CN106868430A - A kind of alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability - Google Patents

A kind of alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability Download PDF

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CN106868430A
CN106868430A CN201710085143.0A CN201710085143A CN106868430A CN 106868430 A CN106868430 A CN 106868430A CN 201710085143 A CN201710085143 A CN 201710085143A CN 106868430 A CN106868430 A CN 106868430A
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王建强
吴念初
杨柏俊
孙文海
张锁德
吕威闫
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Institute of Metal Research of CAS
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    • C22C45/00—Amorphous alloys
    • C22C45/08—Amorphous alloys with aluminium 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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Abstract

The invention discloses a kind of alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability, belong to Al-based Amorphous Alloys technical field.The method be according to micro addition TM different from RE elements electronic action mechanism in Al TM (transition element) RE (rare earth element) ternary non-crystaline amorphous metal system, formulation formula (1) for δ=| KP‑2KF|, in formula (1)：When δ values level off to 0 when, the gross energy of system tends to minimum, and amorphous formation ability then strengthens；The amorphous formation ability of system is regulated and controled according to the rule, so as to prepare large-sized al based amorphous alloy；The proposition of the method solves the ample resources waste problem that conventional al based amorphous alloy composition design is present, and have devised current five yuan of complete block of aluminum non-crystaline amorphous metals maximum sized in the world.The present invention has important progradation to the range of application for expanding light high-intensity aluminum base non-crystaline amorphous metal.

Description

A kind of alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability
Technical field
The present invention relates to Al-based Amorphous Alloys technical field, and in particular to a kind of conjunction of regulation and control aluminium-based amorphous alloy Forming ability Golden composition design method.
Background technology
At present, the exploitation of lighting material has important progradation for energy saving, all kinds of equipment efficiency of raising. Therefore, Research Emphasis have been turned into fields such as all kinds of automobiles, aircraft, naval vessel, weaponrys.For example, all kinds of lightweight materials in recent years Expect that the application percentage in weapon model is in rapid increase trend.Wherein aluminium alloy, particularly high strength alumin ium alloy is due to matter Gently, the advantage of high specific strength, high specific stiffness, is widely used in the every field of the development of the national economy and national defense construction, in aviation Industry is even more and is largely used.Compared with traditional aluminium alloy, amorphous aluminum alloy has specific strength high, good toughness With excellent decay resistance, its tensile strength can exceed 1000MPa, and more than the level of current high-strength steel, specific strength can be with Ceramics match in excellence or beauty, and maintain good plasticity and high-temperature stability.It appear as develop lightweight superelevation strong metal structural material There is provided a new approach.However, the principal element for limiting such materials application at present is the glass shape of Al base noncrystal alloys Into poor ability, currently acquired maximum amorphous critical dimension is 1mm, the need for cannot still meeting practical engineering application.Therefore, The Forming ability for improving al based amorphous alloy is the primary factor for expanding its range of application.
To determine the aluminum-based alloy compositions with optimal amorphous formation ability, need to be to the knot of influence Al base amorphous formation abilities Structure essence is analyzed.Wherein, the atomic structure of Al base metal glass has important decisive role to its amorphous formation ability, Effective cluster piles up (Efficient Cluster Packing, ECP) model and the close heap model of quasi-equivalence cluster discloses Al- The structural nature of TM-RE ternary system amorphous formation abilities.But based on hard sphere it is assumed that the cluster centered on RE (TM) atom is total to Al atoms are enjoyed, and whole space is booked according to fcc modes.And this orderly crystal structure is not in unordered glassy metal Exist, influence of the chemical action to glassy metal stability is not considered.Therefore, using model prediction Al-TM-RE tri- During first system, experiment value and predicted value there are about the deviation of 4.6-19.8at.%.It is worth noting that, microalloying is for Al bases Vital effect is played in the development and design of metallic glass alloys system, for example：In Al86Ni8Y6On the basis of alloy only The Co and La of 2at.% replace Ni and Y can just make amorphous formation ability lift twice, finally successfully obtain the Al bases of a diameter of 1mm Block metal glass bar；The Ti or V of 0.5at.% are added to Al88Y7Fe5It can be just significantly improved in alloy amorphous Into ability.Microalloying effect can increase the stability of liquid phase, suppress the formation of crystal phase, so as to improve amorphous formation energy Power.But, microalloying is still unclear for the structure origin of quaternary and five yuan of Al bases amorphous formation ability influences.Forefathers attempt The structure origin that microalloying influences on Al bases amorphous formation ability is disclosed from atomic structure angle, for example：Using X-ray absorption Spectroscopic methodology research La and Co elements are added to Al86Ni8Y6In alloy, using Extended X-ray Absorption Fine Structure method research La and Hf elements are added to Al88Y7Fe5Al base noncrystal alloy atomic structures do not have in alloy, but before and after result of study shows microalloying It is variant.
According to glassy metal electronic structure principle, there is strong electron orbit hydridization effect in Al base metal glass systems Should, there is important influence to structure, but conventional meanses cannot be analyzed to this result, so should deeply understand that aluminium base is non- Peritectic alloy electronic structure level to the mechanism of action of amorphous formation ability, to seek to be applied to al based amorphous alloy into setting up separately Meter method.
The content of the invention
It is an object of the invention to provide a kind of alloy component design method for improving aluminium-based amorphous alloy Forming ability, solve Conventional al based amorphous alloy composition design complicates problem, have devised the completely amorphous alloy that critical dimension is 1.5mm, is mesh The preceding full-size Al-based block body amorphous alloy for preparing in the world, expands light high-intensity aluminum base non-crystaline amorphous metal as structural material Range of application.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability, the method is according in Al-TM-RE ternarys Electronic action mechanism micro addition TM different from RE elements in non-crystaline amorphous metal system, formulates presentation in formula (1), formula (1) Rule be：When δ values level off to 0 when, the gross energy of system tends to minimum, and amorphous formation ability then strengthens；According in formula (1) Rule regulates and controls to the amorphous formation ability of the Al-TM-RE ternarys non-crystaline amorphous metal system, so as to prepare large-sized aluminium base Non-crystaline amorphous metal；
δ=| KP-2KF| (1)；
In formula (1)：2KFIt is the diameter of Fermi surface, 2KFCalculation such as formula (2)；KPIt is the straight of pseudo- Brillouin zone Footpath, KPCalculation such as formula (3)；
In formula (2), ZFEMIt is the electron number of free electron contribution, ZhybIt is the electron number of electronics hydridization effect contribution, n0 It is atom number density；
In formula (3), λ is the wavelength of X-ray, and θ is that master disperses the corresponding angle of diffraction in peak in X-ray diffraction spectrum.
In the Al-TM-RE ternarys non-crystaline amorphous metal system：TM is transition element, and RE is rare earth element.
In Al-TM-RE alloy systems, by micro addition Co or La elements, when δ=0.009, quaternary aluminium-based amorphous alloy The amorphous formation ability of alloy is optimal, can prepare the al based amorphous alloy bar that critical dimension is 1mm (diameter).By atom hundred Divide content meter, the critical dimension is for the alloying component of the al based amorphous alloy bar of 1mm (diameter)：Al 86%, Ni 6.75%, Co 2.25%, Y 5%；Or, the critical dimension for 1mm (diameter) al based amorphous alloy bar alloy into It is divided into：Al 86%, Ni 9%, Y 3.25%, La 1.75%.
In Al-TM-RE alloy systems, by micro addition Co or La elements, when δ=0.001, five yuan of aluminium-based amorphous alloy The amorphous formation ability of alloy system is optimal, can prepare five yuan of complete block aluminum-bases that critical dimension is 1.5mm (diameter) non- Peritectic alloy.Based on atomic percentage conc, the critical dimension is the alloying component of the al based amorphous alloy bar of 1.5mm (diameter) For：Al 86%, Ni 6.75%, Co 2.25%, Y 3.25%, La 1.75%.
Design principle of the invention and have the beneficial effect that：
On the basis of Al-TM (transition element)-RE (rare earth element) ternary non-crystaline amorphous metal system, micro addition TM and RE There are different electronic action mechanism in element, wherein, micro addition TM elements can cause the change of Fermi surface diameter in system, and Change of the micro addition RE elements then to pseudo- Brillouin zone diameter is related, and the change of the two is respectively to the amorphous formation ability of system With different influences.According to above-mentioned analysis, make δ=| KP-2KF|, wherein, 2KFIt is the diameter of Fermi surface, KPIt is pseudo- Brillouin The diameter in area.Specifically calculation is：λ is the wavelength of X-ray, and θ is that master disperses peak pair in X-ray diffraction spectrum The angle of diffraction answered；ZFEMIt is the electron number of free electron contribution, ZhybIt is electronics The electron number of hydridization effect contribution, n0It is atom number density.According to glassy metal electronic structure principle, when δ values level off to 0 when, The gross energy of system tends to minimum, and amorphous formation ability then strengthens.Therefore can be according to this method to the amorphous formation of the system Ability is regulated and controled and is prepared large-sized al based amorphous alloy.Result of calculation shows：When δ=0.009, quaternary aluminium-based amorphous alloy The amorphous formation ability of alloy is optimal, can prepare critical dimension be 1mm diameters al based amorphous alloy bar, one of which into Distribution ratio is：Al86, Ni6.75, Co2.25, Y5 (at.%), another composition proportion is：Al86, Ni9, Y3.25, La1.75 (at.%)；And when δ=0.001, five yuan of al based amorphous alloy systems can reach optimum state, and prepare a diameter of 1.5mm Five yuan of complete block al based amorphous alloy, its composition proportion is：Al86, Ni6.75, Co2.25, Y3.25, La1.75 (at.%).The proposition of the method solves the ample resources waste problem that conventional al based amorphous alloy composition design is present, and sets Current five yuan of complete block of aluminum non-crystaline amorphous metals maximum sized are in the world counted out.The present invention is to expanding light high-intensity aluminum base amorphous The range of application of alloy has important progradation.
Brief description of the drawings
Fig. 1 is alloy component design method figure of the present invention；All make to be designed to tap in wherein (a)-(l) to be bordering on 2KF=Kp；
Fig. 2 is 2KFAnd KpGraph of a relation；
Fig. 3 is a diameter of 1.5mm bars (Al86Ni6.75Co2.25Y3.25La1.75) sample DSC and XRD photos；
Fig. 4 is Al86Ni6.75Co2.25Y3.25La1.75The high-resolution TEM photos of alloy.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, but embodiments of the present invention not limited to this.
The present invention is the alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability, and the method is according in Al-TM (mistakes Cross race's element) electronic action mechanism micro addition TM different from RE elements in-RE (rare earth element) ternary non-crystaline amorphous metal system, Make δ=| KP-2KF|, wherein, 2KFIt is the diameter of Fermi surface, KPIt is the diameter of pseudo- Brillouin zone.Specifically calculation is：λ is the wavelength of X-ray, and θ is that master disperses the corresponding angle of diffraction in peak in X-ray diffraction spectrum；ZFEMIt is the electron number of free electron contribution, ZhybIt is the contribution of electronics hydridization effect Electron number, n0It is atom number density.And when δ values level off to 0 when, the gross energy of system tends to minimum, and amorphous formation ability is then Enhancing.Therefore the amorphous formation ability of the system can be regulated and controled according to this method and is prepared large-sized aluminium-based amorphous alloy and closed Gold.
In Al-TM (transition element)-RE (rare earth element) alloy system, by micro addition Co or La elements, work as δ When=0.009, the amorphous formation ability of quaternary al based amorphous alloy is optimal, can prepare the aluminium base that critical dimension is 1mm diameters Non-crystaline amorphous metal bar, one of which composition proportion is (at.%)：Al 86%, Ni 6.75%, Co2.25%, Y5%, it is another Composition proportion is (at.%)：Al 86%, Ni 9%, Y 3.25%, La 1.75%；When δ=0.001, five yuan of aluminium-based amorphous alloy Alloy system can reach optimum state, and prepare five yuan of a diameter of 1.5mm complete block al based amorphous alloy, and its composition is matched somebody with somebody Than being (at.%)：Al86%, Ni6.75%, Co2.25%, Y3.25%, La1.75%.
Embodiment 1
The most strong alloying component (Al of amorphous formation ability in selection aluminium base ternary non-crystaline amorphous metal86Ni9Y5), as shown in figure 1, By micro addition La atoms, change the diameter (K of pseudo- Brillouin zoneP)；By micro addition Co atoms, change the straight of Fermi surface Footpath (2KF), according to δ value criterions：δ=| KP-2KF|, wherein,λ is the wavelength of X-ray, and θ is X-ray diffraction spectrum Middle master disperses the corresponding angle of diffraction in peak；ZFEMIt is the electronics of free electron contribution Number, ZhybIt is the electron number of electronics hydridization effect contribution, n0It is atom number density (n0=ρ NAv/ M, ρ are the density of glassy metal, M It is molal weight, NAvIt is Avogadro's number)；And when δ values level off to 0 when, the gross energy of system tends to minimum, amorphous formation Ability then strengthens.For five yuan of al based amorphous alloy compositions：Al86；Ni6.75；Co2.25；Y3.25；La1.75 (at.%), its In, ZFEM=∑iCiZi, C is atom percentage content, Z (Ni, Co)=2, Z (Al)=3, Z (Y, La)=3, due to Al atoms and There is electron orbit hydridization effect, Z in Ni (Co) atomhyb=CNi(nNi-8)+CCo(nCo- 7), nNiWith nCo values by measuring electronics Ni the and Co atom white lines peak of energy loss spectroscopy (EELS) draws.Thus calculate δ=0.001 (shown in Fig. 2), its value close to Zero.Size has been prepared accordingly for 1.5mm alloy bar materials, DSC the and XRD photos of Fig. 3 and the high-resolution TEM photos of Fig. 4 fill It is completely amorphous point to demonstrate this alloy bar material.
Embodiment 2
Difference with embodiment 1 is：
Micro addition La with Co elemental compositions are different, and alloying component is：Al86Ni6Co3Y4La1。
As a result：δ (=| KP-2KF|)=0.008, more than embodiment 1, critical dimension is 1.08mm, and amorphous formation ability is low In embodiment 1.
Embodiment 3
Difference with embodiment 1 is：
Micro addition La elemental compositions are different, and alloying component is：Al86Ni6.75Co2.25Y4La1。
As a result：δ (=| KP-2KF|)=0.006, more than embodiment 1, critical dimension is 1.25mm, and amorphous formation ability is low In embodiment 1.
Embodiment 4
Difference with embodiment 1 is：
Without addition Co elements, alloying component is：Al86Ni9Y3.25La1.75。
As a result：δ (=| KP-2KF|)=0.009, more than embodiment 1, critical dimension is 1mm, and amorphous formation ability is less than real Apply example 1.
Embodiment 5
Difference with embodiment 1 is：
Without addition La elements, alloying component is：Al86Ni6.75Co2.25Y5。
As a result：δ (=| KP-2KF|)=0.009, more than embodiment 1, critical dimension is 1mm, and amorphous formation ability is less than real Apply example 1.
Embodiment 6
Difference with embodiment 1 is：
Micro addition La with Co elemental compositions are different, and alloying component is：Al86Ni6Co3Y3.5La1.5。
As a result：δ (=| KP-2KF|) more than embodiment 1, amorphous formation ability is less than embodiment 1 to value.
Embodiment 7
Difference with embodiment 1 is：
Micro addition La elemental compositions are different, and alloying component is：Al86Ni6.75Co2.25Y3.5La1.5。
As a result：δ (=| KP-2KF|)=0.003, more than embodiment 1, critical dimension is 1.32mm, and amorphous formation ability is low In embodiment 1.
Embodiment 8
Difference with embodiment 1 is：
Micro addition Co elemental compositions are different, and alloying component is：Al86Ni6Co3Y3.25La1.75。
As a result：δ (=| KP-2KF|)=0.011, more than embodiment 1, critical dimension is 0.92mm, and amorphous formation ability is low In embodiment 1.
Embodiment 9
Difference with embodiment 1 is：
Micro addition Co elemental compositions are different, and alloying component is：Al86Ni4.5Co4.5Y3.25La1.75。
As a result：δ (=| KP-2KF|)=0.015, more than embodiment 1, critical dimension is 0.74mm, and amorphous formation ability is low In embodiment 1.

Claims (6)

1. it is a kind of regulate and control aluminium-based amorphous alloy Forming ability alloy component design method, it is characterised in that：The method is according in Al- Electronic action mechanism micro addition TM different from RE elements in TM-RE ternary non-crystaline amorphous metal systems, formulates formula (1), formula (1) rule of presentation is in：When δ values level off to 0 when, the gross energy of system tends to minimum, and amorphous formation ability then strengthens；According to Rule regulates and controls to the amorphous formation ability of the Al-TM-RE ternarys non-crystaline amorphous metal system in formula (1), so as to prepare big The al based amorphous alloy of size；
δ=| KP-2KF| (1)；
In formula (1)：2KFIt is the diameter of Fermi surface, 2KFCalculation such as formula (2)；KPIt is the diameter of pseudo- Brillouin zone, KP Calculation such as formula (3)；
2 K F = 2 2 π 2 n 0 Z F E M 3 - 2 2 π 2 n 0 Z h y b 3 - - - ( 2 ) ;
In formula (2), ZFEMIt is the electron number of free electron contribution, ZhybIt is the electron number of electronics hydridization effect contribution, n0It is atom Number density；
K P = 4 π s i n θ λ - - - ( 3 ) ;
In formula (3), λ is the wavelength of X-ray, and θ is that master disperses the corresponding angle of diffraction in peak in X-ray diffraction spectrum.
2. it is according to claim 1 regulation and control aluminium-based amorphous alloy Forming ability alloy component design method, it is characterised in that：Institute In stating Al-TM-RE ternary non-crystaline amorphous metal systems：TM is transition element, and RE is rare earth element.
3. the alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability according to claim 1 and 2, its feature exists In：In Al-TM-RE alloy systems, by micro addition Co or La elements, when δ=0.009, quaternary al based amorphous alloy Amorphous formation ability it is optimal, can prepare critical dimension be 1mm al based amorphous alloy bar.
4. it is according to claim 3 regulation and control aluminium-based amorphous alloy Forming ability alloy component design method, it is characterised in that：Press Atomic percentage conc meter, the critical dimension is that the alloying component of the al based amorphous alloy bar of 1mm is：Al 86%, Ni 6.75%, Co 2.25%, Y 5%；Or, the critical dimension is for the alloying component of the al based amorphous alloy bar of 1mm： Al 86%, Ni 9%, Y 3.25%, La 1.75%.
5. the alloy component design method of regulation and control aluminium-based amorphous alloy Forming ability according to claim 1 and 2, its feature exists In：In Al-TM-RE alloy systems, by micro addition Co or La elements, when δ=0.001, five yuan of al based amorphous alloy The amorphous formation ability of system is optimal, can prepare five yuan of complete block al based amorphous alloy that critical dimension is 1.5mm.
6. it is according to claim 5 regulation and control aluminium-based amorphous alloy Forming ability alloy component design method, it is characterised in that：Press Atomic percentage conc meter, the critical dimension is that the alloying component of the al based amorphous alloy bar of 1.5mm is：Al 86%, Ni 6.75%, Co 2.25%, Y 3.25%, La 1.75%.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107779683A (en) * 2017-11-02 2018-03-09 济南大学 A kind of Al base noncrystal alloys and preparation method thereof
CN109252060A (en) * 2018-09-30 2019-01-22 山东大学 A kind of preparation method of crystal-amorphous aluminum matrix composite
CN109440048A (en) * 2018-12-21 2019-03-08 中国特种飞行器研究所 A kind of aluminium-based amorphous alloy coating of ultrahigh relative density and preparation method thereof
CN109604547A (en) * 2019-02-01 2019-04-12 中国科学院金属研究所 A method of improving Al-Y-TM system al based amorphous alloy corrosion resistance
CN109881125A (en) * 2019-04-17 2019-06-14 常州大学 A method of widening aluminium-based amorphous alloy primary crystal Precipitation Temperature section
CN110938786A (en) * 2019-06-20 2020-03-31 中国科学院金属研究所 High-corrosion-resistance Al-TM-RE amorphous aluminum alloy

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107779683A (en) * 2017-11-02 2018-03-09 济南大学 A kind of Al base noncrystal alloys and preparation method thereof
CN107779683B (en) * 2017-11-02 2019-08-27 济南大学 A kind of Al base noncrystal alloy and preparation method thereof
CN109252060A (en) * 2018-09-30 2019-01-22 山东大学 A kind of preparation method of crystal-amorphous aluminum matrix composite
CN109440048A (en) * 2018-12-21 2019-03-08 中国特种飞行器研究所 A kind of aluminium-based amorphous alloy coating of ultrahigh relative density and preparation method thereof
CN109604547A (en) * 2019-02-01 2019-04-12 中国科学院金属研究所 A method of improving Al-Y-TM system al based amorphous alloy corrosion resistance
CN109881125A (en) * 2019-04-17 2019-06-14 常州大学 A method of widening aluminium-based amorphous alloy primary crystal Precipitation Temperature section
CN110938786A (en) * 2019-06-20 2020-03-31 中国科学院金属研究所 High-corrosion-resistance Al-TM-RE amorphous aluminum alloy

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Application publication date: 20170620