CN108385039A - A kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof - Google Patents

A kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof Download PDF

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CN108385039A
CN108385039A CN201810122693.XA CN201810122693A CN108385039A CN 108385039 A CN108385039 A CN 108385039A CN 201810122693 A CN201810122693 A CN 201810122693A CN 108385039 A CN108385039 A CN 108385039A
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zirconium
alloy
amorphous
composite material
base
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CN108385039B (en
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李丹
王晶
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AAC Precision Manufacturing Technology Changzhou Co Ltd
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    • 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • 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

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Abstract

The present invention relates to the Material Field of high-mechanical property, more particularly to a kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof.The material is mainly made of zirconium-base amorphous alloy and the second phase.The application in original non-crystaline amorphous metal matrix by being added the second phase, there is the extension for preventing single shear band in amorphous in the second phase, induce the formation of more shear bands, under the premise of not reducing script alloy material fracture bending strength, the bending fracture strain of material is improved, method provided by the present invention improves material intrinsic property from raw material end, product after molding need not be surface-treated etc., and in addition to foundry alloy melting step, without introducing additional process, it is suitble to volume production.

Description

A kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof
Technical field
The present invention relates to consumer electronics product, accurate device (such as robot), medical instrument, space flight and aviation application necks The material of the high-mechanical property in domain, more particularly to the superhigh intensity Zirconium base non-crystalline composite material of a kind of high tenacity and its preparation side Method.
Background technology
Non-crystaline amorphous metal is gained the name because it has apparent structure to distinguish with common crystalline material.General material is with crystal Form exists, and the characteristic of amorphous is longrange disorder (shortrange order), metastable state (certain temperature crystallization), object to a certain extent Manage characteristic isotropism, no definite fusing point, there is glass transition temperature point etc..Have simultaneously with common glass because of it similar Structure, with solid-state, metal, the characteristic of glass, also referred to as glassy metal (Metallic Glass).Due to its maximum knot Structure feature is exactly no grain structure, is directly uniformly distributed by atom is random, is keyed by metal between atom.Due to not having There is grain structure, also just there is no the features such as the defects of crystal boundary and lattice period translational symmetry, therefore possesses traditional crystalline state and close The excellent properties that golden material does not have, such as high mechanical properties, high rigidity, low elastic modulus, high-wearing feature, high anti-corrosion capability, with And excellent soft magnet performance.This internal structure of non-crystaline amorphous metal is formed by super be quenched and solidified of the master alloy melted, former Son has little time in process of setting by periodic arrangement, therefore forms the non-crystalline state of longrange disorder.After non-crystaline amorphous metal is found, inhale The research and discovery of the decades of scientific research personnel is drawn, it has now been found that such as Zr bases, Cu bases, Al bases, Fe bases, Pd bases, Ni The non-crystaline amorphous metal system of the systems such as base, Ti bases, Mg bases, rare-earth-based.
It is wherein notable with Zr base block amorphous alloy investigation of materials achievements, although Zr base noncrystal alloys are in the industry High using restricting for the practical factor still applied by various aspects, such as cost of material, process conditions are harsh, and post-processing processing is again It is miscellaneous etc..Wherein it is that non-crystaline amorphous metal does not have plasticity using maximum restraining factors, thus market application feedback is always to hesitate not Before.So the toughness for improving non-crystaline amorphous metal becomes the active demand that this material is used for volume production.
It adds the second phase and prepares one kind that amorphous composite material is improvement non-crystaline amorphous metal toughness method, but additional phase and amorphous Often there are problems that between matrix in conjunction with (wetability) so that the second phase and noncrystal substrate boundary strength are relatively low.In addition, additional phase Addition generally requires larger volume score (being more than 40%) and can be only achieved toughening effect, thus it is uneven to easily cause additional distributed mutually The problem of.Since the shape of additional phase is different, for threadiness, the second phase of sheet and three-dimensional framework shape, generally require to lead to It crosses the methods of infiltration or hot pressing and prepares amorphous composite material, be not suitable for industrial production.Therefore, micro- addition of the second phase of graininess at For the research emphasis of industrial production amorphous composite material.
Invention content
It is an object of the invention to overcome the above problem, a kind of high tenacity Zirconium-base non-crystalline alloy compound material is provided.This Shen Please by the way that the second phase is added in original non-crystaline amorphous metal matrix, there is the extension for preventing single shear band in amorphous in the second phase, The formation for inducing more shear bands improves material under the premise of not reducing script alloy material fracture bending strength Bending fracture strain, method provided by the present invention improve material intrinsic property from raw material end, need not be to product after molding It is surface-treated etc., and in addition to foundry alloy melting step, without introducing additional process, is suitble to volume production.
It is another object of the present invention to provide a kind of above-mentioned preparation method of Zirconium-base non-crystalline alloy compound material.
The purpose of the present invention can be achieved by the following measures:
A kind of Zirconium-base non-crystalline alloy compound material, the material are mainly made of zirconium-base amorphous alloy and the second phase.
The alloy composite materials of the present invention can only be made of zirconium-base amorphous alloy and the second phase, can also further be added Other do not influence the component of alloy composite materials main performance, the also alloy composite materials with other performances are made
The second phase in the present invention is metal or non-metal powder, and the application is by by the second phase and amorphous master alloy material By smelting in suspension and evacuated die-casting process, the Zirconium base non-crystalline composite material with very good mechanical properties is made.
Be in terms of 100% by zirconium-base amorphous alloy and the total volume of the second phase, the dosage of the second phase be 20% hereinafter, it is preferred that 10% hereinafter, further preferred 5% hereinafter, most preferably 3% hereinafter, preferred ranging from 0.5-3%.
The present invention the second phase include but not limited to:I. non-metal powder (such as carbon dust), II. materials with high melting point powder (carbon Change tungsten, aluminium oxide, zirconium carbide, tungsten powder, niobium powder, molybdenum powder, tantalum powder etc.), III. ductile metals powder (nickel powder, zirconium powder) etc..
The addition of the second phase of non-metal powder I, it is expected that generating chemical combination with the pick element reaction in-situ in pick base noncrystal alloy Object, the presence of compound can prevent the extension of shear band in noncrystal substrate, while the compound and amorphous base of reaction in-situ generation Body will have a preferable interface cohesion, thus the mechanical performance of product is improved on the basis of not changing alloy original performance.
The second phase of materials with high melting point II will on a small quantity dissolve in amorphous composite material preparation process, be formed with noncrystal substrate Interface is crossed, dissolving part is not reacted with noncrystal substrate, and not molten second phase then prevents shear band in noncrystal substrate by bypass mechanism Extension, thus improve on the basis of not changing alloy original performance the mechanical performance of product.
The second phase of ductile metal III will be partly dissolved in amorphous composite material preparation process, and dissolving part does not influence non- Brilliant matrix Forming ability, not molten second phase can only prevent shear band in noncrystal substrate from extending by bypass mechanism, and can be by certainly Body plastic deformation absorbs shear band and extends energy, thus the mechanicalness of product is improved on the basis of not changing alloy original performance Energy.
The zirconium-base amorphous alloy of the present invention includes but not limited to zirconium-base amorphous alloy material i, zirconium-base amorphous alloy material ii With zirconium-base amorphous alloy material iii.
About zirconium-base amorphous alloy material i,
The chemical composition of zirconium-base amorphous alloy material i is:(ZraHf1-a)x(Cu1-b-c-dNibAlcLd)yNbzM100-x-y-z;Its In:L is III B or the element of IV B races, and M is the element of VIII race, I B races, III A or IV A races, 45≤x≤65,10≤y≤45,0≤z ≤ 10,0.9885≤a≤0.9894,0.05≤b≤0.2,0.05≤c≤0.3,0≤d≤0.05.
In a kind of preferred embodiment, in zirconium-base amorphous alloy material i, L Y, Er or Gd elements, M Fe, Co or Sn are first Element, a=0.989 or 0.9889,50≤x≤60,20≤y≤45,1≤z≤10,0.10≤b≤0.20,0.10≤c≤0.35, 0.001≤d≤0.05。
About zirconium-base amorphous alloy material ii,
In the zirconium-base amorphous alloy material ii, (ZraMbRE100-a-b)x(AlcCu100-c)y(NidCoeFe100-d-e)1-x-y- zAgzWherein:
0.45≤x≤0.65,0.30≤y≤0.40,0≤z≤0.02,85≤a≤95,2≤b≤10,20≤c≤40, 60≤d≤80,5≤e≤25, RE are rare earth element, and M represents Ti or Nb;
It is wherein preferred:
0.50≤x≤0.55,0.30≤y≤0.40,0≤z≤0.01,88≤a≤93,2≤b≤8,25≤c≤40,66 ≤ d≤75,15≤e≤25, RE are rare earth element, and M represents Ti or Nb;
More preferred:
0.53≤x≤0.57, y=0.35,1-x-y-z=0.10;0≤z≤0.01,85≤a≤95,2≤b≤10, c= 28.57, d=70, e=20, RE are rare earth element, and M represents Ti or Nb.
About zirconium-base amorphous alloy material iii,
Zirconium-base amorphous alloy material iii is:Zr-Cu-Ni-Al-Ag-Y bulk amorphous alloy is closed by atomic percentage Gold composition range be:Zr 41-63%, Cu 18-46%, Ni 1.5-12.5%, Al 4-15%, Ag 0.01-5%, Y 0.01-5%.
By atomic percentage, preferred Zr-Cu-Ni-Al-Ag-Y bulk amorphous alloy composition range is:Zr 49- 55%, Cu 28-36%, Al 4-10%, Ni 2-7%, Ag 0.02-1.45%, Y 0.05-3%.
Material involved in CN201410078957.8 specifically can be used in zirconium-base amorphous alloy material iii.
Preparation method about Zirconium-base non-crystalline alloy compound material
The present invention provides the preparation methods of zirconium-base amorphous composite alloy material:Noncrystal substrate is corresponded into alloy each element After each high-purity raw material weighs in proportion, the method for electric arc melting is used to prepare amorphous master alloy material under inert gas protection Material, then smelting in suspension prepares amorphous composite material master alloy under inert gas protection with amorphous master alloy material by the second phase, Amorphous composite material is finally prepared using vacuum die casting machine.
Each high-purity raw material of the present invention is the purity of corresponding each element in 99.3% or more metal or nonmetallic Material.
The present invention provides a kind of preparation method of more specific Zirconium base non-crystalline composite material comprising following steps:
1. employed in the present invention is all high-purity raw material, wherein the purity of Zr is 99.4%, remaining element it is pure Degree is all 99.9%, according to formula rate precise;
2. the amorphous master alloy material of billet shape is prepared by the method for electric arc melting under the protection of argon gas;
3. the amorphous composite material master alloy of billet shape is prepared by the method for smelting in suspension under the protection of argon gas;
3. choosing the sample that a certain amount of master alloy material prepares 2mm thickness with vacuum die casting machine;
4. with SEM observe the second phase structural form and with noncrystal substrate interface;
5. amorphous composite material sample is carried out three-point bending and impulse machine performance test respectively.
For above each step detailed description are as follows:
In step 1, device therefor is assay balance, precision 0.0001g.
In step 2, the method for preparing amorphous master alloy has very much, and this patent uses the melting of electric arc furnaces copper mold and copper mold Smelting in suspension in conjunction with mode prepare.
In step 3, the equipment that AAC develops cooperatively with other research units can be used in vacuum die casting machine.This equipment is played into The molding of type national standard three-point bending and impact flexibility sample shape, mold are AAC interior designs, simulation and making.
In step 4, SEM tests are completed in AAC analysis centers, and specific test sample size specification unifies sample preparation according to AAC Standard.
In step 5, sample carries out three-point bending respectively and impulse machine performance test is completed inside AAC, specific to survey Test agent size specification unifies sample preparation standard according to AAC.
Beneficial effects of the present invention:
For the application by the way that the second phase is added in original non-crystaline amorphous metal matrix, the second phase, which exists, prevents single in amorphous cut The extension for cutting band induces the formation of more shear bands, under the premise of not reducing script alloy material fracture bending strength, carries The high bending fracture strain of material.Limited experimental data shows that composite material of the invention can be strong in script fracture bending 2280MPa is spent, is broken on the zirconium-base amorphous alloy material substrate of bending strain 2.3%, before maintaining fracture bending strength originally It puts, is broken bending strain up to 3.5%;This range is different from the material substrate of non-crystaline amorphous metal according to the second phase material is added, There is different improvements;Improve material intrinsic property from raw material end, product after molding need not be surface-treated etc.; And in addition to foundry alloy melting step, without introducing additional process, it is suitble to volume production.
Description of the drawings
Fig. 1 is noncrystal substrate optical microscope in embodiment 1 and 3;
Fig. 2 is the SEM figures of amorphous composite material A1 prepared by embodiment 1;
Fig. 3 is the SEM figures of amorphous composite material C1 prepared by embodiment 3;
Fig. 4 is bending stress-strain curve of amorphous composite material C1 prepared by embodiment 3.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, it is carried out below in conjunction with each embodiment detailed Elaboration.However, it will be understood by those skilled in the art that in each embodiment of the present invention, in order to keep reader more preferable Ground understands the present invention and proposes many technical details.But even if without these technical details and it is based on following embodiment party The various changes and modifications of formula can also realize each claim technical solution claimed of the present invention.
Embodiment summarizes, see following table:
Composite material Substrate 1 Substrate 2 Substrate 3 (F1)
Second phase C / / Embodiment 1-A1
Second phase W Embodiment 2-B1 Embodiment 5-E1 Embodiment 4-D1
Second phase Ni / / Embodiment 3-C1
Embodiment 1
This example demonstrates that the preparation of pick base amorphous composite material A1 provided by the invention, noncrystal substrate (i.e. substrate) ingredient For Zr51.9Cu31.8Ni6Al10Ag0.1Y0.2, the second phase is C powder, additive amount 3Vol%.The addition of C, it is expected that and additionally add Pick element reaction in-situ generates ZrC, and the presence of ZrC can prevent the extension of shear band in noncrystal substrate, while reaction in-situ generates ZrC and noncrystal substrate will have a preferable interface cohesion, thus improve product on the basis of not changing alloy original performance Mechanical performance.
A. according to the formula Zr of chemical composition51.9Cu31.8Ni6Al10Ag0.1Y0.2, each non-crystaline amorphous metal formula needs to prepare 240g master alloys, a master alloy are prepared according to 80g, need to prepare 3 master alloys altogether.It is converted into and is wanted according to atomic mass Weighing weight (such as following table total weight be 80 grams, 3 parts).Wherein the purity of zirconium is 99.4%, is the sponge zirconium of industrial rank, The purity of remaining element is 99.9%.Before melting, get out to need C to be added and (as follows with the Zr needed for C reaction in-situs Table).
Zr Cu Ni Al Ag Y Zr C
51.205g 21.855g 3.809g 2.918g 0.117g 0.096g 0.8g 0.8g
B. under the protection of argon gas, by the method for electric arc melting by above-mentioned raw material melting, amorphous composite wood is prepared The purpose of material master alloy material, whole process is by all kinds of elements melts into alloy material.The master alloy of melting in order to ensure Billet is uniform, during electric arc melting master alloy billet, needs master alloy billet turn-over 3-4 times, electric arc melting heating Temperature more than master alloy fusing point, vacuum degree 10-1Pa to 10-2Pa。
C. prepare 240 grams of billet master alloy material is put into vacuum die casting machine, using unified die-casting process at The three-point bending and 12, impulse machine performance test sample of profile bar shape, size 2mm*10mm*50mm.
D. the sample prepared is subjected to three-point bending and impulse machine performance test, specific data is shown in Table 1.
To be not added with the non-crystaline amorphous metal of the second phase as a contrast, the preparation method of the reference examples is same as above in addition to not using step b.
1 sample A1 three-point bendings of table and impulse machine performance test data
As shown in Figure 2, the addition of C promotes the formation of ZrC, and ZrC is uniformly distributed in noncrystal substrate.
Embodiment 2
This example demonstrates that the preparation of pick base amorphous composite material B1 provided by the invention, noncrystal substrate ingredient are Zr56.1Hf0.6Cu15.2Ni14.0Al10.4Nb3.5Y0.2, the second phase is W, additive amount 1.75Vol%.W is in amorphous composite material system A small amount of dissolving during standby forms transition interface with noncrystal substrate, and dissolving part is not reacted with noncrystal substrate, and not molten second phase is then It prevents shear band in noncrystal substrate from extending by bypass mechanism, thus product is improved on the basis of not changing alloy original performance Mechanical performance.
A. according to the formula Zr of chemical composition56.1Hf0.6Cu15.2Ni14.0Al10.4Nb3.5Y0.2, each non-crystaline amorphous metal formula need to 240g master alloys are prepared, a master alloy is prepared according to 80g, needs to prepare 3 master alloys altogether.It converts according to atomic mass At desired weighing weight (such as following table total weight is 80 grams, 3 parts).Wherein the purity of zirconium is 99.4%, is industrial rank The purity of sponge zirconium, remaining element is 99.9%.
B. under the protection of argon gas, by the method for electric arc melting by above-mentioned raw material melting, amorphous master alloy is prepared The purpose of material, whole process is by all kinds of elements melts into alloy material.In order to ensure, the master alloy billet of melting is uniform, During electric arc melting master alloy billet, need master alloy billet turn-over 3-4 times, the temperature of electric arc melting heating is in mother It is more than alloy melting point, vacuum degree 10-1Pa to 10-2Pa。
C. under the protection of argon gas, by the melting together with W by above-mentioned master alloy of the method for smelting in suspension, amorphous is prepared The purpose of composite material master alloy material, whole process is that W is made to be uniformly distributed in amorphous master alloy.In order to ensure, melting is non- Crystal composite material master alloy is uniform, in suspension smelting process, needs master alloy billet turn-over 4-6 times, smelting in suspension heating Temperature 100 degree more than master alloy fusing point, overall smelting time 10min, vacuum degree 10-1Pa to 10-2Pa。
D. prepare 240 grams of billet master alloy material is put into vacuum die casting machine, using unified die-casting process at The three-point bending and 12, impulse machine performance test sample of profile bar shape, size 2mm*10mm*50mm.
E. the sample prepared is subjected to three-point bending measuring mechanical property, specific data are shown in Table 2.
To be not added with the non-crystaline amorphous metal of the second phase as a contrast, the preparation method of the reference examples is same as above in addition to not using step c.
2 sample B1 three-point bending measuring mechanical property data of table
Embodiment 3
This example demonstrates that the preparation of pick base amorphous composite material C1 provided by the invention, noncrystal substrate ingredient are Zr51.9Cu31.8Ni6Al10Ag0.1Y0.2, the second phase is Ni, additive amount 3Vol%.Ni is as noncrystal substrate component, non- It is dissolved on a small quantity in crystal composite material preparation process, dissolving part will not influence noncrystal substrate Forming ability, not molten second phase technical ability It prevents shear band in noncrystal substrate from extending by bypass mechanism, and can be plastically deformed by itself and absorb shear band extension energy, The mechanical performance of product is thus improved on the basis of not changing alloy original performance.
A, b, d, step e is same as Example 2, suspension smelting technique difference in only c.Since Ni is magnetic, and it is molten Point is relatively low, therefore, it is molten need to reduce electric current afterwards by charging basket secondary charging, first high current melting 4min after master alloy fusing Refine 2min, vacuum degree 10-1Pa to 10-2Pa。
To be not added with the non-crystaline amorphous metal of the second phase as a contrast, the preparation method of the reference examples is same as above in addition to not using step c.
3 sample C1 three-point bendings of table and impulse machine performance test data
From the figure 3, it may be seen that the micro dissolution of Ni does not influence the formation of matrix, and not molten Ni is uniformly distributed in noncrystal substrate.Not The Ni of dissolving hinders the extension of shear band by bypass mechanism, while being plastically deformed by itself and absorbing shear band extension energy, The formation for promoting multiple shear bands improves the bending strain (see Fig. 4) of noncrystal substrate, and it is more than 200J/ to make its impact flexibility cm2
Embodiment 4
This example demonstrates that the preparation of pick base amorphous composite material D1 provided by the invention, noncrystal substrate ingredient are Zr51.9Cu31.8Ni6Al10Ag0.1Y0.2, the second phase is W, additive amount 1.75Vol%.Principle is the same as embodiment 2.Preparation method is the same as real Apply example 2.To be not added with the non-crystaline amorphous metal of the second phase case as a contrast, the preparation method of the reference examples is same in addition to not using step c On.
4 sample D1 three-point bending measuring mechanical property data of table
Embodiment 5
This example demonstrates that the preparation of pick base amorphous composite material E1 provided by the invention, noncrystal substrate ingredient are Zr50.8Ti4Y0.2Al10Cu25Ni7Co2Fe1, the second phase is W, additive amount 1.75Vol%.Principle is the same as embodiment 2.Preparation method With embodiment 2.To be not added with the non-crystaline amorphous metal of the second phase case as a contrast, the preparation side of the reference examples in addition to not using step c Method is same as above.
5 sample E1 three-point bending measuring mechanical property data of table
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention, And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.

Claims (10)

1. a kind of additional high tenacity Zirconium base non-crystalline composite material, which is characterized in that the material mainly by zirconium-base amorphous alloy and Second phase is made.
2. additional high tenacity Zirconium base non-crystalline composite material according to claim 1, which is characterized in that second phase is One or more of non-metal powder, materials with high melting point powder or ductile metal powder.
3. additional high tenacity Zirconium base non-crystalline composite material according to claim 1 or 2, which is characterized in that described second It is mutually one or more of carbon dust, tungsten carbide, aluminium oxide, zirconium carbide, tungsten powder, niobium powder, molybdenum powder, tantalum powder, nickel powder, zirconium powder.
4. additional high tenacity Zirconium base non-crystalline composite material according to claim 1 or 2, which is characterized in that with the zirconium Base noncrystal alloy and the total volume of the second phase are 100% meter, and the dosage of the second phase is 20% hereinafter, it is preferred that 10% hereinafter, into one Step preferably 5% is hereinafter, most preferably 3% or less.
5. additional high tenacity Zirconium base non-crystalline composite material according to claim 1, which is characterized in that described zirconium-base amorphous Alloy is selected from:
Zirconium-base amorphous alloy material i:[(ZraHf1-a)x(Cu1-b-c-dNibAlcLd)yNbz]M100-x-y-z, wherein L is III B or IV B The element of race, M are the element of VIII race, I B races, III A or IV A races, 45≤x≤65,10≤y≤45,0≤z≤10,0.9885≤a ≤ 0.9894,0.05≤b≤0.2,0.05≤c≤0.3,0≤d≤0.05;
Zirconium-base amorphous alloy material ii:(ZraMbRE100-a-b)x(AlcCu100-c)y(NidCoeFe100-d-e)1-x-y-zAgzWherein:
0.45≤x≤0.65,0.30≤y≤0.40,0≤z≤0.02,85≤a≤95,2≤b≤10,20≤c≤40,60≤d ≤ 80,5≤e≤25, RE are rare earth element, M represent Ti or Nb alternatively,
Zirconium-base amorphous alloy material iii:Zr-Cu-Ni-Al-Ag-Y bulk amorphous alloy, by atomic percentage, the alloy Composition range is:Zr41-63%, Cu18-46%, Ni1.5-12.5%, Al4-15%, Ag0.01-5%, Y0.01-5%;
One or more of.
6. additional high tenacity Zirconium base non-crystalline composite material according to claim 5, which is characterized in that described zirconium-base amorphous In alloy material i, the L be Y, Er or Gd element, the M be Fe, Co or Sn element, a=0.989 or 0.9889,50≤x≤ 60,20≤y≤45,1≤z≤10,0.10≤b≤0.20,0.10≤c≤0.35,0.001≤d≤0.05.
7. additional high tenacity Zirconium base non-crystalline composite material according to claim 5, which is characterized in that described zirconium-base amorphous In alloy material ii, 0.50≤x≤0.55,0.30≤y≤0.40,0≤z≤0.01,88≤a≤93,2≤b≤8,25≤c≤ 40,66≤d≤75,15≤e≤25, RE are rare earth element, and M represents Ti or Nb.
8. additional high tenacity Zirconium base non-crystalline composite material according to claim 7, which is characterized in that described zirconium-base amorphous In alloy material ii, 0.53≤x≤0.57, y=0.35,1-x-y-z=0.10;0≤z≤0.01,85≤a≤95,2≤b≤ 10, c=28.57, d=70, e=20, RE are rare earth element, and M represents Ti or Nb.
9. additional high tenacity Zirconium base non-crystalline composite material according to claim 5, which is characterized in that described zirconium-base amorphous In alloy material iii, by atomic percentage, the composition range of the alloy is:Zr 49-55%, Cu 28-36%, Al 4- 10%, Ni 2-7%, Ag 0.02-1.45%, Y 0.05-3%.
10. a kind of preparation method of additional high tenacity Zirconium base non-crystalline composite material described in claim 1, which is characterized in that Noncrystal substrate is corresponded to alloy each element each high-purity raw material weigh in proportion after, it is molten using electric arc under inert gas protection The method of refining prepares amorphous master alloy material, then by the second phase and the smelting in suspension under inert gas protection of amorphous master alloy material Amorphous composite material master alloy is prepared, amorphous composite material is finally prepared using vacuum die casting machine.
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CN109338252A (en) * 2018-11-30 2019-02-15 昆明理工大学 A kind of zirconium base porous amorphous alloy and preparation method
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
CN113981335A (en) * 2021-10-29 2022-01-28 盘星新型合金材料(常州)有限公司 Trace element modified Be-free block amorphous alloy and preparation method and application thereof

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CN109338252A (en) * 2018-11-30 2019-02-15 昆明理工大学 A kind of zirconium base porous amorphous alloy and preparation method
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
CN113981335A (en) * 2021-10-29 2022-01-28 盘星新型合金材料(常州)有限公司 Trace element modified Be-free block amorphous alloy and preparation method and application thereof

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