Ce-based amorphous metallic plastic

FIELD OF INVENTION

The present invention belongs to the field of amorphous metal alloys and especially concerns a Ce based amorphous metallic plastic.

BACKGROUNDS

Compared with metallic glasses, polymeric glasses have superior glass forming ability, low glass transition temperature (T_g) and wider supercooled liquid region (ΔT, defined as the difference between T_gand the onset crystallization temperature T_x), thus have a very wide range of applicability. The thermoplasticity nature of common glassy polymers is exploited in molding and imprinting. Since chemical scientists invented the thermoplastics in 1940's, they became the basic materials for the 2^ndindustrial revolution. Although their strength is only about one fiftieth of that of steels, thermoplastics products became very cheap because they could be prepared repeatedly using the same mold at a temperature near room temperature. Now thermoplastics are widely used in our daily lives.

In the early 1960's, non-crystalline alloys (so called metallic glasses) were firstly fabricated in laboratories. Compared with polymers, metallic glasses also have advantages in mechanical, electrical, magnetic and chemical properties. Amorphous metal alloys have a supercooled liquid region ΔT above T_g. When an amorphous metal alloy was heated into this region, it still keeps its glassy state and does not crystallized immediately. In general, the wider range of ΔT suggests better deformability of the supercooled state. Therefore, the stability against crystallization is crucial for deformation of an amorphous metal alloy in its supercoolied state. The stability during a heating process is closely related with the critical cooling rate necessary for forming a glass from its liquid. For a good glass former, it is expected that the time-temperature-transformation (TTT) curve will move toward the long time direction.

The conventional melt-spin glasses have a limited ΔT and could not be used to investigate the related properties of the supercooled liquid region. In the early 1990's, bulk metallic glasses (BMGs) with large size up to millimeters even centimeter scales in three dimensions were developed using conventional casting methods. For most of BMGs, their values of ΔT are larger than 45 K and even larger than 100 K in some case. The supercooled liquids of these BMGs show typical Newtonian flow characteristics at low strain rates or low stresses and the maximum elongation could reach about 15000%. For crystalline alloys, they are unable to deform as easily as the viscous supercooled liquids of BMGs, which are capable of remaining the glassy structure and original properties even after large plastic deformation. The unique combination of these superior properties and homogeneous microstructure makes BMGs a new type of engineering materials in applications such as manufacturing the micro-electro-mechanical components. Meanwhile, high strain rates and superplasticity are suitable for quality control, thus make it possible for the mass production.

For most of the known BMGs, however, their industrial applications are still impeded by the limitation of alloy size and the lack of workability and machinability. The polymerlike exploitation of the supercooled viscous flow of many BMGs was also postponed due to low T_gand low stability against crystallization. Additionally, some BMGs based on noble metals like Pd, Pt and Au can only be used in the experimental laboratory because of their high cost although they have good glass forming ability and superplasticity in the supercooled liquid region.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is aimed to overcome the problems in the known BMGs and thus to provide a new type of BMGs named Ce-based amorphous metallic plastics. These problems are the limitation of the small size, poor workability and machinability, the limitation in exploitation of the viscous supercooled liquid due to high T_gand low crystallization resistance and the high cost in some BMGs containing the noble metals such as Pd, Pt and Au. The present amorphous metallic plastics have extremely low T_g, wide supercooled liquid region ΔT and low cost coming from the cheap raw materials having low purity.

The invention is realized using the following techniques and methods.

The invention provides amorphous metallic plastics based on Cerium which can be represented by the following formula:

Ce_aAl_bM_c

in which 55≦a≦75, 5≦b≦25, 10≦c≦25, and a+b+c=100.

The M can be one of three elements Co, Cu and Ni.

The purities of the said Ce, Al and M are no less than 99.5.wt. % (weight percent).

The present invention provides Ce-based amorphous metallic plastics which can be represented by the following formula:

Ce_dAl_eCu_fZ_g

in which 55≦d≦75, 5≦e≦15, 15≦f≦25, 0.01≦g≦10, and d+e+f+g=100.

Z is one element selected from Co, Fe, Hf, Mg, Mo, Nb, Sc, Ta, Ti, W, Zn and Zr.

The purities of the said Ce, Al, Cu and Z are no less than 99.5.wt. % (weight percent).

Furthermore, the present invention provides Ce-based amorphous metallic plastics which can be represented by the following formula:

Ce_hAl_iCu_jNi_k.

in which 55≦h≦75, 5≦i≦15, 15≦j≦25, 0.01≦k≦55, and h+i+j+k=100.

The purities of the Ce, Al, Cu and Ni are no less than 99.5.wt. % (weight percent).

The above-described Ce-based amorphous metallic plastics can be prepared using the conventional method known in the field of metallic glasses. Specifically, the preparation method includes the following steps:

1) Preparation of mother ingots: In a Ti-absorbed arc melting furnace under Argon atmosphere, a mixture of elements Ce, Al and M according to the above formula Ce_aAl_bM_c, or a mixture of Ce, Al, Cu and Z according to the above formula Ce_dAl_eCu_fZ_g, or a mixture of Ce, Al, Cu and Ni according to the above formula Ce_hAl_iCu_jNi_kis blended and melted until homogeneity, and then cooled to form a mother ingot.

2) Suction casting: In a Ti-absorbed arc melting furnace under Argon atmosphere, the mother ingot prepared in the first step is remelted and then suction casted into a copper mold with different cavities to form a sample in the form of rod or sheet.

It should be stressed that many modifications and changes can be made to the present invention without departing the spirit and scope thereof. Although what the instant invention illustrates is to produce Ce-based amorphous metallic plastics by forming an amorphous ingot in a way of suction casting, it is well-known to the person ordinarily skilled in the art that any suitable technique for fabricating non-crystalline alloys or any related casting method under a protective atmosphere such as spray casting, single- or twin-roll melt-spinning, planar flow casting and metal pulverization and so on can also be used to prepare Ce-based amorphous metallic plastics.

For the present Ce based amorphous metallic plastics, the amorphous nature and the volume fraction of the amorphous phase can be determined and evaluated using known techniques such as X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In the examples of the present invention, XRD measurements were carried out on a MAC M03 XHF diffractometer with Cu K_aradiation and HRTEM measurements on a TECNAI-F20 instrument operated at 200 kV. The thin foils for the HRTEM measurements were prepared by mechanical thinning and chemical polishing.

Similarly, any suitable methods can also be used to examine the thermal properties of the Ce-based amorphous metallic alloys. By way of an example, the thermal properties of our samples were determined by differential scanning calorimetry (DSC) under a purified argon atmosphere in a Perkin-Elmer DSC-7, calibrated for temperature and energy with high-purity indium and zinc. Both isothermal and continuous heating (at a rate of 10 K min⁻¹) were used

The mechanical properties and density data, etc of the present Ce based alloys can be measured using many universal instruments. In the present invention, the mechanical properties including yield strength and elastic strain were measured at room temperature and at 90° C. by an MTS 880 system. Compression tests were conducted at a strain rate of 1×10⁻³s⁻. Acoustic velocities were determined by a pulse echo overlap method on a MATEC 6600 ultrasonic system with a measuring sensitivity of 0.5 ns and a frequency of 10 MHz. Young's modulus E, bulk modulus B, Poisson's ratio v and shear modulus G were derived from the acoustic velocities. The density was determined by the Archimedean technique and the accuracy lies within 0.1%. Vickers hardness was measured with a Polyvar Met microhardness tester using a load of 1.96 N. The electrical resistance of the sample at room temperature was measured on a PPMS 6000 instrument (Quantum Design Instrument, Inc.).

The Ce based amorphous metallic plastics defined in the present invention should contain the amorphous phase with a volume fraction of at least 50%. In most cases, the Ce based amorphous metallic plastics prepared according to the present invention have a single amorphous phase, a wide supercooled liquid region ΔT of no less than 20 K and a low T_gof no more than 430 K. These thermal parameters (ΔT and T_g) can be examined using DSC method at a scanning rate of 10 K/min.

The Ce based amorphous metallic alloys in this invention have an extremely low T_gclose to room temperature, a wide supercooled liquid region and high stability against crystallization, thus can be deformed homogeneously in their viscous supercooled liquid state in low temperatures like the near boiling point of water. This polymerlike superplasticity (homogenous deformation) of these Ce based amorphous metallic alloys makes them very easy to form or imprint a complex product with an amorphous structure. For example, in this invention, a precise shape or article can be imprinted on the surface of a Ce based amorphous metallic sample in near boiling water under a pressure of 30˜300 MPa.

Generally, compared with the prior arts, the present Ce based amorphous metallic plastics contain Ce as a main component and also several addition elements like Al, Co, Cu, Fe, and Nb, and have advantages as follows:

- 1. They have high glass forming ability, and easily cast into bulk glasses with different sizes ranging from millimeter to centimeter;
- 2. They have extremely low T_gand can deform like polymeric thermoplastics;
- 3. They have wide supercooled liquid regions and high thermal stability against crystallization, thus are suitable for industrial production (i.e. a long manufacturing time before crystallization);
- 4. They have high thermostability at low temperatures near the boiling point of water in their supercooled liquid states, thus are able to deform repeatedly in a precise die.
- 5. They contain the addition components selected from commonly used metals like Al, Co, Cu, Fe, Zn, Nb and so on, which can obviously decrease the cost of materials.

DESCRIPTION OF FIGURES

FIG. 1 shows the appearance of Ce-based amorphous metallic plastics of the present invention. A Ce₇₀Al₁₀Cu₂₀glassy sheet with a size of 1.5×12×70 mm³(A) is the sample prepared in Example 1. An as-cast Ce₆₈Al₁₀Cu₂₀Nb₂glassy rod of 8 mm in diameter (B) is prepared in Example 3.

FIG. 2 shows XRD results of a Ce₇₀Al₁₀Cu₂₀glassy sheet of 2 mm in diameter (A) with a size of 1.5×12×70 mm³prepared in Example 1 and an as-cast Ce₆₈Al₁₀Cu₂₀Nb₂glassy rod of 8 mm in diameter (B) prepared in Example 3.

FIG. 3 shows HRTEM image and selected-area electron diffraction pattern for the 1 mm diameter Ce₇₀Al₁₀Cu₂₀as-cast sample prepared in Example 1, showing a single glassy phase with no evidence for nanocrystallization.

FIG. 4 shows DSC results at a heating rate of 10 K/min for the Ce₇₀Al₁₀Cu₂₀glassy sample (A) prepared in Example 1 and the Ce₆₈Al₁₀Cu₂₀Nb₂glassy sample (B) prepared in Example 3.

The inset picture in the right corner in FIG. 4 shows isothermal DSC traces for Ce₇₀Al₁₀Cu₂₀glass (prepared in Example 1) held at 120° C.: (a) immediately after casting, and (b) after three months at room temperature (20-38° C.).

FIG. 5 shows the time-temperature-transformation (TTT) diagram for crystallization of Ce₇₀Al₁₀Cu₂₀glass in Example 1. Isothermal DSC traces have been used to estimate the times to 1% (open circle) and 99% (solid circle) crystallized at each temperature. The dashed line extrapolated to room temperature (˜20° C.) shows the onset time for crystallization at that temperature to be ˜10¹⁰s (˜200 years).

FIG. 6 shows the true stress-true strain curve of a 2 mm diameter Ce₇₀Al₁₀Cu₂₀glassy rod (in Example 1) tested under compression at RT and at 90° C.

The inset of FIG. 6 shows the starting sample, 2 mm in diameter and 3 mm in height, on the left and the sample compressed at 90° C., 5 mm in diameter and 0.3 mm in height, on the right.

FIG. 7 shows the 1 mm diameter glassy rods (prepared in Example 1) formed into letters by simple manipulation in near-boiling water.

FIG. 8 shows the impression of a UK five-pence coin made on the surface of a Ce₇₀Al₁₀Cu₂₀glassy sheet (prepared in Example 1) held in near-boiling water, demonstrating excellent imprintability and viscous deformability.

FIG. 9 shows XRD results of the 10 mm diameter as-cast Ce_69.5Al₁₀Cu₂₀Co_0.5glassy rod prepared in Example 2.

FIG. 10 shows DSC results at a scanning rate of 10 K/min for the 10 mm diameter as-cast Ce_69.5Al₁₀Cu₂₀Co_0.5glassy rod prepared in Example 2.

MODE OF CARRYING OUT THE INVENTION
EXAMPLE 1
Ce₇₀Al₁₀Cu₂₀Amorphous Metallic Plastic

Ingots with nominal compositions of Ce₇₀Al₁₀Cu₂₀(at. %) were prepared by arc melting commercial-purity Ce (99.5 wt. %) with high-purity Al (99.99%), Cu (99.99%) and Nb (99.9%) under a purified argon atmosphere. The ingots were remelted and suction-cast into a Cu-mould with different cavities (cylinder or sheet) to obtain bulk form such as a sheet with dimension of 1.5×12×70 mm³(see FIG. 1A) and the rods with 1 mm (see FIG. 7) and 2 mm (see the inset in FIG. 6) in diameter.

The as-cast 2 mm diameter Ce₇₀Al₁₀Cu₂₀rod is fully glassy. As shown in FIG. 1, the samples can be cast in rod and in sheet form with lustrous surfaces. As expected for casting of glassy alloys, when solidification does not involve crystallization, there is very little volume shrinkage, with consequent good castability. Earlier work on BMGs based on rare earth metals, for example on neodymium, has shown that it can be difficult to obtain fully glassy structures; often there is a significant proportion of nanocrystals in the glassy matrix. For this reason particular care was taken to establish the structures of the cast alloys in the present work.

The XRD pattern of the 2 mm diameter Ce₇₀Al₁₀Cu₂₀rod is shown as curve A in FIG. 2. The XRD patterns show only two broad maxima associated with an amorphous phase and no detectable Bragg peaks corresponding to crystalline phases. This shows that the alloy is fully amphous.

HRTEM is more sensitive than XRD to minitor volume fractions of dispersed crystals. As seen in FIG. 3, HRTEM results for 1 mm diameter Ce₇₀Al₁₀Cu₂₀rod still show only the uniform contrast expected for a single glassy phase.

The DSC trace for the as-cast Ce₇₀Al₁₀Cu₂₀alloy at 10 K/min is shown in FIG. 4. The clear exothermic peak indicates its glassy nature, in contrast to the decaying exothermic signal expected for coarsening of a polycrystalline structure. The Ce₇₀Al₁₀Cu₂₀sample shows a T_gof 68° C. (341 K), lower than any previous BMGs, and a large supercooled liquid region (ΔT=T_x−T_g=69 K). The T_gof the sample is very close to those of typical polymers like Nylon (˜43° C./316 K) and polyvinylchloride (75-105° C./348-378 K).

The stability of the Ce₇₀Al₁₀Cu₂₀glassy alloy is examined by isothermal DSC method. As shown in the inset of FIG. 4, the isothermal DSC curves at 120° C. suggested that a sample stored at RT (20 to 38° C.) for three months is still glassy. The stability was further investigated over a range of temperature. Isothermal DSC was used to determine the time-temperature-transformation (TTT) diagram (see FIG. 5) to estimate the times to 1% and 99% crystallized at each temperature. As an empirical guide to stability, FIG. 5 gives an Arrhenius extrapolation with a predicted lifetime at 20° C. of ˜10¹⁰s (or 200 years), which suggests that Ce₇₀Al₁₀Cu₂₀glassy alloy has considerably high stability.

As seen in FIG. 6, at room temperature the Ce₇₀Al₁₀Cu₂₀glassy alloy is brittle, even in compression showing ˜1.5% elastic strain followed by catastrophic failure. However, raising the temperature to 90° C. (in the supercooled liquid state) gives a complete change in behavior, to perfect superplasticity. The sample can be compressed to about 10% of its original height without cracking (see the inset of FIG. 6). Just as expected for a conventional polymeric thermoplastic, the material can be repeatedly compressed, stretched, bent and formed into complicated shapes.

The temperature required for this excellent deformability is approximately 100° C., which is normal for polymers but highly unusual for metallic alloys. The ease of thermoplastic forming can be demonstrated using near-boiling water (FIG. 7). It has been verified by XRD that samples remain fully amorphous after 10 min in near-boiling water, consistent with the TTT diagram (FIG. 5).

Although showing thermoplastic behaviour like nylon or PVC, the Ce₇₀Al₁₀Cu₂₀metallic thermoplastics show mechanical and physical properties, which are very different from polymeric materials. Their density (6738 kg m⁻³), Vickers hardness (1.50 GPa), fracture toughness (10.0 MPa m^1/2), E=29.91 GPa, K=29.18 GPa, G=11.25 GPa, Poisson's ratio (0.32) and tensile strength (490 MPa) are all much higher than those of typical polymers. The electrical resistivity of the BMG is ˜119 μΩ-cm; it is thus a metallic conductor, in contrast to the insulating properties of typical polymers.

The excellent imprintability and viscous deformability of the Ce₇₀Al₁₀Cu₂₀metallic thermoplastics can also be demonstrated by the impression of a UK five-pence coin made on the surface of its sheet held in near-boiling water by hand pressure.

It may also be very useful that this imprintability is combined with electrical conductivity.

EXAMPLE 2
Ce_69.5Al₁₀Cu₂₀Co_0.5Amorphous Metallic Plastic

Using the same preparation methods described in Example 1, Ce_69.5Al₁₀Cu₂₀Co_0.5amorphous metallic plastic was developed. Compared with Ce₇₀Al₁₀Cu₂₀, Ce_69.5Al₁₀Cu₂₀Co_0.5shows larger glass forming ability with a critical diameter of 10 mm. The amorphous nature of Ce_69.5Al₁₀Cu₂₀Co_0.5as-cast alloy was also demonstrated by the XRD method as shown in FIG. 9. The T_gvalue of Ce_69.5Al₁₀Cu₂₀Co_0.5glass was not obviously changed and remained as the same value as that of Ce₇₀Al₁₀Cu₂₀, while the ΔT of Ce_69.5Al₁₀Cu₂₀Co_0.5increased to ˜78 K (˜10 K larger than that of Ce₇₀Al₁₀Cu₂₀). The DSC results of the Ce_69.5Al₁₀Cu₂₀Co_0.5glassy alloy were presented in FIG. 10. This alloy is most characterized in that a dramatic change in glass forming ability can be achieved by adding a very small amount of Co into Ce₇₀Al₁₀Cu₂₀alloy. Its elastic constants E, G and K are 31.1 GPa, 11.6 GPa and 31.3 GPa, respectively. All these thermal and mechanical data are listed in Table I.

EXAMPLE 3
Ce₆₈Al₁₀Cu₂₀Nb₂Amorphous Metallic Plastic

For this composition, a glassy rod with at least 8 mm in diameter can be prepared using the same preparation methods described in Example 1. Its appearance picture is shown in FIG. 1, DSC results in FIG. 4 and XRD results in FIG. 2. The thermal parameters and elastic constants of the Ce₆₈Al₁₀Cu₂₀Nb₂alloy are also listed in Table I. Compared with Ce₇₀Al₁₀Cu₂₀in Example 1, the glass forming ability of Ce₆₈Al₁₀Cu₂₀Nb₂alloy is greatly improved from about 2 mm to at least 8 mm in the critical diameter. The ΔT of Ce₆₈Al₁₀Cu₂₀Nb₂glassy alloy is ˜76 K, which is about 7 K larger than that of Ce₇₀Al₁₀Cu₂₀, suggesting a higher stability of the Ce₆₈Al₁₀Cu₂₀Nb₂glass forming liquid against crystallization. Elastic constants including E (31 GPa), G (11.7 GPa) and K (30 GPa) are nearly the same as those of Ce₇₀Al₁₀Cu₂₀(Example 1) and Ce_69.5Al₁₀Cu₂₀Co_0.5(Example 2).

EXAMPLE 4˜8

Five Ce based ternary Ce_aAl_bM_camorphous metallic plastics of Examples 4 to 8 were prepared using the same method as that of Example 1, where M is one element selected from Co, Cu and Ni. The detailed composition for these five ternary alloys are listed in Table I. Their glass forming ability indicated by the critical diameter d_cand thermal properties including T_g, T_x, ΔT, T_m(the melting temperature) and T_l(the liquidus temperature) are all listed in Table I.

EXAMPLE 9˜35

All the Ce-based amorphous metallic plastics of Examples 9 to 35 can be prepared using the same method described in Example 1. Their compositions all come from the formula Ce_dAl_eCu_fZ_gand Ce_hAl_iCu_jNi_k, where Z is one element selected from Co, Fe, Ni, Hf, Mg, Mo, Nb, Sc, Ta, Ti, W, Zn and Zr. Their XRD results are similar to those of Example 3. For the alloys of Examples 9 to 19, their compositions and thermal data detected by the DSC method are listed in Table I. For Examples 9-11, 13 and 14, their elastic constants (E, G and K) are also listed in Table I. For the alloys of Examples 20-35, the compositions and the minimum volume fraction of the glass phase in each alloy are shown in Table II. Compared with the ternary alloy Ce₇₀Al₁₀Cu₂₀(Example 1), the introduction of the fourth element like Z and Ni in these quaternary alloys can improve its glass forming ability more or less, but does not change its elastic properties very much.

TABLE I□

Critical diameter(d_c), thermal parameters and elastic constants of Ce based amorphous metallic plastics

d_c
T_g
T_x
ΔT
T_m
T_l
E
G
K

Example No.
Composition
(mm)
(K)
(K)
(K)
(K)
(K)
(GPa)
(GPa)
(GPa)

1.
Ce₇₀Al₁₀Cu₂₀
2
341
410
69
647
722
29.91
11.25
29.18

2.
Ce_69.5Al₁₀Cu₂₀Co_0.5
10
341
419
78
639
716
31.08
11.64
31.25

3.
Ce₆₈Al₁₀Cu₂₀Nb₂
8
345
421
76
646
721
30.95
11.65
30.06

4.
Ce₆₅Al₁₅Cu₂₀
2
363
425
62
677
773

5.
Ce₇₀Al₁₅Cu₁₅
2
364
406
42
660
775

6.
Ce₆₀Al₂₀Co₂₀
5
424
468
44
684
798

7.
Ce₇₀Al₁₀Ni₂₀
1
373
399
26
687
775

8.
Ce₇₀Al₁₅Ni₁₅
1
368
387
19
691
738

9.
Ce_69.8Al₁₀Cu₂₀Co_0.2
8
339
414
75
643
721
30.82
11.54
31.22

10.
Ce₆₉Al₁₀Cu₂₀Co₁
10
340
421
81
634
713
31.13
11.68
31.07

11.
Ce₆₈Al₁₀Cu₂₀Co₂
10
352
419
67
615
716
31.34
11.80
30.33

12.
Ce₆₅Al₁₀Cu₂₀Co₅
8
363
414
51
615
695

13.
Ce₆₈Al₁₀Cu₂₀Fe₂
5
352
423
71
646
708
32.70
12.32
31.35

14.
Ce₆₈Al₁₀Cu₂₀Ni₂
5
352
421
69
647
710
31.93
11.98
31.77

15.
Ce₆₉Al₁₀Cu₂₀Nb₁
10
352
412
60
646
728

16.
Ce₆₇Al₁₀Cu₂₀Nb₃
5
355
404
49
646
723

17.
Ce₇₀Al₁₀Cu₁₉Zn₁
1
343
391
58
635
743

18.
Ce₇₀Al₁₀Cu₁₈Zn₂
2
345
399
54
633
730

19.
Ce₇₀Al₁₀Cu₁₇Zn₃
3
341
412
71
634
733

Note:

1) d_cis the smallest critical diameter for the fully glassy rod prepared under our own experimental conditions

2) Thermal parameters were measured by DSC at a constant heating rate of 10 K/min.

In general, in the present invention, most of the Ce based amorphous metallic plastics show extremely low T_gin the range of 341-364 K, very close to those of typical polymeric glasses like Nylon (˜316 K) and PVC (348-378 K). By introducing the additional element, the T_gof Ce based amorphous metallic plastics can be adjusted to meet the requirements of manufacturing and application. Therefore, the Ce-based amphous metallic plastics provided by the present invention can be deformed so as to form desired shapes, as with thermoplastic plastics.

TABLE II

□Compositions, critical diameter(d_c) and

critical volume fraction(f ) of the glassy phase for Ce

based amorphous metallic plastics

Example No.
Composition
d_c(mm)
f

20.
Ce₆₅Al₁₀Cu₂₀Zn₅
5
>60%

21.
Ce₆₉Al₁₀Cu₂₀Hf₁
2
>90%

22.
Ce₆₈Al₁₀Cu₂₀Hf₂
2
>80%

23.
Ce₆₉Al₁₀Cu₂₀Mg₁
2
>50%

24.
Ce₆₈Al₁₀Cu₂₀Mg₂
3
>70%

25.
Ce₆₉Al₁₀Cu₂₀Mo₁
2
>85%

26.
Ce₆₈Al₁₀Cu₂₀Mo₂
4
>60%

27.
Ce₆₉Al₁₀Cu₂₀Sc₁
5
>90%

28.
Ce₆₉Al₁₀Cu₂₀Ta₁
2
>90%

29.
Ce₆₉Al₁₀Cu₂₀Ti₁
3
>70%

30.
Ce₆₉Al₁₀Cu₂₀W₁
2
>70%

31.
Ce₆₉Al₁₀Cu₂₀Y₁
1
>70%

32.
Ce₆₉Al₁₀Cu₂₀Zr₁
1
>60%

33.
Ce₆₉Al₁₀Cu₂₀Bi₁
2
>60%

34.
Ce₆₉Al₁₀Cu₂₀Sn₁
3
>50%

35.
Ce₆₈Al₁₀Cu₂₀Sn₂
4
>50%

Number	Name	Date	Kind
5362339	Horimura et al.	Nov 1994	A
6214480	Hosoe et al.	Apr 2001	B1

Ce-based amorphous metallic plastic

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