CN1632149A

CN1632149A - Scandium-base large amorphous alloy and method for preparing same

Info

Publication number: CN1632149A
Application number: CN 200510001972
Authority: CN
Inventors: 郗学奎; 赵德乾; 潘明祥; 汪卫华
Original assignee: Institute of Physics of CAS
Current assignee: Institute of Physics of CAS
Priority date: 2005-01-13
Filing date: 2005-01-13
Publication date: 2005-06-29
Anticipated expiration: 2025-01-13
Also published as: CN1294285C

Abstract

The present invention discloses a scandium based block amorphous alloy adopting scandium as its essential component and rare-earth as one of its basic alloy elements, which constitution can be represented by the formulae as follows: Sc[60-x]Co[20](Y, Gd)[20]Al[x] or Sc[56-y]Co[20](Y, Gd)[10+y]Al[24] or Sc[45-z]Co[10+z](Y, Gd)[20]Al[25], wherein x-14-25, y=5-10 and z=5-10. The present invention possesses the following benefits: 1, the scandium based block amorphous alloy has a low critical cooling rate; 2, its has specific modulus; 3, it has high heat endurance; 4, it is suitable for industrial usages, can be thoroughly heated to above the glass transformation temperature for process executing without crystallization occurring; 5, it exhibits high fabricating performances. The purity requirement of rare-earth alloy element is not high, the preparing process is simple and easy to manipulate.

Description

Scandium-base large amorphous alloy and preparation method thereof

Technical field

The present invention relates to non-crystaline amorphous metal or metallic glass field, specifically relating to a kind of is main component with the scandium, has added an amount of transition element and yttrium rare earth element, and comprises the high ratio modulus scandium-base large amorphous alloy of 50% above volume percent amorphous phase.

Background technology

Since people such as H.S.Chen, A.Inoue, W.L.Johnson prepare multiple bulk amorphous alloys is as Pd-Cu-Si, La-Al-(Ni, Cu)-Co, Mg-(Cu, Ni)-(Y, Nd), since Zr-Al-Ni-Cu, the Zr-Ti-Cu-Ni-Be, bulk amorphous material is because its unique physicals and mechanical property have caused physicist and material scholars' very big concern.At present, the glass transition of bulk amorphous material, glass forming ability or mechanism, crystallization Mechanism, deformation mechanism etc. have become the research focus in Materials science and engineering field.Zr base alloy system is as one of alloy system with the strongest glass forming ability, and its intensity can reach more than the 2000MPa, surpasses the highest steel of present intensity, and specific tenacity and specific rigidity are then considerably beyond steel.Zirconium base massive non-crystalline material specific rigidity reaches 15N.m, is one of the highest material of present specific rigidity.

Summary of the invention

The invention provides novel scandium base (ScAlCo) bulk amorphous alloys of a kind of more high specific stiffness and preparation method thereof, this be the specific rigidity of amorphous alloy material more up to 20N.m, system improves about 33% than the Zr base noncrystal alloy.

The objective of the invention is to realize by the following technical solutions:

Scandium-base large amorphous alloy provided by the invention is to be main component with the scandium, and rare earth is as alloying element, and it forms available following formulate:

Sc _60-xCo ₂₀(Y，Gd) ₂₀Al _x

Or Sc _56-yCo ₂₀(Y, Gd) _10+yAl ₂₄

Or Sc _45-zCo _10+z(Y, Gd) ₂₀Al ₂₅

X=14～25 wherein, y=5～10, z=5～10, described each component purity is not less than 90at%, and described scandium-base large amorphous alloy comprises at least 50% volume percent amorphous phase.

The invention provides a kind of preparation method of above-mentioned scandium-base large amorphous alloy, comprise the steps:

1) in the electric arc furnace of the argon atmospher that titanium adsorbs, it is even by needed atom proportioning above-mentioned component to be mixed the back melting;

2) use conventional permanent mold casting method, water and cast from the metal pattern, obtain scandium-base large amorphous alloy Sc _60-xCo _20-y(Y, Gd) _20-zAl _x(x=14～24, y=5～15, z=5～15).

Further, the metal pattern that is adopted can be anhydrous cold or water-cooled metal mould.

Scandium-base large amorphous alloy provided by the invention is compared with existing non-crystaline amorphous metal, and its advantage is:

1, the critical cooling rate of this scandium-base large amorphous alloy is low.Rate of cooling (Rc) can reach the order of magnitude of 100K/s, and it is strong to suppress crystallizing power, is easy to form large-sized non-crystaline amorphous metal, and its size is not less than 1 millimeter in each dimension, and the critical diameter size is not less than 3 millimeters.

2, has high specific modulus.Glassy alloy density is 4.2g/cm ³About, specific modulus is 20N.m, surpass most of crystalline materials and zirconium-base amorphous material (being about 15N.m) as Vitl, and the latter is considered to one of the highest material of specific modulus and specific tenacity usually, the specific Young's modulus of this base amorphous material far surpasses zirconium-base amorphous alloy, and keep quite high limit recoverable strain, demonstrating this is that alloy has excellent elastic performance.

3. high thermostability.Second-order transition temperature surpasses other rare earth based bulk amorphous material and most of Zr base massive non-crystalline material up to 630-670K, has wide supercooling liquid phase region width, and Tx is 98K.

4, this scandium-base large amorphous alloy is suitable for industrial use, can fully be heated to more than the glass transformation temperature and process under the situation that crystallization does not take place.

5, this scandium-base large amorphous alloy has high manufacturing property.The purity requirement of rare earth alloy element is not high, and preparation technology is simple, easy handling.

Description of drawings

The X-ray diffraction analysis spectrum and the selected diffraction style of the non-crystaline amorphous metal of Fig. 1 embodiment 1 (3mm diameter pole).

The DSC graphic representation of Fig. 2 non-crystaline amorphous metal provided by the invention.

Fig. 3 Sc ₃₆Co ₂₀Al ₂₄Y ₂₀The DTA graphic representation.

The relation of Fig. 4 ScAlCo base amorphous material elastic performance and other rare earth based bulk amorphous material and second-order transition temperature.

The comparison of Fig. 5 Sc base amorphous material limit recoverable strain and other non-crystalline material.

Embodiment:

Embodiment 1

Sc ₃₆Co ₂₀Al ₂₄Y ₂₀The preparation of column bulk amorphous alloys

Use purity as more than the 90at.%, atomic ratio is 36: 20: 24: 20 Sc, Co, Al and Y prepare scandium-base large amorphous alloy.At first, mix, obtain alloy cast ingot after the cooling they meltings in the electric arc furnace of the argon atmospher of titanium absorption; Melt back 5-10 minute again, until ingot casting fusing evenly, use the permanent mold casting method at last, water in the copper mold that casts from water-cooled or do not have water-cooled, obtain uniform ingredients, diameter and be 3 millimeters scandium pilum shape bulk amorphous alloys.

After tested, the density of this alloy is 4.214g/cm ³, Young's modulus of elasticity is about 85.2GPa, and specific modulus reaches 20N.m, considerably beyond general Zr base non-crystalline material.And the latter is considered to one of the highest bulk amorphous material of present specific modulus or specific rigidity.

The X-ray diffractogram at this alloy center position is not observed any crystallization peak as shown in Figure 1 in the effective resolution of X-ray diffractometer, have only a wide diffuse scattering peak, illustrates that this alloy is complete non-crystaline amorphous metal.Under transmission electron microscope, observe and confirmed that also this alloy is complete amorphous.Listed dsc analysis result confirms that also the working sample major part is an amorphous in the table 1.In addition, from table 1, also can find reduction glass transformation temperature (T _Rg) and vitrifying index (γ value) all higher, illustrate that the amorphous formation ability of this alloy is fine, as shown in Figure 3, its stronger amorphous formation ability partly cause is that it is near eutectic composition.Glassy alloy density is 4.2g/cm ³About, specific modulus is 20N.m, surpass most of crystalline materials and zirconium-base amorphous material (being about 15N.m) as Vitl, and the latter is considered to one of the highest material of specific modulus and specific tenacity usually, this base amorphous material and other non-crystalline material relatively see Fig. 4, the specific Young's modulus of New type of S c base noncrystal alloy far surpasses famous zirconium-base amorphous alloy as can be seen, and keeps quite high limit recoverable strain, and demonstrating this is that alloy has excellent elastic performance.Second-order transition temperature surpasses other rare earth based bulk amorphous material and most of Zr base massive non-crystalline material, in detail with reference to Fig. 5 and table 1 up to 630-670K.Have wide supercooling liquid phase region width, Tx is 98K.High Tg and wide supercooling liquid phase region mean high thermostability or thermotolerance.

Embodiment 2～11

Prepare the scandium-base large amorphous alloy of various proportionings by the method for embodiment 1, it is formed and thermal physical property parameter is listed in table 1.DSC temperature rise rate: 20K/min.

The composition of table 1, scandium-base large amorphous alloy and thermal physical property parameter

T _g T _x T _m T _l T T _rg γ

Composition

(K) (K) (K) (K) (K) (K)

Sc ₆₀Co ₂₀Al ₂₀ 670 730 1000 1100 60 0.609 0.395

Sc ₃₆Co ₂₀Y ₂₀Al ₂₄ 662 760 970 1048 98 0.632 0.444

Sc ₄₀Co ₂₀Y ₂₀Al ₂₀ 657 743 990 1051 86 0.625 0.435

Sc ₄₆Y ₂₀Co ₂₀Al ₁₄ 633 684 994 1053 51 0.601 0.406

Sc ₅₀Co ₂₀Y ₂₀Al ₁₀ 632 670 950 1052 38 0.601 0.398

Sc ₄₁Co ₂₀Y ₁₅Al ₂₄ 667 750 956 1045 83 0.638 0.438

SG ₄₆Co ₂₀Y ₁₀Al ₂₄ 664 730 950 1100 66 0.604 0.414

Sc ₃₅Co ₂₀Y ₂₀Al ₂₅ 660 740 945 1115 80 0.592 0.417

Sc ₄₀Co ₁₅Y ₂₀Al ₂₅ 658 748 980 1045 90 0.63 0.439

Sc ₄₅Co ₁₀Y ₂₀Al ₂₅ 645 690 980 1042 45 0.619 0.409

Sc ₃₅Co ₂₀Gd ₂₀Al ₂₅ 650 765 985 1052 115 0.618 0.449

Annotate: 1) T wherein _Rg=T _g/ T _m, γ=T _x/ (T _g+ T _l).

The heat physical properties of the bulk amorphous material of other system of table 2 comparative example

Composition T _gT _xT _mT _lT T _Rgγ

(K) (K) (K) (K) (K) (K)

Ce ₆₀Cu ₂₀Ni ₁₀Al ₁₀ 374 441 645 672 67 0.57 0.422

Gd ₄₀Y ₁₆Al ₂₄Co ₂₀ 598 653 972 995 55 0.60 0.410

Dy ₄₀Y ₁₆Al ₂₄Co ₂₀ 633 682 1011 1031 49 0.61 0.409

^*Pr ₆₀Cu ₂₀Ni ₁₀Al ₁₀ 409 452 705 806 43 0.51 0.372

Nd ₆₀Cu ₂₀Ni ₁₀Al ₁₀ 438 478 728 755 40 0.58 0.401

Zr ₄₁Ti ₁₄Cu _12.5Ni ₁₀B 623 672 932 996 49 0.625 0.415

e _22.5

Zr ₆₅Al _7.5Cu _17.5Ni ₁₀ 656 735 1108 1168 79 0.56 0.403

Pd ₄₀Ni ₁₀Cu ₃₀P ₂₀ 575 670 804 840 95 0.68 0.473

Annotate: DSC temperature rise rate: 10K/min.

By table 1 and table 2 data as can be known, the glass heat stability of different rare earths is different, with reference to comparative example (table 2) as can be known, and Sc ₃₆Co ₂₀Y ₂₀Al ₂₄Has higher relatively thermostability.It is worthy of note that in addition the glass forming ability (GFA) of different systems also is inequality.Rare earth atom electronic structure, atomic size have remarkable influence to the GFA of Sc base large amorphous alloy.Atomic size and its electronic structure, especially closely related with the electronics number of inferior outer 4f electronic shell.Be embodied in the increase along with atomic size (as atom effect volume), GFA increases afterwards earlier and reduces, when atom effect volume is 19cm ³During/mol, the GFA maximum.For example, La-Al-Co-Y can not form large block amorphous.Sm base large amorphous alloy its critical size under the die cast condition can reach about 3mm, and the critical size of Dy base and Er base large amorphous alloy can reach 5～8mm.

Table 3 Sc-BMG and other non-crystalline material elastic constant

T _g E G B

Composition

(K)?(GPa)?(GPa)?(GPa)

Sc ₃₆Co ₂₀Y ₂₀Al ₂₄ 662 85.2 32.3 77.5

Dy ₄₆Y ₁₀Al ₂₄Co ₁₈Fe ₂ 627 64.2 24.4 58.5

Gd ₃₆Y ₂₀Al ₂₄Co ₂₀ 603 62.2 23.6 57.4

Nd ₆₀Fe ₂₀Ni ₁₀Al ₁₀ 485 54.1 20.7 54.1

Pr ₆₀Al ₁₀Ni ₁₀Cu ₂₀ 417 37.2 13.6 45.2

La ₆₆Al ₁₄Cu ₁₀Ni ₁₀ 405 35.7 13.4 34.9

Ce ₇₀Al ₁₀Ni ₁₀Cu ₁₀ 359 30.3 11.5 27.0

Claims

1, a kind of scandium-base large amorphous alloy is to be main component with the scandium, and rare earth is characterized in that as one of basic alloy element it forms available following formulate:

Sc _60-xCo ₂₀(Y，Gd) ₂₀Al _x

Or Sc _56-yCo ₂₀(Y, Gd) _10+yAl ₂₄

Or Sc _45-zCo _10+z(Y, Gd) ₂₀Al ₂₅

X=14～25 wherein, y=5～10, z=5～10.

2, scandium-base large amorphous alloy as claimed in claim 1 is characterized in that, the purity of described rare earth element is not less than 90at%.

3, scandium-base large amorphous alloy as claimed in claim 2 is characterized in that, described scandium-base large amorphous alloy comprises at least 50% volume percent amorphous phase.

4, the preparation method of the described scandium-base large amorphous alloy of a kind of claim 1 comprises the steps:

1) according to

Sc _60-xCo ₂₀(Y，Gd) ₂₀Al _x

Or Sc _56-yCo ₂₀(Y, Gd) _10+yAl ₂₄

Or Sc _45-zCo _10+z(Y, Gd) ₂₀Al ₂₅Ratio prepare raw material, x=14～25 wherein, y=5～10, z=5～10;

2) in the electric arc furnace of the argon atmospher of titanium absorption, by needed atom proportioning with above-mentioned component mix, melting is even;

3) use conventional permanent mold casting method, water and cast from the metal pattern, obtain scandium-base large amorphous alloy.

5, the preparation method of the scandium-base large amorphous alloy of stating as claim 4 is characterized in that the purity of described rare earth element is not less than 90at%.

6, the preparation method of the scandium-base large amorphous alloy of stating as claim 5 is characterized in that described metal pattern can be anhydrous cold or water-cooled metal mould.