CN105132834B - A kind of high intensity non-crystaline amorphous metal and preparation method thereof - Google Patents
A kind of high intensity non-crystaline amorphous metal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high intensity non-crystaline amorphous metal, the non-crystaline amorphous metal composition is ZraAlbCucNidBeeSnfM1gM2h, wherein a, b, c, d, e, f, g, h is corresponding atomic molar percentage composition, respectively 40≤a≤70,5≤b≤25,5≤c≤15,5≤d≤15,0.2≤e≤3,0.2≤f≤4,0.5≤g≤5,1≤h≤5 in the non-crystaline amorphous metal；M1 is one or more mixtures in Hf, Ta, lanthanide series, and M2 is one or more mixtures in Ti, Sc, Fe, Co element.Non-crystaline amorphous metal intensity height in the present invention, plasticity are good, are particularly suitable as grinding tool material, mechanical structural material and are applied.
Description
Technical field
The present invention relates to a kind of amorphous alloy material, and in particular to a kind of high intensity, the zirconium base that amorphous formation ability is good
Amorphous alloy material and preparation method thereof.
Background technology
Mechanical structural material refers to the class engineering material using the machinery or mechanical property of material as main application index,
Particularly, it is including the yield strength of material, fracture strength, fracture toughness, plastic elongation rate, modulus of elasticity, deep drawability, tired
The critical index such as labor performance.Traditional mechanical structural material have mould steel, stainless steel, heat resisting steel, aluminium alloy, nickel alloy,
Titanium alloy, in addition to all kinds of composites, such as Ceramic Reinforced MMCs, above-mentioned material respectively has excellent in the application
Gesture, also has the shortcomings that each overcome, and such as steel class is perishable, intensity of aluminum alloy is low, composite material interface control technique
Difficulty etc..In some special fields, structural material can all run into some special requirements, and often traditional material can not be looked forward to
And.Compared with traditional crystal alloy material, block amorphous alloy material very advantageous in terms of multinomial performance, with more
It is excellent mechanical property, processing characteristics, the expansion characteristics of soft magnetism Hard Magnetic and uniqueness, the ability of anti-medium corrosion, good
Biocompatibility etc., these good characteristics cause non-crystaline amorphous metal to be had broad application prospects in many fields.So far, it is non-
Peritectic alloy system has developed many products with excellent properties and can be used for mechanical structural material, such as CoFeTaB bulk amorphous alloy
The compressive strength of alloy can reach 5185MPa, create the highest record of nature Strength of Metallic Materials；ZrTiCuNiBe blocks
Non-crystaline amorphous metal has brittleness at room temperature but elastic strain limit is up to 2%；CuZrAl block amorphous alloys have temperature-room type plasticity to process again
Hardening.In many non-crystaline amorphous metal systems, Zr-Al-Cu-Ni quaternary alloys system can prepare amorphous formation ability and thermally-stabilised
Property all extraordinary amorphous alloy material, such as Zr65Al7.5Ni10Cu17.5.Also by change on the basis of the quaternary alloy system
Preparation technology and alloying component formula test have gone out many new amorphous alloy materials for possessing other functions.
Application No. 201510222401.6 it is entitled《A series of Zr-Al- with room temperature compression plasticity and high intensity
Ni-Cu block amorphous alloys》A series of non-crystaline amorphous metal of Zr-Al-Ni-Cu systems is disclosed in Chinese patent and its work is prepared
Skill, has prepared Zr51.5Al13.6Ni14.9Cu20、Zr52Al12.9Ni13.8Cu21.3、Zr52.5Al12.2Ni12.6Cu22.7、
Zr53Al11.6Ni11.7Cu23.7、Zr53.5Al10.9Ni10.6Cu25、Zr54Al10.2Ni9.4Cu26.4、Zr54.5Al9.6Ni8.4Cu27.5And Zr55Al8.9Ni7.3Cu28.8.The yield strength of alloy is 1737.5-2041.9MPa, and compression strength is 1892.6-2184.6MPa, modeling
Property strain be 0.4-19.1%.
Application No. 201210435848.8 it is entitled《A kind of aluminum matrix composite with superhigh intensity and controllable plasticity
Preparation method》Chinese patent in disclose a kind of Ni-Co-Y-La-Al quinary alloys system, the aluminium-based amorphous alloy of the system is closed
Gold prepares the aluminium base with more than 1500MPa fracture strengths and meets material by improving formula and technique, and plasticity can reach
21%。
How to prepare both has more excellent mechanical property, but also with good amorphous formation ability and forming ability,
The non-crystaline amorphous metal for possessing large-scale steady production ability is still the direction that research is made great efforts.
The content of the invention
The invention provides a kind of high intensity, plasticity is good, amorphous formation ability is excellent, fine and close, amorphous forming ability is good
Zr base noncrystal alloys and preparation method thereof, the Zr base noncrystal alloys especially improve fracture strength.
The technical problems to be solved by the invention are achieved by the following technical programs：
1st, composition of raw materials
Non-crystaline amorphous metal composition is ZraAlbCucNidBeeSnfM1gM2h, wherein a, b, c, d, e, f, g, h is the non-crystaline amorphous metal
In corresponding atomic molar percentage composition, respectively 40≤a≤70,5≤b≤25,5≤c≤15,5≤d≤15,0.2≤e≤
3,0.2≤f≤4,0.5≤g≤5,1≤h≤5；M1 be Hf, Ta, lanthanide series in one or more mixtures, M2 be Ti,
One or more mixtures in Sc, Fe, Co element.
Non-crystaline amorphous metal stability on the whole and certain amorphous formation can be ensured by Main elements of Zr, Al, Cu, Ni
Ability.Atomic molar percentage composition is respectively 40%-70%, 5%-25%, 5%-15%, 5%-15%, preferably 55%-65%, 10%-
25%th, 7%-12%, 7%-12%, more preferably 55%-60%, 10%-20%, 8%-10%, 8%-10%.
Further preferably, M1 is one or both of Hf, Ta mixture.
The present inventor show that the addition of very small amount Be elements may be such that all kinds of atoms in non-crystaline amorphous metal by many experiments
Cluster is more fine and close.During non-crystaline amorphous metal melting, can will become apparent from adding a small amount of Be elements can lift amorphous conjunction on the whole
The viscosity of golden molten mass, so as to lift the compactness extent of non-crystaline amorphous metal global formation ability and finished product.Because Be members have
Certain toxicity, and the addition of Be elements can also influence the Forming ability of amorphous, therefore Be additions should not be excessive, atomic molar
Percentage composition accounts for the 0.2-3% of Integral alloy, is preferably 0.5%-2%, much further preferably from 1%-2%, the addition scope
Interior Be elements toxicity can be neglected.
The high non-crystaline amorphous metal processability of many intensity and plasticity are poor, although excellent in mechanical performance itself, does not have
The practicality applied in the industry.Sn elements are added in the present invention, Sn fusing points are low oxidizable, a small amount of addition helps to lift amorphous
Alloy product plasticity, can strengthen the practical performance of the amorphous alloy material, and on intensity without influence.
Lanthanide series, Hf, Ta are that property is close with cycle adjacent element, can different journeys in zirconium-base amorphous alloy
The substitution Main elements Zr of degree, adds the active force between different Elements Atoms, macro manifestations for alloy structure after cooling compared with
It is good for fine and close, processability.Group of the lanthanides, the addition of Hf, Ta element can suppress the crystallization of non-crystaline amorphous metal, improve the steady of melt
It is qualitative, that is, lift amorphous formation ability.Under equal additive capacity, preferred sequence is Hf ＞ Ta ＞ lanthanide series.The dvielement adds
It is preferably 1%-4%, much further preferably from 1%- plus atomic molar percentage composition 0.5%-5% can obtain preferable effect
3%。
Ti, Sc, Fe, Co are period element, and nature is highly stable, while Ti, Sc, Fe, Co can be with Zr, Be, Al
Form linking atom pair, it is microcosmic it is upper form the high close pile structure of randomness, can greatly be lifted non-crystaline amorphous metal intensity and
Become sexuality.Ti, Sc, Fe, Co element can greatly reduce amorphous when being separately added to Zr-Al-Cu-Ni quaternary system alloys
Into ability, addition can excessively cannot get bulk amorphous alloy with practical value, it is necessary to while adding group of the lanthanides, Hf, Ta element
The reduction for the amorphous formation ability that Ti, Sc, Fe, Co element can be brought is offseted.Ti, Sc, Fe, Co element add atomic molar
Percentage composition is 1%-5%, is preferably 2%-5%, much further preferably from 3%-5%.
Further, the Mn elements that atomic molar percentage composition is 0.1-0.5% can be also added in above-mentioned non-crystaline amorphous metal.Mn
Elemental stable, Al, Cu are may replace in non-crystaline amorphous metal phase, add the active force between different Elements Atoms, are improved amorphous
Into ability, while intensity and the deformation of non-crystaline amorphous metal can also greatly be lifted with Zr, Be, Al formation linking atom pair
Ability.
2nd, preparation method
Step one, raw metal is weighed according to non-crystaline amorphous metal proportion of composing, the purity of raw metal is more than 99.5%.
In general, the good non-crystaline amorphous metal of amorphous formation ability is obtained, the material purity of amorphous is very high, often needs
More than 99.9%, once because impurity is excessive in raw material, can be with the oxygen element generation oxide in raw material, the mistake being molded in amorphous
As kind of a brilliant induction alloy crystal inside in journey, so as to influence the formation of amorphous metal.The group of the lanthanides member added in the present invention
Element, Hf, Ta, Sn element then can just suppress the crystallization, absorb the oxygen in alloy, suppress the formation of nucleus, improve and close
The Forming ability of amorphous metal in gold.Amorphous can be made using proportioning addition lanthanide series, Hf, Ta, Sn element in the present invention
The purity requirement reduction of alloy raw material, and the quality of the non-crystaline amorphous metal product of output is not influenceed, reduce production cost.
Step 2, passes through electric arc melting or other conventional melting sides under argon gas atmosphere or vacuum condition after raw material is mixed
Raw material melting is obtained non-crystaline amorphous metal ingot casting by formula after cooling；When formula in the present invention carries out melting, without low-down vacuum
Degree so that smelting apparatus requires time length increase cost that is high, vacuumizing.Vacuum is 10 in fusion process-1-10-2Pa is
Can, requirement can be reached in a short time, be adapted to industrialized production；Argon gas atmosphere remains 0.05MPa, is also very easy
Reach requirement.Cooling velocity is 10 after melting2-103K/s, you can obtain the excellent non-crystaline amorphous metal of forming ability.
Step 3, above-mentioned non-crystaline amorphous metal product is obtained by inhaling the conventional non-crystaline amorphous metal preparation method such as casting, die casting.The present invention
In zirconium-base amorphous alloy can prepare consumer electronics product, medical device product, apply also for aerospace industry and vapour
In turner industry.Because of the plasticity that there is high intensity to become reconciled, it is particularly suitable as grinding tool material, mechanical structural material and is applied.
The present invention has the advantages that：
1st, in the present invention zirconium-base amorphous alloy intensity height, plasticity are good, are particularly suitable as grinding tool material, mechanical structure material
Material is applied.
2nd, the zirconium-base amorphous alloy compact structure in the present invention, forming ability is good.
3rd, the zirconium-base amorphous alloy Forming ability in the present invention is excellent, and amorphous formation ability can reach 35mm.
4th, the zirconium-base amorphous alloy preparation technology in the present invention is simple, and process conditions are not harsh, is adapted to industrialized production.
5th, the zirconium-base amorphous alloy ingredient requirement scope in the present invention is loose, it is possible to decrease manufacturing cost.
Embodiment
1st, embodiment 1
Amorphous raw material is constituted into Zr according to alloyaAlbCucNidBeeSnfM1gM2hProportioning, wherein a, b, c, d, e, f, g, h are
Corresponding atomic molar percentage composition in the non-crystaline amorphous metal, M1 is one or more mixtures in Hf, Ta, lanthanide series,
M2 is one or more mixtures in Ti, Sc, Fe, Co element.Melting, metal are carried out under vacuum or in argon atmosphere
The purity of raw material is more than 99.5%, and vacuum is 10-1-10-2In the range of Pa all can, if from argon atmosphere, Ar Pressure
Power remains 0.05MPa.Cooling velocity is 102-103K/s all can, do not make significant difference.Zirconium-base amorphous alloy is obtained after melting cooling
Ingot casting, non-crystaline amorphous metal product is obtained by inhaling the conventional non-crystaline amorphous metal preparation method such as casting, die casting.
The mechanical property of non-crystaline amorphous metal is characterized according to the result of bend test and compression test in the present invention, bend test
According to《YB/T 5349-2014 metal material bending mechanical performance test methods》Carry out, compression test according to《GB/T
7314-2005 metal material room temperature compression test methods》Carry out.
Alloy composition is ZraAlbCucNidBeeSnfM1gM2h, wherein a-h is Elements Atom molar content, under
Table carries out melting, shaping：
M1, M2 selection proportioning are as follows（Numerical value after the symbol of element is Elements Atom molar content）：
Test result is as follows：
It can be seen that by embodiment 1, the non-crystaline amorphous metal product strength in the present invention is high, plasticity is good, and the Forming ability of amorphous is good.
2nd, embodiment 2
Non-crystaline amorphous metal product and characterizing method are same as Example 1.
Alloy composition is ZraAlbCucNidBeeSnfM1gM2hMnx, wherein a-h, x is Elements Atom molar content,
Ratio between the element and element of M1, M2 selection is same as Example 1, and melting, shaping is carried out according to the following table：
Test result is as follows：
It can be seen that there are different journeys to the intensity of non-crystaline amorphous metal, plasticity and formation size after addition Mn elements by embodiment 2
The improvement of degree.
3rd, comparative example
Non-crystaline amorphous metal product and characterizing method are same as Example 1.
Alloy composition is ZraAlbCucNid, wherein a-d be Elements Atom molar content, be carried out according to the following table melting,
Shaping：
Test result is as follows：
It can be seen that by the test result of comparative example, the non-crystaline amorphous metal in the present invention is to the strong of Zr-Al-Cu-Ni quaternary alloys
Degree and formation size have extraordinary improvement result.
It is last it should be noted that above example is only entered to the technical scheme that illustrates the embodiment of the present invention rather than to it
Row limitation, although the embodiment of the present invention is described in detail with reference to preferred embodiment, one of ordinary skill in the art
It should be understood that the technical scheme of the embodiment of the present invention can still be modified or equivalent substitution, and these are changed or waited
It can not also make the scope of amended technical scheme disengaging technical scheme of the embodiment of the present invention with replacing.
Claims (6)
1. a kind of high intensity non-crystaline amorphous metal, it is characterised in that：
The non-crystaline amorphous metal composition is ZraAlbCucNidBeeSnfM1gM2h, wherein a, b, c, d, e, f, g, h is amorphous conjunction
Corresponding atomic molar percentage composition, respectively 40≤a≤70,5≤b≤25,5≤c≤15,5≤d≤15,0.2≤e in gold
≤ 3,0.2≤f≤4,0.5≤g≤5,1≤h≤5；
M1 is one or more mixtures in Hf, Ta, lanthanide series, and M2 is the one or more in Sc, Fe, Co element
Mixture；
Also comprising the Mn elements that atomic molar percentage composition is 0.1-0.5% in the non-crystaline amorphous metal；
The preparation method of the non-crystaline amorphous metal is：
Step one, raw metal is weighed according to non-crystaline amorphous metal proportion of composing, the purity of raw metal is more than 99.5%,
Step 2, will by electric arc melting or other conventional melting modes under argon gas atmosphere or vacuum condition after raw material is mixed
Non-crystaline amorphous metal ingot casting is obtained after raw material melting, cooling；Vacuum is 10 in fusion process-1-10-2Pa, argon atmospheric pressure is
0.05MPa；Cooling velocity is 10 after melting2-103K/s；
Step 3, above-mentioned non-crystaline amorphous metal product is obtained by inhaling casting, the conventional non-crystaline amorphous metal preparation method of die casting.
2. the non-crystaline amorphous metal according to claim 1, it is characterised in that：M1 is one or both of Hf, Ta mixture.
3. the non-crystaline amorphous metal according to claim 1 or 2, it is characterised in that：The non-crystaline amorphous metal atomic molar percentage composition
Respectively 55≤a≤65,10≤b≤25,7≤c≤12,7≤d≤12,0.5≤e≤2,1≤f≤3,1≤g≤4,2≤h≤
5。
4. the non-crystaline amorphous metal according to claim 1 or 2, it is characterised in that：The non-crystaline amorphous metal atomic molar percentage composition
Respectively 55≤a≤60,10≤b≤20,8≤c≤10,8≤d≤10,1≤e≤2,2≤f≤3,1≤g≤3,3≤h≤5.
5. the application of non-crystaline amorphous metal described in a kind of claim 1, it is characterised in that：The non-crystaline amorphous metal is applied to consumer electricity
In sub- product, medical device product, aerospace industry and auto industry.
6. the application of non-crystaline amorphous metal described in a kind of claim 1, it is characterised in that：The non-crystaline amorphous metal is used as grinding tool material, machine
Tool structural material is applied.
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| CN105714216A (en) * | 2016-02-29 | 2016-06-29 | 宋佳 | High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof |
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| CN101314838B (en) * | 2007-05-30 | 2012-05-30 | 中国科学院金属研究所 | Zr-Cu-Ni-Al-Ag alloy with higher amorphous forming ability and production method thereof |
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