CN101298650A - Ce-La-based block amorphous alloy - Google Patents
Ce-La-based block amorphous alloy Download PDFInfo
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- CN101298650A CN101298650A CNA2008100400174A CN200810040017A CN101298650A CN 101298650 A CN101298650 A CN 101298650A CN A2008100400174 A CNA2008100400174 A CN A2008100400174A CN 200810040017 A CN200810040017 A CN 200810040017A CN 101298650 A CN101298650 A CN 101298650A
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Abstract
The invention relates to a bulk Ce-La-base amorphous alloy, which takes two lanthanon of cerium (Ce) and lanthanum (La) as essential components and contains at least 50 percent of amorphous phase materials by volume. The composition of the bulk Ce-La-base amorphous alloy can be expressed by following formula: (Ce 1-x La x) a Ni b Al c, wherein, the x lies in a closed interval between 0.1 and 0.9, the a lies in a closed interval between 50 and 75, the b lies in a closed interval between 15 and 20, the c lies in a closed interval between 5 and 35, and the sum of a, b and c equals to 100. The bulk Ce-La-base amorphous alloy takes the radix of raw materials of industrial cerium and lanthanum, and does not require high purity, thus having lower cost in comparison with bulk noble-metal-base amorphous alloys. Simultaneously the bulk Ce-La-base amorphous alloy has low critical cooling rate and is easy to form amorphous alloys with larger size. The bulk Ce-La-base amorphous alloy has higher rupture strength and ultra-low elasticity modulus, is a soft amorphous alloy that is similar to polymerized substances, and has potential industrial application prospect in the fields of micro mechanism and precise instruments as well as micro and nano stamping materials, etc.
Description
Technical field
The present invention relates to a kind of bulk amorphous alloys, specifically, is a kind of Ce-La base large amorphous alloy with low melting point, high amorphous formation ability, high strength, low modulus, belongs to the non-crystaline amorphous metal technical field.
Background technology
Solid material generally is divided into crystal, quasicrystal and noncrystal three classes, and atomic arrangement is very regular in the ideal crystal, and main performance is that atomic arrangement has periodically, perhaps is called long-range order; Quasicrystal between crystal and noncrystal between, have the orientation preface of long-range and do not have the translation symmetry preface (periodically) of long-range; Noncrystal then is (it is generally acknowledged 10 of the unordered and short range order of long-range
-10Orderly in the m scope), be the very important unordered solid of a class, have thermodynamics metastable state structure.This constructional feature causes amorphous material to have physical properties and other a lot of unique chemical character such as power, heat, light, electricity, magnetic of the not available a lot of brilliances of general crystalline material.Therefore, the research of amorphous substance has become an important topic in material and the physical field.
In recent years, along with various science and technology development, people use formation theory, physics, chemistry, mechanics and the engineering of non-crystaline amorphous metal and have carried out deep research and discussion, thereby found multiple non-crystaline amorphous metal system, such as the Zr base, the Fe base, the Ti base, Cu base, Mg base, the Ce base, the Ni base, La bases etc. are because amorphous alloy has high strength, high tenacity, high soft magnetism and superior corrosion resistance energy, therefore non-crystaline amorphous metal has caused increasing concern as a kind of type material, and part is applied in the real life.
Ce-La base non-crystalline material is meant that with two kinds of rare earth element coexistences of Ce, La be the amorphous alloy material of matrix.The rare earth resources of China is extremely abundant, and its reserves account for the first in the world.So this is a kind of large block amorphous system that is well suited for the china natural resources characteristics.In addition, because the fusing point of Ce-La base alloy is generally lower, and under suboxide atmosphere, its material surface can generate survivable sull, thereby hinder further carrying out of oxidation, therefore in its industrial preparation process, needed plant and instrument is simple relatively, and each preparation process condition can be very not harsh.
Summary of the invention
Shortcomings such as it mainly is to be base with the noble metal that the present invention has overcome most of bulk amorphous alloy, and cost is higher, and the formation ability is low.At first seek cerium base large amorphous alloy with high formation ability from the dark eutectic composition of cerium nickel, substitute Ce by structural similitude atom La again, thereby formed a series of have low melting point, high amorphous formation ability, low modulus, high-intensity Ce-La base noncrystal alloys.
The technical solution adopted for the present invention to solve the technical problems is as follows:
A kind of Ce-La base large amorphous alloy is characterized in that, is to be main component with cerium, two kinds of rare earth elements of lanthanum, and composition can be used following formulate:
(Ce
1-xLa
x)
aNi
bAl
c
Wherein, 0.1≤x≤0.9,50≤a≤75,15≤b≤20,5≤c≤35, and a+b+c=100.
Above-mentioned Ce-La base large amorphous alloy, it is characterized in that, when seeking composition,, change the content of Al on this basis, and partly substitute similar atom Ce with La at first from the dark eutectic point (atomic percent of Ce and Ni is 78: 22) of Ce and Ni binary phase diagram.Composition can be used following formulate:
[(Ce
1-xLa
x)
0.78Ni
0.22]
dAl
c
0.1≤x≤0.9,65≤d≤95,5≤c≤35 wherein, c+d=100.
The material purity of component Ce, La, Ni and the Al of described non-crystaline amorphous metal is 99.5～99.999% (weight percents).
Described Ce-La base large amorphous alloy comprises at least 50% volume percent amorphous phase.
Above-mentioned Ce-La base noncrystal alloy specifically comprises the steps: by the preparation of this area ordinary person's known method
1) takes by weighing element: press general formula (Ce
1-xLa
x)
aNi
bAl
cConverting each atoms of elements consumption of non-crystaline amorphous metal of the present invention to quality takes by weighing.Each element surface polishes off and makes its rule of surface smooth oxide compound with file.Be accurate to during weighing ± 0.002g; Then raw material is put into the anti-oxidation of acetone, and in the ultrasonic cleaning instrument, cleaned 3 minutes;
2) preparation of mother alloy: each element of the Ce in the said components that takes by weighing, La, Ni and Al is placed in the crucible of electric arc furnace from top to bottom successively by the fusing point height.Be evacuated to 2 * 10
-3Below, charge into argon shield gas.And with electric arc with the raw material mixed smelting, in order to guarantee the homogeneity of mother alloy, the melt back 5 times at least of each ingot casting obtains mother alloy ingot after the cooling;
3) suction casting: with step 2) the mother alloy ingot refuse in electric arc furnace that makes, same argon gas atmosphere protection.After treating that mother alloy is melt into uniform liquid, utilize the absorbing and casting device in the electric arc furnace, rapidly the melt of mother alloy is inhaled the bar-shaped sample of formation in the copper mold of casting different inner diameters.
Use diamond slicing machine intercepting middle portion a bit of the bulk amorphous alloys of method for preparing, and polish the whole X ray phase structure test that is used for silicon carbide paper.Can find that can prepare large block amorphous greater than diameter 3mm by preparation method provided by the invention and composition, the part composition can obtain the non-crystaline amorphous metal bar of diameter greater than 5mm.
Sample thief centre 10-20mg when carrying out hot analytical test with differential scanning calorimeter (DSC), heating rate is 0.333K/S.Alloy among the present invention has the glass transformation temperature of 410K-470K, the crystallization temperature of 480K-540K, and the subregion reaches the above super wide supercooling liquid phase region of 90K.
Getting specification is that length-to-diameter ratio is 2: 1 a 2mm amorphous bar, carries out the quasistatic compression experiment, during strain rate during test 1 * 10
-3/ S.The result shows that this Ce-La base noncrystal alloy system not only has higher breaking tenacity 650MPa-900MPa, and has a lower Young's modulus, its Young's modulus (E) even be low to moderate 20GPa, in the bulk amorphous alloys that has been found that, be minimum, similar with the modulus value of amorphous carbon, and approach the modulus value of some amorphous polymers.
Ce-La base large amorphous alloy provided by the invention is compared with existing non-crystaline amorphous metal, and its excellent part is:
1, formation ability is strong.The critical cooling rate of this Ce-La base large amorphous alloy is low, 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 3mm in each dimension, and the part composition can also obtain the non-crystaline amorphous metal bar of diameter greater than 5mm.
2, cost is low.Cerium of the presently claimed invention, lanthanum are industrial starting material, and purity is 99.5%, and cost is large block amorphous lower than precious metal-based.And China's rare earth resources is abundant, so this is a kind of large block amorphous system that is well suited for the china natural resources characteristics.
3, excellent performance.Cerium lanthanum base noncrystal alloy provided by the invention has very low glass transformation temperature and wide supercooling liquid phase region, can be out of shape as thermoplastics in supercooling liquid phase region, the processing of shaping and the marking.Compression experiment has also shown higher breaking tenacity and ultralow Young's modulus, its Young's modulus is minimum in the bulk amorphous alloys that has been found that, therefore, Ce-La base large amorphous alloy provided by the invention is that a kind of elastic performance is similar to polymkeric substance " soft " non-crystaline amorphous metal, at micromechanics, fields such as precision instrument and micro-nano imprint material have the potential prospects for commercial application.
Description of drawings
Fig. 1 is embodiment 1 [(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The XRD figure of bulk amorphous alloys 5mm as cast condition pole.
Fig. 2 is embodiment 1 [(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The DSC curve of bulk amorphous alloys, heating rate are 0.333K/S.
Fig. 3 is embodiment 2[(Ce
0.5La
0.5)
0.78Ni
0.22]
80Al
20DSC curve and XRD figure, wherein the DSC heating rate is 0.333K/S, XRD is a 5mm as cast condition pole.
Fig. 4 is embodiment 1 [(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The stress-strain(ed) curve of bulk amorphous alloys.
Fig. 5 is embodiment 2 [(Ce
0.5La
0.5)
0.78Ni
0.22]
80Al
20The stress-strain(ed) curve of bulk amorphous alloys.
Fig. 6 is embodiment 3 (Ce
0.5La
0.5)
60Ni
15Al
25DSC curve and XRD figure, wherein the DSC heating rate is 0.333K/S, XRD is a 5mm as cast condition pole.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.
Embodiment 1[(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The series bulk amorphous alloys
According to preparation provided by the invention and testing method to [(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The amorphous formation ability of system, mechanical property is studied.0.1≤x≤0.9 wherein.
At first prepare burden, in the process of batching, convert quality to according to each atoms of elements consumption and take by weighing the common practise that this is this area according to the chemical ingredients proportioning.Be accurate to when taking by weighing ± 0.002g.Then raw material is put into acetone and cleaned 3 minutes at the ultrasonic cleaning instrument.Then Ce, La, Ni and each element of Al are placed in the crucible of electric arc furnace from top to bottom successively by the fusing point height.Be evacuated to 2 * 10
-3Below, charge into argon shield gas.And with electric arc with the raw material mixed smelting, in order to guarantee the homogeneity of mother alloy, the melt back 5 times at least of each ingot casting obtains mother alloy ingot after the cooling; Mother alloy is put on the copper mold of electric arc furnace, regulated vacuum tightness to 2 * 10 then
-3Below, charge into argon gas and make the air pressure of furnace chamber be slightly larger than normal atmosphere.Under the electric current of 60A, use the electrode striking, progressively regulate electric current to 200A, and after mother alloy is melt into uniform liquid, utilize the absorbing and casting device in the electric arc furnace, rapidly the melt of mother alloy is inhaled in the copper mold of casting different inner diameters, treat the copper mold cooling, obtain the bar-shaped sample of different amorphous, test its calorifics and mechanical property by the above-mentioned method that provides then.
Part is implemented the thermodynamic property of alloy and partial crit size referring to table 1.[(Ce as can be seen from the table
1-xLa
x)
78Ni
22]
75Al
25The reduction glass temperature T of bulk amorphous alloys system
RgGreater than 0.55, part reaches 0.58.Also between 0.39 to 0.43, these two glass forming abilities that are commonly used to judge non-crystaline amorphous metal understand that thus this example alloy system has very high glass forming ability to the vitrifying exponent gamma.This alloy system has low glass transformation temperature and good thermodynamic stability simultaneously, and the composition in the subregion has the super wide supercooled liquid tagma of big 90K.So alloy can just can be out of shape and be processed into needed amorphous alloy goods in lower temperature as thermoplastics, have the potential application prospect in fields such as micromachined and precision instruments.
Table 1 is prepared [(Ce
1-xLa
x)
0.78Ni
0.22]
75Al
25The thermodynamic property of bulk amorphous alloys and critical size
Annotate: 1) Dc---the critical size that records under this experiment condition, T
g---glass transformation temperature, T
x---crystallization temperature, T
l---liquidus temperature, Δ T
x---the supercooling liquid phase region width
2) T wherein
Rg=T
g/ T
l, γ=T
x/ (T
g+ T
l).
To implementing amorphous alloy component is [(Ce
0.8La
0.2)
0.78Ni
0.22]
75Al
25, [(Ce
0.5La
0.5)
0.78Ni
0.22]
75Al
25[(Ce
0.2La
0.8)
0.78Ni
0.22]
75Al
25Alloy carry out the test of mechanical property, the stress-strain(ed) curve of its compression process is as shown in Figure 4.The alloy of composition has higher breaking tenacity described in this embodiment as can be seen, has reached about 850MPa.And alloy has lower Young's modulus, and its Young's modulus (E) is low to moderate 23GPa, in the bulk amorphous alloys that has been found that, be minimum and the modulus value of amorphous carbon similar, and approach the modulus value of some amorphous polymers.Therefore, Ce-La base large amorphous alloy provided by the invention is that a kind of elastic performance is similar to polymkeric substance " soft " non-crystaline amorphous metal, so it has the potential industrial application value in micro-nano processing and impression materials.
Embodiment 2[(Ce
0.5La
0.5)
0.78Ni
0.22]
80Al
20Bulk amorphous alloys
Preparation method according to embodiment 1 is prepared [(Ce
0.5La
0.5)
0.78Ni
0.22]
80Al
20Bulk amorphous alloys.Becoming diameter by the suction cast is the pole of 5mm.Carry out the detection of calorifics and mechanical property then by above-mentioned testing method.
X-ray diffractogram as shown in Figure 3 (XRD) proves that the 5mm pole of this alloy is a complete amorphous.From thermogram shown in Figure 3 (DSC) as can be seen, its glass transformation temperature T
g, crystallization begins temperature T
xWith the supercooling liquid phase region width Delta T
xBe respectively 422K, 489K and 67K.Its glass transformation temperature is low than embodiment 1 described alloy, and the supercooling liquid phase region width of 67K illustrates that also this alloy also has thermostability preferably simultaneously.In addition, this alloy has higher reduction glass temperature T
RgWith the vitrifying exponent gamma, they are respectively 0.55 and 0.41.T
RgUsually can be used for judging the glass forming ability of non-crystaline amorphous metal with γ, therefore [(Ce as can be known
0.5La
0.5)
0.78Ni
0.22]
80Al
20Non-crystaline amorphous metal has stronger glass forming ability.
To implementing bulk amorphous alloys [(Ce
0.5La
0.5)
0.78Ni
0.22]
80Al
20Carry out the test of mechanical property, the stress-strain(ed) curve of its compression process as shown in Figure 5.The breaking tenacity of this alloy is 660MPa as can be seen, and is low than embodiment 1 described alloy.But its Young's modulus of elasticity (E) is also lower simultaneously, reaches 20GPa, is a kind of more non-crystaline amorphous metal of " soft ".
Embodiment 3 (Ce
0.5La
0.5)
60Ni
15Al
25Bulk amorphous alloys
Preparation method according to embodiment 1 is prepared (Ce
0.5La
0.5)
60Ni
15Al
25Bulk amorphous alloys.Becoming diameter by the suction cast is the pole of 5mm.Carry out the detection of calorifics and mechanical property then by above-mentioned testing method.
X-ray diffractogram as shown in Figure 6 (XRD) proves that the 5mm pole of this alloy is a complete amorphous.From thermogram shown in Figure 6 (DSC) as can be seen, its glass transformation temperature T
g, crystallization begins temperature T
xWith the supercooling liquid phase region width Delta T
xBe respectively 452.85K, 538.7K and 86K.Its glass transformation temperature and embodiment 1 described alloy phase are worked as, and are higher than embodiment 2.The super wide supercooling liquid phase region width of 86K illustrates that also this alloy also has good thermostability simultaneously.In addition, this alloy has higher reduction glass temperature T
RgWith the vitrifying exponent gamma, they are respectively 0.55 and 0.42.T
RgUsually can be used for judging the glass forming ability of non-crystaline amorphous metal with γ, therefore (Ce as can be known
0.5La
0.5)
60Ni
15Al
25Non-crystaline amorphous metal has stronger glass forming ability.
Claims (4)
1. Ce-La base large amorphous alloy is characterized in that the chemical constitution of this bulk amorphous alloys is as follows:
(Ce
1-xLa
x)
aNi
bAl
c, 0.1≤x≤0.9,50≤a≤75,15≤b≤20,5≤c≤35 wherein, a+b+c=100.
2. Ce-La base large amorphous alloy as claimed in claim 1 is characterized in that the chemical constitution of bulk amorphous alloys is: [(Ce
1-xLa
x)
0.78Ni
0.22]
dAl
c, 0.1≤x≤0.9,65≤d≤95,5≤c≤35 wherein, c+d=100.
3. Ce-La base large amorphous alloy as claimed in claim 1 or 2 is characterized in that: the weight percentage of the material purity of Ce, La, Ni and Al is 99.5～99.999%.
4. Ce-La base large amorphous alloy as claimed in claim 1 or 2 is characterized in that described Ce-La base large amorphous alloy comprises the amorphous phase of at least 50% volume percent.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952649A (en) * | 2014-05-16 | 2014-07-30 | 辽宁石化职业技术学院 | Magnesium-based amorphous solid and preparation method thereof |
| CN110681387A (en) * | 2019-10-24 | 2020-01-14 | 合肥工业大学 | Ce-based amorphous alloy-based nanocomposite and preparation method thereof and application of nanocomposite in treatment of dye wastewater |
-
2008
- 2008-07-01 CN CNA2008100400174A patent/CN101298650A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952649A (en) * | 2014-05-16 | 2014-07-30 | 辽宁石化职业技术学院 | Magnesium-based amorphous solid and preparation method thereof |
| CN110681387A (en) * | 2019-10-24 | 2020-01-14 | 合肥工业大学 | Ce-based amorphous alloy-based nanocomposite and preparation method thereof and application of nanocomposite in treatment of dye wastewater |
| CN110681387B (en) * | 2019-10-24 | 2022-03-22 | 合肥工业大学 | Ce-based amorphous alloy-based nanocomposite and preparation method thereof and application of nanocomposite in treatment of dye wastewater |
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