CN105316604B - High-hardness amorphous alloy and preparation method thereof - Google Patents
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Abstract
The invention discloses high-hardness amorphous alloy which comprises a base alloy part, a hard adding part and an adhesion adding part. The base alloy part comprises, by atom molar content, 45%-62% of Zr, 5%-10% of Hf, 5%-15% of Al, 8%-22% of Ni and 6%-14% of Cu. The hard adding part includes ZrC nano-micro powder or WC nano-micro powder, the adding amount of the hard adding part is 12%-26% of the mass of the base alloy part, and the particle size of the nano-micro powder is 10-100 nm. The adhesion adding part includes one or two of Re, W and Mo, and the adding amount of the adhesion adding part is 4%-8% of the mass of the base alloy part. The amorphous alloy is good in forming ability and excellent in forming property and has the characteristic of high hardness.
Description
Technical field
The present invention relates to a kind of non-crystaline amorphous metal, more particularly to a kind of non-crystaline amorphous metal of high rigidity and preparation method thereof.
Background technology
Non-crystaline amorphous metal atom is not presented periodicity and translational symmetry in spatial arrangements, but in the small chi of 1-2nm
There is certain regularity with neighbouring interatomic bonding in degree, it is very many that such architectural feature has non-crystaline amorphous metal
Excellent properties, such as high intensity, high resiliency, good corrosion resistance, etc., this causes non-crystaline amorphous metal to have boundless application front
Scape, the performance for how further lifting non-crystaline amorphous metal is the important directions of AMORPHOUS ALLOY at this stage.
The hardness of metal is to weigh an important performance indications of metal material soft or hard degree, the opposing elasticity with material
The ability of deformation, plastic deformation or destruction has very big association, is the mechanical properties such as elastic properties of materials, plasticity, intensity and toughness
A synthesis sign.In order to lift the hardness of non-crystaline amorphous metal, many research worker have done substantial amounts of research.Currently acquired height
The main method of hardness non-crystaline amorphous metal is that the matrix of non-crystaline amorphous metal uses refractory metal, such as W-Fe-B, Mo-Ru-Si, W-Ru-B-
The non-crystaline amorphous metal of Hf systems, these non-crystaline amorphous metals are limited by alloying component, not only the Forming ability of non-crystaline amorphous metal generally compared with
It is low, and be difficult to be processed by the method for thermoplastic shaping, largely limit the range of application of such material.Also have
A little technical schemes are improved for these shortcomings, and such as Application No. 201410769681.8 is entitled《It is a kind of to have height hard
Re-B-M non-crystaline amorphous metals of degree and preparation method thereof》Chinese patent, by adding transiting group metal elements in Re-B alloys
Co, Fe obtain the non-crystaline amorphous metal between higher hardness and wide supercooling liquid phase region.The program still uses refractory metal sill,
Improvement threshold is limited, and the machine-shaping ability of non-crystaline amorphous metal is not significantly improved.
Zr base noncrystal alloys are one of non-crystaline amorphous metal systems for being most widely used at present, Zr-Al-Ni-Cu quaternary alloys
System is because its Forming ability is preferable, alloy raw material is with respect to the alloy body being most widely used in becoming Zr base noncrystal alloys being easy to get
One of system.
The content of the invention
The present invention is improved by the composition to the alloy system based on Zr-Al-Ni-Cu, adds new component unit
Element, adjusts constituent content, there is provided the high rigidity Zr base noncrystal alloy that a kind of Forming ability is good, formability is good.Simultaneously, there is provided one
The technique for being adapted to prepare the non-crystaline amorphous metal is planted, makes the technique for preparing the non-crystaline amorphous metal be adaptable to the production of mass.
The technical problem to be solved is achieved by the following technical programs：
1st, composition of raw materials
Non-crystaline amorphous metal of the present invention, including base alloy part, hard addition part and bonding addition part.Close on basis
The elementary composition and atomic molar percentage composition of golden part is Zr：45-62%、Hf：5-10%、Al：5-15%、Ni：8-22%、Cu：
6-14%；Hard addition part is ZrC or WC nano powders, and addition is the 12-26% of above-mentioned base alloy part mass, nanometer
The particle diameter of micropowder is 10-100nm；Bonding addition part is one or two in Re, W, Mo element, and addition is above-mentioned basis
The 4-8% of alloy component quality.
Further preferably, the elementary composition and atomic molar percentage composition of the base alloy part is Zr：54-58%、
Hf：6-8%、Al：10-15%、Ni：15-20%、Cu：8-12%.
Zr-Al-Ni-Cu quaternary alloy System forming abilities are good, the present invention in base alloy part not only have adjusted Zr,
The content of tetra- kinds of elements of Al, Ni, Cu, while with the addition of the Hf elements of 5-10%.Congenerss of the Hf elements for Zr elements, molten
There are certain metalepsis to Zr atoms during refining, increase the active force in alloy between Zr atoms and the atom of other elements
By force, make the close pile structure of non-crystaline amorphous metal more stable, macroscopically show as non-crystaline amorphous metal more fine and close.Zr-Al-Ni-Cu-Hf five
Alloy based on first alloy system, can either ensure the Forming ability of the non-crystaline amorphous metal system, and the alloy system is molten
Liquid covering property is good, can form extraordinary syncretizing effect with the hard of addition addition part and bonding addition part.
The present inventor is in practice, it has been found that addition ZrC or WC nano powders can be effectively increased Zr-Al-Ni-
The hardness of Cu-Hf systems non-crystaline amorphous metal.But individually addition ZrC or WC nano powders can cause the fried of alloy system in fusion process
Split, one or two for adding in Re, W, Mo element in right amount then can avoid the occurrence of such case well.ZrC or WC nanometers are micro-
Powder can in Zr base noncrystal alloys crystalline state similar with disordered metal bond formed present in alloy system structure, these are unordered
Structure when non-crystaline amorphous metal matrix local is subject to external force to act on, the external force deformation that bring of destruction can be prevented to expand as buffer strip
, so as to realize the ability of macroscopically good anti-strike, resistance to deformation, that is, improve the hardness of non-crystaline amorphous metal.ZrC or WC nanometers
The particle diameter of micropowder is unsuitable excessive, is otherwise difficult to incorporate in alloy system, and particle diameter is too small, can increase the cost of raw material, in the present invention
The particle diameter of nano powder is elected 10-100nm as and is advisable.
Further preferably, ZrC nano powders, alloy component quality based on addition can only be selected in hard addition part
12-18%.Addition ZrC nano powders are in addition to strengthening the hardness of alloy system, and do not draw for Zr base noncrystal alloys
Enter other impurities element, it is to avoid cross multielement addition may caused by alloy crystallization.
Period elements of the Re and W for Hf, period elements of the Mo for Zr, Re, W, Mo atom and Zr, Hf atom are in structure
Electrically go up closely similar.Re, W, Mo atom can have different degrees of metalepsis in alloy system to Zr, Hf, strengthen and close
Interatomic adhesion in golden system, can play a part of such as binding agent in alloy system, can make base alloy part with
More it is tight that ZrC or WC nano powders are combined, it is to avoid the alloy in fusion process bursts.Simultaneously.Addition Re, W, Mo element is also
The entropy of non-crystaline amorphous metal system can be increased, strengthen the Forming ability of non-crystaline amorphous metal.
Further preferably, bonding addition part can be Re, the 8% of alloy component quality based on addition.
To further enhance the hardness of non-crystaline amorphous metal in the present invention, can also add base alloy part mass 0.5-2%'s
B or Si elements.
For the Forming ability for further lifting non-crystaline amorphous metal in the present invention, base alloy part mass 0.5- can also be added
2% Nd elements.
2nd, the preparation method of the non-crystaline amorphous metal in the present invention
Alloy raw material is carried out proportioning according to the non-crystaline amorphous metal composition in the present invention, hard is added part by step one
Alloy raw material is positioned over the bottom of base alloy part material after mixing homogeneously with the alloy raw material of bonding addition part.
Step 2, by raw material in step one in an inert atmosphere by way of electric arc melting by raw material melting, at twice
Carry out melting；First time Melting control electric current is 10-50A, and slow heating makes alloy raw material all become liquid, second
Secondary melting then high current, controls melting electric current for 200-900A, the alloy raw material of liquid is uniformly mixed rapidly；Inert atmosphere
Pressure be 0.01-0.05MPa, non-crystaline amorphous metal ingot casting is obtained after cooling, rate of cooling is 102-103K/s。
The present inventor is in practice, it has been found that ZrC or WC nano powders and the base alloy portion of hard addition part
The non-crystaline amorphous metal syncretizing effect for dividing is not good, directly mixes the non-crystaline amorphous metal obtained by all raw materials conventionally carry out melting
Easily burst.According to the method in the present invention, the alloy raw material that hard is first added part is former with the alloy of bonding addition part
The bottom of base alloy part material is positioned over after material mix homogeneously, is swept using small current arc ring during first time melting, controlled
Electric current is 10-50A, slow heating, makes alloy raw material all become liquid, strengthens the mobility of raw material, the base alloy of liquid
Raw material is slowly coated to ZrC the or WC nano powders of hard addition part, bonding addition part melt after also gradually with firmly
ZrC the or WC nano powders fusion of matter addition part, carries out second melting after raw material tentatively merges, and controlling melting electric current is
200-900A, high current mix the alloy raw material Quick uniform of liquid.If the non-crystaline amorphous metal of second melting output is uniform
Property is not good, then may be repeated 1-2 melting makes each raw material mix homogeneously of non-crystaline amorphous metal.
Step 3, obtains above-mentioned non-crystaline amorphous metal product, the system of conventional non-crystaline amorphous metal by conventional non-crystaline amorphous metal preparation method
Preparation Method includes die casting, inhales casting etc..
Condition prepared by the non-crystaline amorphous metal in the present invention is than conventional non-crystaline amorphous metal preparation condition without particular/special requirement, inert atmosphere
Pressure be 0.01-0.05MPa, rate of cooling be 102-103K/s can be reached during routine prepares non-crystaline amorphous metal
Condition.
Non-crystaline amorphous metal in the present invention can be applied as the material of high rigidity, can be applicable to consumer electronics product,
In medical device product, aerospace industry, machine instrumentation industry, auto industry and jewelry and ornament materials industry, can prepare
Part that structural member, case hardness have high demands etc..
The present invention has the advantages that：
1st, the amorphous alloy material in the present invention has the characteristic of high rigidity.
2nd, the amorphous alloy material in the present invention forms the maximum reachable 22mm of size, is adapted to make complex structural member.
3rd, preparation is simple, does not need specific condition produce for the amorphous alloy material in the present invention, fits
Close mass production.
Specific embodiment
Embodiment 1
The alloy raw material purity selected in embodiment is more than 99.9%, and ZrC, WC nano powder particle diameter is 10nm.
Non-crystaline amorphous metal hardness is characterized with Vickers hardness number, and testing tool is Vickers, method of testing according to
《GB/T 7997-2014 hard alloy vickers hardness test methods》Carry out, unification is characterized using HV10.
The preparation method of non-crystaline amorphous metal in embodiment：
Alloy raw material is carried out proportioning according to list of ingredients by step one, and the alloy raw material of hard addition part is added with bonding
Plus after partial alloy raw material mix homogeneously, it is positioned over the bottom of base alloy part material.
Step 2, by raw material in step one in an inert atmosphere by way of electric arc melting by raw material melting, at twice
Carry out melting；The electric arc of first time melting is swept using small coin, and control electric current is 50A, slow heating, makes alloy raw material whole
Become liquid, second melting then high current controls melting electric current for 900A, the alloy raw material of liquid is uniformly mixed；It is lazy
Property atmosphere pressure be 0.01MPa, non-crystaline amorphous metal ingot casting is obtained after cooling, rate of cooling is 102K/s。
Step 3, obtains non-crystaline amorphous metal product by die casting.
The elementary composition and atomic molar percentage composition of base alloy part is as shown in the table：
It is obtained using conventional arc melting mode according to Zr-Hf-Al-Ni-Cu quinary alloys shown in upper table, is tested no added
The case hardness of partial quinary alloy；
In having addition part, based on hard addition part, the ZrC nano powders or WC nanometers of alloy component quality 12% are micro-
The Re elements of alloy component quality 8% based on powder, bonding addition part, hardness test result are as follows：
In embodiment 1, obtained amorphous alloy forming ability is all not less than 10cm, and maximum Forming ability can reach 22cm.
From hardness test result, add the hardness of non-crystaline amorphous metal of hard addition part and bonding addition part compared with un-added
Quinary alloy has very big lifting, and Forming ability is also very good.
Embodiment 2
The component content of base alloy part is from the non-crystaline amorphous metal that numbering in embodiment 1 is 14, preparation method and enforcement
Example 1 is identical, as follows from the hardness test result of different hard addition parts and bonding addition part（Based on numerical value content
The percentage ratio of alloy component quality）：
In embodiment 2, obtained amorphous alloy forming ability is all not less than 10cm, and maximum Forming ability also can reach
20cm.When the quality that hard adds the nano powder addition of part is more than the 22% of base alloy part mass, the hardness of alloy
Value has declined on the contrary, and more than 26% then no matter using which kind of bonding addition portion of material, obtained non-crystaline amorphous metal has different journeys
The surface checking of degree, the phenomenon for bursting.
Bonding addition part is better than the addition of single-element using the addition manner of multiple element, and the addition of Re, Mo element is right
The fusion faculty of the Forming ability of non-crystaline amorphous metal and hard addition part is better than W elements.
Embodiment 3
The component content of base alloy part is from the non-crystaline amorphous metal that numbering in embodiment 1 is No. 14, preparation method and reality
Apply that example 1 is identical, the ZrC nano powders of alloy component quality 12% based on hard addition part, bonding addition are closed based on part
The Re elements of golden part mass 8%, add B, Si, Nd element, and hardness test result is as follows（Alloy component based on numerical value content
The percentage ratio of quality）：
In above-described embodiment, add B, Si element and can further lift the hardness of non-crystaline amorphous metal, addition more than 2% with
Afterwards then without significant changes.Add appropriate Nd elements, contribute to lifting the Forming ability of non-crystaline amorphous metal.In embodiment 3, only add B
Or the amorphous alloy forming ability of Si is unchanged with the non-crystaline amorphous metal without B or Si, can send out in fusion process after addition Nd
The amorphous state of existing alloy is more easy to shaping, and the crystallized ability of non-crystaline amorphous metal is up to 22cm.
It should be noted that in the present inventor's non-crystaline amorphous metal fusion process in the present invention, finding melting institute
Size of current is closely related with the alloying component of addition, when the addition that hard adds part is larger, can be lifted in right amount
Electric current used by melting, when bonding is added part or also continues to add B, Si, Nd element, the electric current of electric arc melting should be than molten
Refine high during the alloy without these elements.
It is last it should be noted that above example is only to illustrate the technical scheme of the embodiment of the present invention rather than which is entered
Row is limited, although being described in detail to the embodiment of the present invention with reference to preferred embodiment, one of ordinary skill in the art
It should be understood that still the technical scheme of the embodiment of the present invention can be modified or equivalent, and these are changed or wait
Amended technical scheme can not be also made to depart from the scope of embodiment of the present invention technical scheme with replacement.
Claims (9)
1. a kind of high rigidity non-crystaline amorphous metal, including base alloy part, hard addition part and bonding addition part, its feature exist
In：The elementary composition and atomic molar percentage composition of the base alloy part is Zr：45-62%、Hf：5-10%、Al：5-15%、
Ni：8-22%、Cu：6-14%；Hard addition part is ZrC or WC nano powders, and addition is above-mentioned base alloy part matter
The 12-26% of amount, the particle diameter of nano powder is 10-100nm；The bonding addition part for the one kind in Re, W, Mo element or
Various, addition is the 4-8% of above-mentioned base alloy part mass；
The preparation method of the high rigidity non-crystaline amorphous metal is：
Step one, by alloy raw material according to above-mentioned non-crystaline amorphous metal composition carry out proportioning, by hard add part alloy raw material with
The bottom of base alloy part material is positioned over after the alloy raw material mix homogeneously of bonding addition part；
Step 2, by raw material in step one in an inert atmosphere by way of electric arc melting by raw material melting, is carried out at twice
Melting；First time Melting control electric current is 10-50A, and slow heating makes alloy raw material all become liquid, molten for the second time
Then high current is refined, it is 200-900A to control melting electric current, the alloy raw material of liquid is uniformly mixed rapidly；The pressure of inert atmosphere
Power is 0.01-0.05MPa, and non-crystaline amorphous metal ingot casting is obtained after cooling, and rate of cooling is 102-103K/s ；
Step 3, obtains above-mentioned non-crystaline amorphous metal product by conventional non-crystaline amorphous metal preparation method.
2. the non-crystaline amorphous metal according to claim 1, it is characterised in that：The elementary composition and atom of the base alloy part
Molar content is Zr：54-58%、Hf：6-8%、Al：10-15%、Ni：15-20%、Cu：8-12%.
3. the non-crystaline amorphous metal according to claim 1, it is characterised in that：Hard addition part is ZrC, is closed based on addition
The 12-18% of golden part mass.
4. the non-crystaline amorphous metal according to claim 1, it is characterised in that：The bonding addition part is Re, based on addition
The 8% of alloy component quality.
5. the non-crystaline amorphous metal according to claim 1, it is characterised in that：Base alloy part mass 0.5-2% can also be added
B or Si elements.
6. the non-crystaline amorphous metal according to claim 1, it is characterised in that：Base alloy part mass 0.5-2% can also be added
Nd elements.
7. non-crystaline amorphous metal according to claim 1, it is characterised in that：1-2 melting is carried out after second melting also.
8. the application of the arbitrary non-crystaline amorphous metal of a kind of claim 1-7, it is characterised in that：The non-crystaline amorphous metal can be applicable to
Consumer electronics product, medical device product, aerospace industry, machine instrumentation industry, auto industry and jewelry and decoration material
In material industry.
9. the application of the arbitrary non-crystaline amorphous metal of a kind of claim 1-7, it is characterised in that：The non-crystaline amorphous metal can be used as height
The material of hardness is applied.
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| 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 |
| CN105714216A (en) * | 2016-02-29 | 2016-06-29 | 宋佳 | High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof |
| CN113564579B (en) * | 2021-07-06 | 2022-10-28 | 燕山大学 | Method for preparing copper-based amorphous composite coating by laser cladding |
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