result in its decreased glass froming ability, decreased manufacturability and limited practical application.
  • The present invention comprehensively considers the glass froming ability and manufacturability of Zr—Cu—Ni—Al type amorphous alloy, and aims to solve the bottleneck problem that restricts its application. It is found that the Zr—Cu—Ni—Al alloy can easily precipitate CuZr compound during the solidification process. If the precipitation of CuZr compound is effectively inhibited, the manufacturability of Zr—Cu—Ni—Al can be improved.
  • In the present invention, a small amount of Cu-like and Zr-like and rare earth RE elements are added: Cu-like element: N (Ag), Zr-like element M (Hf, Ti), so during the precipitate process, Cu and N elements compete with each other to form the compounds (CuZr and AgCu compounds) with Zr element, and Zr and M (Hf, Ti) elements compete with each other to form the compounds (such as CuZr, CuHf). The result of competing with each other is that the solidification process is complicated, the precipitation of CuZr is inhibited, and the glass froming ability and manufacturability of Zr—Cu—Ni—Al are improved.
  • The addition of rare earth element RE can effectively reduce the effect of the increase of the oxygen content on the glass froming ability due to the low degree of vacuum. On the one hand, the rare earth element RE is combined with oxygen to form oxide, floating on its surface, thus inhibiting the combination of oxygen and other elements, on the other hand, the addition of RE increases the complexity of alloying elements, to enhance the glass froming ability thereof. The simultaneous addition of M, N and RE in the Zr—Cu—Ni—Al alloy significantly increases the forming ability and manufacturability of the alloy. Adding separately M, N or RE have a certain role, but simultaneously adding these elements will generate a best result.
  • The technical solution of the present invention is as follows:
  • A (ZrM)-(CuN)—Ni—Al-RE amorphous alloy for manufacturing a mechanical component, which containing:
  • 40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti, and N is Ag, the rare earth element RE is Y, Gd, Er, Sc or a combination thereof.
  • The preferably composition ratio: Zr: 50˜55%, Cu: 28˜35%, Ni: 4˜7%, Al: 5˜11%, M: 0.1˜1.0%, N: 0.05˜1.0%, rare earth element RE: 0.1˜1.0%.
  • The present invention is characterized in that a small amount of M, N and RE elements are simultaneously added into the basis alloy of Zr—Cu—Ni—Al. In practical applications, the factors such as cost, mechanical properties and surface quality of samples are taken into account. The atomic percentages of Hf, Ag and RE elements are controlled at 1%, and the atomic percentage of Ti is controlled at ≦2%.
  • The method for preparing (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to the present invention, is characterized in that, preparing a mother alloy ingot by an arc melting process or an induction melting process, by using Zr, Cu, Ni, Al, M, N and RE as raw materials; heating the mother alloy ingot by arc heating or induction heating process; and then preparing the amorphous alloy by casting or die casting process, wherein the process parameter is: vacuum degree is 1×101˜10−3, or being filled with argon, the melting temperature is 860˜1200° C., and the cooling rate is 10˜103 K/s.
  • The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy of the present invention can be used in the fields of consumer electronics, medical and health, aerospace or transportation, for manufacturing complex components.
  • The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy described in the present invention has the following characteristics:
  • 1, The amorphous alloy has a high forming ability, in particular, has a good manufacturability, and its optimal glass froming ability is greater than 20 mm. Utilizing industrial manufacturing technology, the alloy repeated melting-casting preparation samples more than 4 times, still able to form amorphous, so as to ensure the quality and meet the actual production needs.
  • 2, The mechanical properties of the amorphous alloy are as follows: the compressive fracture strength is greater than 1500 Pa, and the amorphous alloy has a more excellent antibacterial and bacteriostatic function, for the presence of Ag element is in the alloy.
  • 3, The preparation raw materials can be industrial grade of metal Zr, Cu, Ni, Al, M, N and RE, and the vacuum is not demanding.
  • 4, The amorphous alloy can be widely used in consumer electronics, health care, transportation and other fields, and is an ideal material for manufacturing complex, thin-walled parts, which has a broad application prospect.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a schematic diagram of an amorphous alloy component.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
  • All raw materials (Zr, Hf, Ti, Cu, Ni, Al, Ag, Y, Gd, Sc) used in this embodiment are industrial grade metals, Zr and Ti metals are sponge zirconium, sponge titanium, Hf can be sponge zirconium containing a certain amount of Hf, which are prepared according to the atomic percentage. And then, prepare the mother alloy ingot by arc melting or induction melting, under the protection of argon. In order to ensure the uniform of the refined alloy ingot, the refined alloy ingot need to be flipped 3 to 4 times during the arc melting process of the mother alloy ingot, and then obtaining the mother alloy ingot by Cu mold casting and induction heating, wherein the heating temperature is about 1000° C., the vacuum is 10−1˜10−2 Pa.
  • Examples 1 to 23 shown in Table 1 (the same preparation process):
  • TABLE 1
    Composition of (ZrM)—(CuN)—Ni—Al—RE alloy, amorphous
    size and mechanical properties
    Amorphous Strength
    NO Alloy Composition (%) size (mm) (Mpa)
    1 Zr50.4Hf0.4Cu35.9Ag0.1Ni4Al9Y0.2 ≧8 1830
    2 Zr50.4Hf0.4Cu35.9Ag0.1Ni4Al9Gd0.2 ≧5 1620
    3 Zr51.6Hf0.4Cu34.9Ag0.1Ni5Al7.5Y0.5 ≧8 1800
    4 Zr51.6Hf0.4Cu34.9Ag0.1Ni5Al7.5Gd0.5 ≧6 1630
    5 Zr50Ti2Cu34.9Ag0.1Ni5Al7.5Y0.5 ≧6 1820
    6 Zr50Ti2Cu34.9Ag0.1Ni5Al7.5Gd0.5 ≧6 1650
    7 (Zr51.8Hf0.4Cu35Ag0.1Ni6Al6.7)98Y2 ≧8 1780
    8 (Zr54.6Hf0.4Cu29.9Ag0.1Ni5Al10)98Y2 ≧12 1800
    9 (Zr63.9Hf0.5Cu18Ag0.1Ni10Al7.5)98Y2 ≧5 1780
    10 (Zr54.6Hf0.4Cu29.9Ag0.1Ni5Al10)99.5Y0.5 ≧15 1820
    11 (Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10)99.5Y0.5 ≧20 1800
    12 (Zr49.96Hf0.5Cu35.19Ni2.65Ag2.15Al9.55)99.5Y0.5 ≧12 1812
    13 (Zr49.72Hf0.4Cu35.22Ni2.69Ag2.69Al9.28)99.5Y0.5 ≧20 1810
    14 (Zr49.40Hf0.4Cu35.20Ni2.73Ag3.24Al9.03)99.5Y0.5 ≧20 1810
    15 (Zr50.1Hf0.4Cu31.5Ni4Al11Ag3)99.5Y0.5 ≧20 1890
    16 (Zr48.2Hf0.3Cu36Ag0.5Ni4Al9Ti2)99.5Y0.5 ≧12 1790
    17 Zr55Cu30Ni5Al10   4 mm 1750
    18 Zr54Ti1Cu30Ni5Al10 4.5 mm 1760
    19 Zr54Hf1Cu30Ni5Al10 4.5 mm 1770
    20 Zr55Cu29.9Ag0.1Ni5Al10   5 mm 1740
    21 Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10   8 mm 1790
    22 (Zr54.8Cu29.9Ag0.3Ni5Al10)99.5Y0.5  15 mm 1800
    23 (Zr48.2Hf0.3Cu36.5Ni4Al9Ti2)99.5Y0.5 ≧10 1785
  • The antimicrobial properties of the amorphous alloy can be measured by a coating method (see JIS Z 2801-2000) to detect its sterilization rate against common Escherichia coli ATCC25922, wherein the concentration of bacteria is 4.2×105 cfu/ml. The results show that the bactericidal rate of the amorphous alloy against Escherichia coli is more than 99.9%.
  • Example 24
  • By utilizing (Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10)99.5Y0.5 alloy to prepare amorphous components by vacuum die casting method, under the conditions of induction melting 30 kg alloy, vacuum 10−1˜10−2 Pa and heating temperature 900˜1000° C. After repeating 5 times, the prepared component can still guarantee the amorphous structure of the alloy material. The prepared component is shown in FIG. 1. After Re-use 4 times, the alloy casted φ5 mm sample can still guarantee the formation of amorphous.
  • Comparative Example 1
  • The Zr55Cu30Ni5Al10 alloy is one of the Zr—Cu—Ni—Al quaternary amorphous alloys having strongest forming capacity, reported in the literature, and its forming capacity is φ30 mm. However, the alloy system requires a very demanding on the purity of the composition and preparation conditions. when employing industrial materials, under vacuum of 1×101˜10−2 Pa, its amorphous size is merely φ4 mm; when adding separately a small amount of Hf or Ti element, the amorphous size of the Zr54Hf1Cu30Ni5Al10 (Zr54Ti1Cu30Ni5Al10) is merely φ4.5 mm; when adding separately a small amount of Ag element, the amorphous size of the Zr55Cu29.9Ag0.3Ni5Al10 is φ5 mm; when adding simultaneously a small amount of Hf and Ag elements, the amorphous size of the Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10 is φ8 mm; when adding simultaneously a small amount of Ag and Y elements, the amorphous size of the (Zr54.8Cu29.9Ag0.3Ni5Al10)99.5Y0.5 is φ15 mm; and when adding simultaneously a small amount of Hf, Ag and Y elements, the amorphous size of the (Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10)99.5Y0.5 is more than φ20 mm.
  • Comparative Example 2
  • Preparing the sample of Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10 amorphous alloy the second time, which has been crystallized partly, however, the sample of (Zr54.4Hf0.4Cu29.9Ag0.3Ni5Al10)99.5Y0.5 amorphous alloy repeats 4 times, which is still amorphous, and the sample is φ5×50 mm round bar.

Claims (6)

1. A (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy adapted for preparing a mechanical component, comprising: by atomic percent, 40-65% of Zr, 18-46% of Cu, 2-15% of Ni, 4-15% of Al, 0.1-3% of M, 0.05-3% of N, 0.1-2% of a rare earth element RE, wherein M is Hf and/or Ti, and N is Ag, the rare earth element RE is Y, Gd, Er, Sc or a combination thereof.
2. The (ZrM)-(CuN)—Ni—Al-(RE) amorphous alloy according to claim 1, wherein by atomic percent, the percentages of Hf, Ag and RE are no more than 1% respectively, and the percentage of Ti is no more than 2%.
3. The (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to claim 1, wherein by atomic percent, the amorphous alloy is optimized to comprise: 50-55% of Zr, 28-35% of Cu, 4-7% of Ni, 5-11% of Al, 0.1-1.0% of M, 0.05-1.0% of N, 0.1-1.0% of a rare earth element RE.
4. A manufacturing method for the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to claim 1, comprising the following steps:
preparing a master ingot by an arc melting process or an induction melting process, by using Zr, Cu, Ni, Al, M, N and RE as raw materials;
preparing the amorphous alloy by casting or die casting process, after melting master ingot by arc heating or induction heating technique, wherein the process parameter is: vacuum degree is 1×101˜10−3 Pa, or being filled with argon, the melting temperature is 860˜1200° C., and the cooling rate is 10˜103 K/s.
5. An application of the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy according to claim 1, the amorphous alloy is capable of being can be used in the fields of electronics, medical and health, aerospace or traffic transport.
6. The application of the (ZrM)-(CuN)—Ni—Al-RE amorphous alloy, recited in claim 5, wherein the amorphous alloy is capable of being used for making can make complex components.
US15/550,895 2015-02-15 2015-09-22 (ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof Abandoned US20180044770A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201510082525.9 2015-02-15
CN201510082525.9A CN104651756B (en) 2015-02-15 2015-02-15 (ZrM)-(CuN)-Ni-Al-(Re) non-crystaline amorphous metal, preparation method and application
PCT/CN2015/000657 WO2016127279A1 (en) 2015-02-15 2015-09-22 (zrm)-(cun)-ni-al-(re) amorphous alloy, preparation method and application thereof

Publications (1)

Publication Number Publication Date
US20180044770A1 true US20180044770A1 (en) 2018-02-15

Family

ID=53243391

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/550,895 Abandoned US20180044770A1 (en) 2015-02-15 2015-09-22 (ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof

Country Status (3)

Country Link
US (1) US20180044770A1 (en)
CN (1) CN104651756B (en)
WO (1) WO2016127279A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems
CN115247243A (en) * 2022-08-24 2022-10-28 盘星新型合金材料(常州)有限公司 HF-containing light large-size block amorphous alloy and preparation method and application thereof
CN115354246A (en) * 2022-08-24 2022-11-18 盘星新型合金材料(常州)有限公司 Rare earth modified light block amorphous alloy and preparation method and application thereof

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104651756B (en) * 2015-02-15 2016-11-23 中国科学院金属研究所 (ZrM)-(CuN)-Ni-Al-(Re) non-crystaline amorphous metal, preparation method and application
CN105154796B (en) * 2015-08-31 2017-03-22 深圳市锆安材料科技有限公司 Zircon-based amorphous alloy and preparation method thereof
CN105220085A (en) * 2015-10-21 2016-01-06 东莞宜安科技股份有限公司 A kind of high strength non-crystaline amorphous metal and its preparation method and application
CN105220083B (en) * 2015-10-21 2017-05-31 东莞宜安科技股份有限公司 A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and its preparation method and application
CN105316603B (en) * 2015-10-26 2017-05-24 深圳市锆安材料科技有限公司 High-toughness amorphous alloy and preparation method thereof
CN105316604B (en) * 2015-10-26 2017-04-19 宋佳 High-hardness amorphous alloy and preparation method thereof
CN105296896B (en) * 2015-11-13 2017-04-05 宋佳 A kind of antibacterial non-crystaline amorphous metal and preparation method thereof
CN105401103B (en) * 2015-11-13 2017-07-28 东莞宜安科技股份有限公司 A kind of amorphous composite material of high tenacity and its preparation method and application
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
CN107099757B (en) * 2016-02-23 2019-12-10 中国科学院金属研究所 Zr-based amorphous alloy capable of being repeatedly smelted and preparation method thereof
CN106947925A (en) * 2017-03-22 2017-07-14 中国科学院金属研究所 A kind of Zr base block amorphous alloys and its preparation method and application
CN107236913B (en) * 2017-05-18 2019-04-26 中国科学院金属研究所 A kind of zirconium-base amorphous alloy and preparation method thereof
CN110295293A (en) * 2019-06-28 2019-10-01 中国科学院金属研究所 A kind of amorphous alloy component and preparation method 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
CN115961221B (en) * 2022-12-08 2024-04-05 大连理工大学 Block amorphous alloy shaped charge liner and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102080196A (en) * 2009-11-30 2011-06-01 比亚迪股份有限公司 Zirconium-based amorphous alloy and preparation method thereof
US20130255837A1 (en) * 2012-03-29 2013-10-03 Atakan Peker Zirconium based bulk metallic glasses
WO2014079188A1 (en) * 2012-11-26 2014-05-30 华为技术有限公司 Zirconium-based amorphous alloy

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102912261A (en) * 2012-10-23 2013-02-06 上海交通大学 Zirconium-based amorphous alloy and preparation method thereof
CN104032240B (en) * 2014-03-05 2016-03-16 中国科学院金属研究所 A kind of Zr-Cu-Ni-Al-Ag-Y bulk amorphous alloy and its preparation method and application
CN104651756B (en) * 2015-02-15 2016-11-23 中国科学院金属研究所 (ZrM)-(CuN)-Ni-Al-(Re) non-crystaline amorphous metal, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102080196A (en) * 2009-11-30 2011-06-01 比亚迪股份有限公司 Zirconium-based amorphous alloy and preparation method thereof
US20130255837A1 (en) * 2012-03-29 2013-10-03 Atakan Peker Zirconium based bulk metallic glasses
WO2014079188A1 (en) * 2012-11-26 2014-05-30 华为技术有限公司 Zirconium-based amorphous alloy

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems
US11821064B2 (en) * 2019-04-30 2023-11-21 Oregon State University Cu-based bulk metallic glasses in the Cu—Zr—Hf—Al and related systems
CN115247243A (en) * 2022-08-24 2022-10-28 盘星新型合金材料(常州)有限公司 HF-containing light large-size block amorphous alloy and preparation method and application thereof
CN115354246A (en) * 2022-08-24 2022-11-18 盘星新型合金材料(常州)有限公司 Rare earth modified light block amorphous alloy and preparation method and application thereof

Also Published As

Publication number Publication date
WO2016127279A1 (en) 2016-08-18
CN104651756B (en) 2016-11-23
CN104651756A (en) 2015-05-27

Similar Documents

Publication Publication Date Title
US20180044770A1 (en) (ZrM)-(CuN)-Ni-Al-RE amorphous alloy and manufacturing method and application thereof
EP3115479A1 (en) Zr-cu-ni-al-ag-y bulk amorphous alloy, and preparation method and application thereof
JP2015507693A (en) Zr-based amorphous alloy
CN103924136B (en) A kind of aluminum alloy for automobile wheel hub material
EP3045557B1 (en) Zirconium-based amorphous alloy and preparation method therefor
CN105525134B (en) A kind of high-strength alloy and preparation method thereof
KR101910539B1 (en) Metal complex
JPWO2011070860A1 (en) Magnetic material sputtering target
JP6393696B2 (en) Cu-Ga-In-Na target
KR102007060B1 (en) Bulk metallic glass forming alloy
EP3872197A1 (en) Composite copper alloy comprising high-entropy alloy, and manufacturing method therefor
CN103774065A (en) Zirconium base amorphous alloy
US20150307975A1 (en) Zirconium based bulk metallic glasses with hafnium
CN109207872B (en) Nickel-free beryllium-free copper-free zirconium-based block amorphous alloy with high amorphous forming capability and preparation method thereof
CN106903294A (en) A kind of preparation method of inexpensive non-crystaline amorphous metal part and inexpensive non-crystaline amorphous metal part
CN103243227B (en) Preparation method of equal-atomic-ratio titanium-nickel alloy ingots
KR101781692B1 (en) Brazing filler alloy composition with lower melting point for the brazing of titanium alloys
CN104178705B (en) Ce-Ga-Cu-Al Al-Cu-Zn block amorphous alloy
CN106244946B (en) A kind of high-strength plasticity zirconium-base amorphous alloy and preparation method containing molybdenum
CN103103406B (en) Antibacterial aluminum alloy for food container
CN105132834B (en) A kind of high intensity non-crystaline amorphous metal and preparation method thereof
CN104498845A (en) Zirconium-based amorphous alloy and preparation method thereof
KR20100133867A (en) A tin-containing amorphous alloy composition
KR101488195B1 (en) Method for manufacturing titanium-based alloy using ferro-vanadium and titanium-based alloy manufactured thereof
Dong et al. Effect of aging temperature on microstructure and hardness of CoCrFeNiTi0. 5 high entropy alloy

Legal Events

Date Code Title Description
AS Assignment

Owner name: INSTITUTE OF METAL RESEARCH, CHINESE ACADEMY OF SC

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHANG, HAIFENG;LI, ZHENGKUN;YU, DECHUAN;AND OTHERS;REEL/FRAME:043541/0196

Effective date: 20170719

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION