CN106756647B - A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel - Google Patents

A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel Download PDF

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CN106756647B
CN106756647B CN201611141148.2A CN201611141148A CN106756647B CN 106756647 B CN106756647 B CN 106756647B CN 201611141148 A CN201611141148 A CN 201611141148A CN 106756647 B CN106756647 B CN 106756647B
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amorphous alloy
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zirconium
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CN106756647A (en
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吕昭平
曹迪
王辉
吴渊
刘雄军
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University of Science and Technology Beijing USTB
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    • 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
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    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

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Abstract

A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel, the atomic percent of the alloys components are as follows: Zr 38-50%, Hf 2-15%, Cu 20-30%, Fe 5-10%, Al 10-15%, Co 0-5%, Ag 0-5%, Nb 0-5%；It is prepared using the method for electric arc melting copper mold.The amorphous alloy improves the biocompatibility of Zr based alloy without containing metallic elements such as Be and Ni；With strong amorphous formation ability, the Zr base block amorphous alloy that critical dimension is not less than 5mm can be prepared using copper mold casting；With high hardness, and Vickers hardness is all larger than 540Hv；With > 3% plastic deformation ability；With wide supercooling liquid phase region range, maximum can reach 92K.There is boundless application prospect in biomedical materials fields such as accurate complicated medical zero device, joint prosthesis and the miscellaneous bones of people.

Description

A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel
Technical field
The invention belongs to block amorphous alloys, and in particular to a kind of high-ductility Zr matrix body without metallic element Be and Ni Amorphous alloy, critical dimension are not less than 5mm, and plastic deformation ability is not less than 3%.
Technical background
Amorphous alloy (glassy metal) is that there is the metals hoped as structure and function application of new generation in recent years Material.Have the arrangement of long-range order different with atom in traditional metal materials, the atom of amorphous alloy is random arrangement, And the defects of not having long-range order, crystal boundary, dislocation are not present in its microstructure, therefore amorphous alloy shows to pass High intensity, high rigidity, high elastic limit, low modulus and the excellent performance such as corrosion-resistant that system crystal alloy cannot achieve.It removes Except this, amorphous alloy shows very high stickiness flowing in supercooling liquid phase region, shows superplastic deformation feature.Amorphous closes This characteristic of gold can make its accurately compression moulding in supercooling liquid phase region.These superior performances make amorphous alloy There is very wide application prospect in many fields.
In recent years, researcher obtains in more than ten alloy systems such as Zr base, Pd base, La base, Mg base, Fe base, Ni base Bulk amorphous materials.Compared with the alloy of other systems, Zr base block amorphous alloy is due to its excellent amorphous formation ability It is concerned.The Zr such as Zr-Ti-Cu-Ni-Be, Zr-Ti-Cu-Ni-Al, Zr-Cu-Ni-Al, Zr-Cu-Al-Be of recent development Amorphous alloy has high-intensitive (2GPa), high tenacity (KIC~60MPam1/2), high elastic limit (2%) and low elastic modulus (50- The characteristics such as 100GPa).However, in the strong Zr base block amorphous alloy system of amorphous formation ability, to improve amorphous formation energy Power, Be or Ni are often indispensable in the alloy system.But unexpected disaster occurs for material containing Be and after reaching elastic limit Property fracture.It can be seen that the biocompatibility and brittleness at room temperature of Zr base noncrystal alloy limit its practical application, therefore, it is necessary to The novel high-ductility Zr base noncrystal alloy without Be and Ni element with strong amorphous formation ability is developed, to widen bulk amorphous alloy Application of the alloy in field of biomedicine.
Summary of the invention
The present invention develops a kind of high-ductility zirconium-based bulk amorphous alloy of the no beryllium without nickel, it is therefore intended that not only removes to people Body has Be the and Ni element of toxic side effect, good biocompatibility, and has strong amorphous formation ability and plastic deformation ability, To obtain amorphous alloy in the three all good resultant effect of aspect of safety, processability and economy.
The technical scheme is that a kind of high-ductility zirconium-based bulk amorphous alloy of no beryllium without nickel, the amorphous alloy Atomic percent expresses ZraHfbCucFedAleLf, and each component: 38≤a≤50,2≤b≤15,20≤c≤30,5≤d≤10, 10≤e≤15,0≤f≤5, and a+b+c+d+e+f=100, wherein L be one of J or K or a variety of, J Mn, Co, Zn, At least one of Au, Ag, Pd, Pt, Cd, Ru, Re, Os, Ir；K is at least one of V, Ta, Nb, Cr, W, Mo, Y.
Further when L is Ag, a=39, b=14, c=26, d=8, e=12, f=1, Zr39Hf14Cu26Fe8Al12Ag1It closes Gold is capable of forming large block amorphous critical dimension not less than 5mm, and Vickers hardness is not less than 558Hv, and plastic strain is not less than 3%, And supercooled liquid phase sector width is not less than 53K.
Further, when L be Co, two kinds of elements of Nb, a=38, b=14, c=26, d=8, e=12, f=2, Zr38Hf14Cu26Fe8Al12(CoNb)2Alloy is capable of forming large block amorphous critical dimension not less than 5mm, and Vickers hardness is not less than 572Hv, plastic strain is not less than 4%, and supercooled liquid phase sector width is not less than 64K.
Further, the atomic percent expression formula of the amorphous alloy is ZraHfbCucFedAle, and each component: 38≤a≤ 50,2≤b≤15,20≤c≤30,5≤d≤10,10≤e≤15, and a+b+c+d+e=100.
Work as a=40, b=14, c=26, when d=8, e=12, Zr40Hf14Cu26Fe8Al12Alloy is capable of forming large block amorphous Critical dimension be not less than 5mm, Vickers hardness is not less than 551Hv, and plastic strain is not less than 5%, and supercooled liquid phase sector width is not Lower than 91K.
It is a further object of the present invention to provide the preparation methods of above-mentioned alloy, specifically includes the following steps:
Step 1. is the metal Zr of 99.0wt%-99.99wt% with purity, and Hf, Cu, Fe, Al, Ag, Nb, Co is according to above-mentioned The atomic percent of expression formula is converted into quality；
Step 2. removes the raw material surface scale in step 1, and cleans raw material using industrial alcohol, and press respective institute Quality is needed to weigh；
Step 2 treated raw material is deposited in non-consumable arc furnace or cold crucible by fusing point sequence by step 3. Melting is carried out in shower furnace.After the abundant melting of master alloy is uniform, using suction pouring equipment, alloy suction is cast into different sizes Water cooled copper mould in, obtain amorphous alloy material.
The beneficial effects of the present invention are:
(1) alloy system does not contain Be and Ni element harmful to organism, and biocompatibility is excellent.
(2) alloy system has strong amorphous formation ability, the amorphous alloy prepared by the method for copper mold, critical Size is not less than 5mm, can satisfy the size requirement of amorphous alloy manufacture field.
(3) alloy has good plastic deformation ability, and plastic strain is greater than 3%, maximum reachable 18% when being broken.
(4) alloy has high hardness, and Vickers hardness is above 540Hv.
(5) alloy has wide critical cooling rate, is not less than 53K, and highest can achieve 92K, be conducive to Superplastic forming processing.
The XRD diagram of Zr-Hf-Cu-Fe-Al Al-Cu-Zn block amorphous alloy prepared by Fig. 1 present example 1；
The compressive stress strain curve of Zr-Hf-Cu-Fe-Al Al-Cu-Zn block amorphous alloy prepared by Fig. 2 present example 1.
Zr-Hf-Cu-Fe-Al-L1 and Zr-Hf-Cu-Fe-Al-L2 prepared by Fig. 3 present example 2,3 is series massive amorphous The XRD diagram of alloy.
The Vickers hardness of Zr-Hf-Cu-Fe-Al-L1 Al-Cu-Zn block amorphous alloy prepared by Fig. 4 present example 2.
Specific embodiment
The following further describes the technical solution of the present invention for son combined with specific embodiments below.
The preparation and its performance of embodiment 1:Zr-Hf-Cu-Fe-Al Al-Cu-Zn block amorphous alloy
Design ZraHfbCu26Fe8Al12Amorphous alloy component, wherein a=46,44,42,40；B=54-a.Obtaining ingredient is Zr46Hf8Cu26Fe8Al12、Zr44Hf10Cu26Fe8Al12、Zr42Hf12Cu26Fe8Al12And Zr40Hf14Cu26Fe8Al12Alloy.
As shown in Figure 1, Zr46Hf8Cu26Fe8Al12、Zr44Hf10Cu26Fe8Al12、Zr42Hf12Cu26Fe8Al12With Zr40Hf14Cu26Fe8Al12The XRD spectrum of alloy 5mm sample, map only have the typical diffusing scattering peak of amorphous, show the alloy of 5mm It is amorphous phase, which has strong amorphous formation ability.
The compression stress strain curve of alloy is as shown in Figure 2.As can be seen that alloy after reaching yield strength not Catastrophic fracture occurs immediately, but passes through one section of plastic deformation (> 5%), wherein Zr40Hf14Cu26Fe8Al12The plasticity of alloy Deformability is maximum, reaches 18% up to plastic deformation before fracture, and it is good to show that the block amorphous alloy of the alloy system has Plastic deformation ability.Related plastic deformation ability force data is referring to table 1.
The preparation and its performance of embodiment 2:Zr-Hf-Cu-Fe-Al-L1 Al-Cu-Zn block amorphous alloy
Design ZraHfbCu26Fe8Al12L1gAmorphous alloy component, wherein L1 is Ag, Co, one of Nb, a=39；B= 14；G=1 or a=39,46；B=6；G=2.Preparation alloying component is Zr46Cu26Fe8Al12Hf6Ag2, Zr46Cu26Fe8Al12Hf6Co2, Zr46Cu26Fe8Al12Hf6Nb2, Zr39Cu26Fe8Al12Hf14Ag1With Zr39Cu26Fe8Al12Hf14Nb1。
Fig. 3 show ZraHfbCu26Fe8Al12L1gIt is the XRD spectrum of alloy 5mm sample, in the XRD spectrum of 5mm sample only There is the typical diffusing scattering peak of amorphous, show that the alloy of 5mm is amorphous phase, which has strong amorphous formation ability.
It is illustrated in figure 4 ZraHfbCu26Fe8Al12L1gIt is alloy Vickers hardness, the hardness of amorphous alloy is all larger than 550Hv, The wherein highest Zr of hardness number39Cu26Fe8Al12Hf14Nb1Alloy reaches 573Hv.Relevant hardness number is referring to table 1.
The preparation of embodiment 3:Zr-Hf-Cu-Fe-Al-L2 Al-Cu-Zn block amorphous alloy and its two kinds in performance, a=38；b =14；G=2 or a=46；B=6；The atomic fraction of two kinds of elements in g=2, L2 is identical.Preparing alloying component is Zr46Cu26Fe8Al12Hf6Nb1Co1And Zr38Cu26Fe8Al12Hf14Nb1Ag1。
Zr in example threeaHfbCu26Fe8Al12L2gThe XRD spectrum of alloy 5mm sample is as shown in figure 3, wherein there was only amorphous allusion quotation The diffusing scattering peak of type shows that the alloy of 5mm is amorphous phase, which has strong amorphous formation ability.
A kind of table 1: composition, mechanical property and thermodynamics of no Be without Ni high-ductility Zr base large amorphous alloy of the invention Parameter

Claims (5)

1. a kind of high-ductility zirconium-based bulk amorphous alloy of no beryllium without nickel, which is characterized in that the atomic percent of the amorphous alloy Expression formula are as follows: Zr38Hf14Cu26Fe8Al12(CoNb)2Alloy is capable of forming large block amorphous critical dimension not less than 5mm, Vickers Hardness is not less than 572HV, and plastic strain is not less than 4%, and supercooled liquid phase sector width is not less than 64K.
2. a kind of high-ductility zirconium-based bulk amorphous alloy of no beryllium without nickel, which is characterized in that the atomic percent of the amorphous alloy Expression formula is Zr40Hf14Cu26Fe8Al12Alloy is capable of forming large block amorphous critical dimension not less than 5mm, and Vickers hardness is not low In 551HV, plastic strain is not less than 5%, and supercooled liquid phase sector width is not less than 91K.
3. a kind of high-ductility zirconium-based bulk amorphous alloy of no beryllium without nickel, which is characterized in that the atomic percent of the amorphous alloy Expression formula is Zr39Hf14Cu26Fe8Al12Ag1；Alloy is capable of forming large block amorphous critical dimension not less than 5mm, Vickers hardness Not less than 558HV, plastic strain is not less than 3%, and supercooled liquid phase sector width is not less than 53K.
4. a kind of prepare the method such as zirconium-based bulk amorphous alloy as claimed in any one of claims 1-3, which is characterized in that specific The following steps are included:
Step 1. is converted into for the raw metal metal of 99.0wt%-99.99wt% according to the atomic percent of expression formula with purity Mass percent；
Step 2. removes the raw metal surface scale in step 1, and cleans raw material using industrial alcohol, and press respective institute Mass percent is needed to weigh；
Step 2 treated raw metal is deposited in non-consumable arc furnace or cold crucible by fusing point sequence by step 3. Melting is carried out in shower furnace, and after the abundant melting of master alloy is uniform, using suction pouring equipment, alloy suction is cast into different sizes Water cooled copper mould in, obtain zirconium-based bulk amorphous alloy material.
5. a kind of zirconium-based bulk amorphous alloy material that method as claimed in claim 4 is prepared is led in bio-medical material Domain application.
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