CN105316604A - High-hardness amorphous alloy and preparation method thereof - Google Patents
High-hardness amorphous alloy and preparation method thereof Download PDFInfo
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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, particularly relate to non-crystaline amorphous metal of a kind of high rigidity and preparation method thereof.
Background technology
Non-crystaline amorphous metal atom does not present periodically and translational symmetry in spatial disposition, but in the miniature scale of 1-2nm, with contiguous interatomic bonding, there is certain regularity, such constitutional features makes non-crystaline amorphous metal have very many excellent properties, as high strength, snappiness, good corrosion resistance, etc., this makes non-crystaline amorphous metal have boundless application prospect, and the performance how promoting non-crystaline amorphous metal is further the important directions of present stage AMORPHOUS ALLOY.
The hardness of metal weighs the important performance index of of metallic substance soft or hard degree, having very large association with the ability of the opposing elastic deformation of material, plastic deformation or destruction, is the comprehensive sign of of the mechanical properties such as elastic properties of materials, plasticity, intensity and toughness.In order to promote the hardness of non-crystaline amorphous metal, many researchists have done large quantifier elimination.The main method of current acquisition high rigidity non-crystaline amorphous metal is the matrix use refractory metal of non-crystaline amorphous metal, as the non-crystaline amorphous metal of W-Fe-B, Mo-Ru-Si, W-Ru-B-Hf system, these non-crystaline amorphous metals are subject to the restriction of alloying constituent, not only the Forming ability of non-crystaline amorphous metal is general lower, and be difficult to be processed by the method for thermoplastic shaping, limit the range of application of such material to a great extent.Also some technical scheme is improved for these shortcomings, be the Chinese patent of " a kind of Re-B-M non-crystaline amorphous metal with high rigidity and preparation method thereof " by name of 201410769681.8 as application number, by adding the non-crystaline amorphous metal between transiting group metal elements Co, Fe acquisition higher hardness and wide supercooling liquid phase region in Re-B alloy.The program still uses refractory metal sill, and improvement threshold is limited, and does not have obvious improvement to the machine-shaping ability of non-crystaline amorphous metal.
Zr base noncrystal alloy is one of non-crystaline amorphous metal system be most widely used at present, and Zr-Al-Ni-Cu quad alloy system is because its Forming ability is better, alloy raw material is relatively easy to get and becomes one of alloy system be most widely used in Zr base noncrystal alloy.
Summary of the invention
The present invention, by improving the composition of the alloy system based on Zr-Al-Ni-Cu, adds new component element, and adjustment component concentration, provides the high rigidity Zr base noncrystal alloy that a kind of Forming ability is good, plasticity is good.Meanwhile, a kind of technique of applicable this non-crystaline amorphous metal of preparation is provided, makes the technique of this non-crystaline amorphous metal of preparation can be adapted to the production of mass.
Technical problem to be solved by this invention is achieved by the following technical programs:
1, composition of raw materials
Non-crystaline amorphous metal of the present invention, comprises base alloy part, hard adding portion and bonding adding portion.Elementary composition and the atomic molar percentage composition of base alloy part is Zr:45-62%, Hf:5-10%, Al:5-15%, Ni:8-22%, Cu:6-14%; Hard adding portion is ZrC or WC nano powder, and addition is the 12-26% of above-mentioned base alloy part mass, and the particle diameter of nano powder is 10-100nm; Bonding adding portion is one or both in Re, W, Mo element, and addition is the 4-8% of above-mentioned base alloy part mass.
Further preferably, the elementary composition and atomic molar percentage composition of described base alloy part is Zr:54-58%, Hf:6-8%, Al:10-15%, Ni:15-20%, Cu:8-12%.
Zr-Al-Ni-Cu quad alloy System forming ability is good, and the base alloy part in the present invention not only have adjusted the content of Zr, Al, Ni, Cu tetra-kinds of elements, with the addition of the Hf element of 5-10% simultaneously.Hf element is the congeners of Zr element, certain metalepsy is had to Zr atom in fusion process, reactive force in alloy between Zr atom and the atom of other elements is strengthened, makes the close pile structure of non-crystaline amorphous metal more stable, macroscopically show as non-crystaline amorphous metal more fine and close.Alloy based on Zr-Al-Ni-Cu-Hf quinary alloy system, the Forming ability of this non-crystaline amorphous metal system can either be ensured, and the liquation covering property of this alloy system is good, extraordinary syncretizing effect can be formed with the hard adding portion of adding and the adding portion that bonds.
The present inventor finds in practice, adds the hardness that ZrC or WC nano powder effectively can increase Zr-Al-Ni-Cu-Hf system non-crystaline amorphous metal.But add separately ZrC or WC nano powder and can cause bursting of fusion process interalloy system, one or both adding in Re, W, Mo element in right amount then can be avoided occurring this situation well.ZrC or WC nano powder can form the structure of similar crystalline state with the disordered metal key that exists in alloy system in Zr base noncrystal alloy, these unordered structures are when non-crystaline amorphous metal matrix local is subject to External Force Acting, can be used as the deformation expansion that buffer strip stops outside destroy to bring, thus realize macroscopically good anti-strike, the ability of resistance to deformation, namely improve the hardness of non-crystaline amorphous metal.The particle diameter of ZrC or WC nano powder is unsuitable excessive, otherwise not easily incorporates in alloy system, and particle diameter is too small, can increase the cost of raw material, and in the present invention, the particle diameter of nano powder is elected 10-100nm as and is advisable.
Further preferably, ZrC nano powder can only be selected in hard adding portion, the 12-18% of alloy component quality based on addition.Add ZrC nano powder except strengthening the hardness of alloy system, and do not introduce other impurity elements for Zr base noncrystal alloy, what avoided multielement adds the alloy crystallization that may cause.
Re and W is the period element of Hf, and Mo is the period element of Zr, Re, W, Mo atom and Zr, Hf atom structure and electrically on closely similar.Re, W, Mo atom can have metalepsy in various degree to Zr, Hf in alloy system, strengthen the bonding force between alloy system Atom, the effect as binding agent can be played in alloy system, what base alloy part can be made to be combined with ZrC or WC nano powder is more tight, avoids the alloy in fusion process to burst.Simultaneously.Add the entropy that Re, W, Mo element also can increase non-crystaline amorphous metal system, strengthen the Forming ability of non-crystaline amorphous metal.
Further preferably, bonding adding portion can be Re, based on addition alloy component quality 8%.
For strengthening the hardness of non-crystaline amorphous metal in the present invention further, B or the Si element of base alloy part mass 0.5-2% can also be added.
For promoting the Forming ability of non-crystaline amorphous metal in the present invention further, the Nd element of base alloy part mass 0.5-2% can also be added.
The preparation method of the non-crystaline amorphous metal 2, in the present invention
Step one, carries out proportioning by alloy raw material according to the non-crystaline amorphous metal composition in the present invention, is positioned over the bottom of base alloy part material with the alloy raw material of bonding adding portion after being mixed by the alloy raw material of hard adding portion.
Step 2, passes through the mode of arc melting in an inert atmosphere by raw material melting, carries out melting at twice by step one Raw; First time, Melting control electric current was 10-50A, and slowly heat, make the whole liquefy of alloy raw material, second time melting then high current, controlling melting electric current is 200-900A, makes the liquid rapid Homogeneous phase mixing of alloy raw material; The pressure of inert atmosphere is 0.01-0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling, and speed of cooling is 10
2-10
3k/s.
The present inventor finds in practice, ZrC or the WC nano powder of hard adding portion and the non-crystaline amorphous metal syncretizing effect of base alloy part not good, directly all raw materials of mixing conventionally carry out the non-crystaline amorphous metal that melting obtains and easily burst.According to the method in the present invention, the bottom of base alloy part material is positioned over after first being mixed with the alloy raw material of bonding adding portion by the alloy raw material of hard adding portion, small area analysis arc ring is used to sweep during first time melting, control electric current is 10-50A, slow heating, make the whole liquefy of alloy raw material, strengthen the mobility of raw material, liquid base alloy raw material slowly carries out coated to ZrC or the WC nano powder of hard adding portion, also merge with ZrC or the WC nano powder of hard adding portion gradually after the fusing of bonding adding portion, second time melting is carried out after raw material tentatively merges, controlling melting electric current is 200-900A, high current makes liquid alloy raw material Quick uniform mixing.If the non-crystaline amorphous metal homogeneity of second time melting output is not good, then can repeats 1-2 melting and each raw material of non-crystaline amorphous metal is mixed.
Step 3, obtains above-mentioned non-crystaline amorphous metal product by conventional non-crystaline amorphous metal preparation method, and the preparation method of conventional non-crystaline amorphous metal comprises 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 requirement, and the pressure of inert atmosphere is 0.01-0.05MPa, speed of cooling is 10
2-10
3k/s is that routine prepares the condition that can reach in non-crystaline amorphous metal process.
The material that non-crystaline amorphous metal in the present invention can be used as high rigidity is applied, can be applicable in consumer electronics product, medical device product, aerospace industry, machine instrumentation industry, automotive industry and jewellery and finishing material industry, structural part can be prepared, surface hardness requires high part etc.
The present invention has following beneficial effect:
1, the amorphous alloy material in the present invention has the characteristic of high rigidity.
2, amorphous alloy material in the present invention forms that size is maximum reaches 22mm, is applicable to making complex structural member.
3, preparation is simple for the amorphous alloy material in the present invention, do not need special conditions to produce, and is applicable to mass production.
Embodiment
Embodiment 1
The alloy raw material purity selected in embodiment is greater than 99.9%, ZrC, WC nano powder particle diameter is 10nm.
Non-crystaline amorphous metal hardness vickers hardness number characterizes, and testing tool is Vickers hardness tester, and testing method is carried out according to " GB/T7997-2014 Wimet Vickers' hardness testing method ", and the unified HV10 of use characterizes.
The preparation method of non-crystaline amorphous metal in embodiment:
Step one, carries out proportioning by alloy raw material according to allocation sheet, is positioned over the bottom of base alloy part material with the alloy raw material of bonding adding portion after being mixed by the alloy raw material of hard adding portion.
Step 2, passes through the mode of arc melting in an inert atmosphere by raw material melting, carries out melting at twice by step one Raw; The electric arc of first time melting uses small coin to sweep, and control electric current is 50A, slowly heats, and makes the whole liquefy of alloy raw material, second time melting then high current, and controlling melting electric current is 900A, makes liquid alloy raw material Homogeneous phase mixing; The pressure of inert atmosphere is 0.01MPa, obtains non-crystaline amorphous metal ingot casting after cooling, and speed of cooling is 10
2k/s.
Step 3, obtains non-crystaline amorphous metal product by die casting.
Elementary composition and the atomic molar percentage composition of base alloy part is as shown in the table:
Utilize conventional arc melting mode to obtain according to Zr-Hf-Al-Ni-Cu quinary alloy shown in upper table, test the surface hardness without the quinary alloy of adding portion;
Have in adding portion, the Re element of alloy component quality 8% based on the ZrC nano powder of alloy component quality 12% or WC nano powder, bonding adding portion based on hard adding portion, hardness test result is as follows:
Amorphous alloy forming ability obtained in embodiment 1 is all not less than 10cm, and maximum Forming ability can reach 22cm.From hardness test result, the hardness of adding the non-crystaline amorphous metal of hard adding portion and bonding adding portion has very large lifting compared with un-added quinary alloy, and Forming ability is also very good.
Embodiment 2
The component content of base alloy part selects in embodiment 1 non-crystaline amorphous metal being numbered 14, preparation method is identical with embodiment 1, selects the hardness test result of different hard adding portions and bonding the adding portion following per-cent of alloy component quality (based on the numerical value content):
Amorphous alloy forming ability obtained in embodiment 2 is all not less than 10cm, and maximum Forming ability also can reach 20cm.When the quality that the nano powder of hard adding portion adds is greater than 22% of base alloy part mass, the hardness value of alloy declines on the contrary to some extent, which kind of bonding adding portion material no matter is used, the phenomenon that obtained non-crystaline amorphous metal has check surface in various degree, bursts more than 26%.
Bonding adding portion uses the addition manner of multiple element to be better than the interpolation of single-element, and the interpolation of Re, Mo element is better than W element to the Forming ability of non-crystaline amorphous metal and the fusion faculty of hard adding portion.
Embodiment 3
The component content of base alloy part selects in embodiment 1 non-crystaline amorphous metal being numbered No. 14, preparation method is identical with embodiment 1, the ZrC nano powder of alloy component quality 12% based on hard adding portion, the Re element of alloy component quality 8% based on bonding adding portion, add B, Si, Nd element, the hardness test result following per-cent of alloy component quality (based on the numerical value content):
In above-described embodiment, add the hardness that B, Si element can promote non-crystaline amorphous metal further, addition is later then without noticeable change more than 2%.Add appropriate Nd element, contribute to the Forming ability promoting non-crystaline amorphous metal.In embodiment 3, the amorphous alloy forming ability only adding B or Si is unchanged with the non-crystaline amorphous metal not adding B or Si, and can find that in fusion process the non-crystalline state of alloy is more easily shaped after adding Nd, the crystallized ability of non-crystaline amorphous metal can reach 22cm.
It should be noted that, in the present inventor's non-crystaline amorphous metal fusion process in the present invention, find that the alloying constituent of the size of current that melting is used and interpolation is closely related, when the addition of hard adding portion is larger, melting electric current used can be promoted in right amount, when boning adding portion or also continuing to add B, Si, Nd element, high when the electric current of arc melting should not add the alloy of these elements than melting.
Finally it should be noted that, above embodiment is only in order to illustrate the technical scheme of the embodiment of the present invention but not to be limited, although be described in detail the embodiment of the present invention with reference to preferred embodiment, those of ordinary skill in the art is to be understood that and still can modifies to the technical scheme of the embodiment of the present invention or equivalent replacement, and these are revised or be equal to the scope that replacement also can not make amended technical scheme disengaging embodiment of the present invention technical scheme.
Claims (10)
1. a high rigidity non-crystaline amorphous metal, comprise base alloy part, hard adding portion and bonding adding portion, it is characterized in that: the elementary composition and atomic molar percentage composition of described base alloy part is Zr:45-62%, Hf:5-10%, Al:5-15%, Ni:8-22%, Cu:6-14%; Hard adding portion is ZrC or WC nano powder, and addition is the 12-26% of above-mentioned base alloy part mass, and the particle diameter of nano powder is 10-100nm; Described bonding adding portion is one or more in Re, W, Mo element, and addition is the 4-8% of above-mentioned base alloy part mass.
2. non-crystaline amorphous metal according to claim 1, is characterized in that: the elementary composition and atomic molar percentage composition of described base alloy part is Zr:54-58%, Hf:6-8%, Al:10-15%, Ni:15-20%, Cu:8-12%.
3. non-crystaline amorphous metal according to claim 1, is characterized in that: hard adding portion is ZrC, the 12-18% of alloy component quality based on addition.
4. non-crystaline amorphous metal according to claim 1, is characterized in that: described bonding adding portion is Re, based on addition alloy component quality 8%.
5. non-crystaline amorphous metal according to claim 1, is characterized in that: B or the Si element that can also add base alloy part mass 0.5-2%.
6. non-crystaline amorphous metal according to claim 1, is characterized in that: the Nd element that can also add base alloy part mass 0.5-2%.
7. prepare a method for non-crystaline amorphous metal as described in any one of claim 1-6, it is characterized in that:
Step one, carries out proportioning by alloy raw material according to above-mentioned non-crystaline amorphous metal composition, is positioned over the bottom of base alloy part material with the alloy raw material of bonding adding portion after being mixed by the alloy raw material of hard adding portion;
Step 2, passes through the mode of arc melting in an inert atmosphere by raw material melting, carries out melting at twice by step one Raw; First time, Melting control electric current was 10-50A, and slowly heat, make the whole liquefy of alloy raw material, second time melting then high current, controlling melting electric current is 200-900A, makes the liquid rapid Homogeneous phase mixing of alloy raw material; The pressure of inert atmosphere is 0.01-0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling, and speed of cooling is 10
2-10
3k/s;
Step 3, obtains above-mentioned non-crystaline amorphous metal product by conventional non-crystaline amorphous metal preparation method.
8. non-crystaline amorphous metal preparation method according to claim 7, is characterized in that: also can carry out 1-2 melting after second time melting.
9. an application for the arbitrary described non-crystaline amorphous metal of claim 1-6, is characterized in that: described non-crystaline amorphous metal can be applicable in consumer electronics product, medical device product, aerospace industry, machine instrumentation industry, automotive industry and jewellery and finishing material industry.
10. an application for the arbitrary described non-crystaline amorphous metal of claim 1-6, is characterized in that: the material that described non-crystaline amorphous metal can be used as high rigidity is applied.
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| CN113564579A (en) * | 2021-07-06 | 2021-10-29 | 燕山大学 | Method for preparing copper-based amorphous composite coating by laser cladding |
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