CN1294289C - Gadolinium-base block amorphous alloy and its preparing method - Google Patents

Gadolinium-base block amorphous alloy and its preparing method Download PDF

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CN1294289C
CN1294289C CNB2004100307656A CN200410030765A CN1294289C CN 1294289 C CN1294289 C CN 1294289C CN B2004100307656 A CNB2004100307656 A CN B2004100307656A CN 200410030765 A CN200410030765 A CN 200410030765A CN 1294289 C CN1294289 C CN 1294289C
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gadolinium
crystaline amorphous
based bulk
alloy
bulk non
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CN1676657A (en
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李松
赵德乾
潘明祥
汪卫华
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Institute of Physics of CAS
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Abstract

The present invention relates to a gadolinium base bulk amorphous alloy. Gadolinium is used as a main component, and the alloy comprises at least the volume percent of 50% of amorphous phases. The alloy has the compositions according to the formulation: GdaAlbNicCudMe, wherein a is more than or equal to 50 and at most 80, b is more than or equal to 5 and at most 20, c is more than or equal to 5 and at most 20, d is more than or equal to 5 and at most 20, e is more than or equal to 0 and at most 15, and the sum of a, b, c, d and e is 100; the transition group metallic element M is Sc, Nb, Ti, Cr, Mn, Fe, Co, Y, La, Pr, Nd or Hf. The alloy is prepared by the following steps: a master alloy cast ingot is obtained by smelting the components according to the required atomic proportion in an electric arc furnace with an argon atmosphere adsorbed by titanium; by a conventional metal mould casting method, the master alloy cast ingot is remelted, and melts are absorbed into a water-cooled copper mould, namely a suction mould device in the electric arc furnace. The alloy has the advantages of strong inhibition capability of crystallization, easy formation of amorphous alloys in a large size, simple preparation, low cost, favorable magnetic performance and favorable magneto-optical property, and can be used as functional materials.

Description

A kind of gadolinium-based bulk non-crystaline amorphous metal and preparation method thereof
Technical field
The present invention relates to a kind of alloy, specifically relating to a kind of is main component with the heavy rare earth element gadolinium, has added an amount of alloying element, and comprises the gadolinium-based bulk non-crystaline amorphous metal of at least 50% amorphous phase (volume percent).
Background technology
Usually, metal or alloy all can crystallization form crystal when liquid cooled is got off.Have now found that some metal or alloy is enough fast in rate of cooling, for example reach p.s. 10 4～10 6During the order of magnitude of K, the extreme viscid state in the time of when solidifying, can keeping liquid state, thus suppress crystallization, obtain the metal or alloy of amorphous phase.
But, in order to obtain so high rate of cooling, molten metal or alloy can only be sprayed onto on the extraordinary conductive substrate of heat conduction, the size of amorphous metal of Huo Deing or alloy is very little like this.For example, the melt alloy is ejected on the copper roller of high speed rotating, obtains strip, or be cast to and obtain thin slice and powder etc. in the cold substrate.
Each non-crystaline amorphous metal that forms is reheated second-order transition temperature (Tg) when above, and there is a humidity province that crystallization does not take place in non-crystaline amorphous metal before crystallization, be called supercooling liquid phase region (SLR).In general, supercooling liquid phase region is wide more, and the superplasticity working ability of amorphous is strong more.For the non-crystaline amorphous metal with good formation ability, people expect the crystallization curve to the right, promptly move to the longer time.The ability of non-crystaline amorphous metal opposing crystallization and alloy are relevant from the melt desired rate of cooling of formation amorphous that cools down, and this is a unordered mutually stable sign during more than the glass transformation temperature non-crystaline amorphous metal being processed.
It is enough low that we expect to suppress the crystalline rate of cooling, obtain larger sized bulk amorphous alloy and make before crystallization takes place, can obtain the longer processing treatment time, be that such bulk amorphous alloys can be under the situation that crystallization does not take place, fully be heated to more than the glass transformation temperature and process, make it be suitable for industrial use.
Bulk amorphous alloy is making a breakthrough aspect preparation and the performance study over past ten years.At present can be under lower rate of cooling, prepare the bulk amorphous alloy of multiple alloy system by ordinary process method such as die cast, shrend, containment heterogeneous nucleation, directional freeze, powder metallurgy, spray to cast shapings, compaction moulding etc.Bulk amorphous alloy is because its excellent mechanical property, good processing properties, excellent in chemical activity and magnetic performance demonstrate wide application prospect in civilian and military field.At present, people are constantly seeking the new system non-crystaline amorphous metal of high glass forming ability, but about the preparation and the performance study of rare-earth-base amorphous alloy also few, heavy rare earths non-crystaline amorphous metal particularly.And rare earth is as the important strategic resource, because its unique light, electricity and magnetic property are widely used in fields such as medical science, agricultural, metallurgy, chemical industry, oil, environmental protection and novel materials.Therefore, development rare earth based bulk amorphous alloy has wide potential application foreground.
Summary of the invention
The object of the present invention is to provide a kind ofly have high glass forming ability, suppress crystallizing power strong, can under very low rate of cooling, make larger sized, be the gadolinium-based bulk non-crystaline amorphous metal of metal matrix with the rare-earth element gadolinium.
Another object of the present invention is to provide a kind of preparation method of described gadolinium-based bulk non-crystaline amorphous metal.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of gadolinium-based bulk non-crystaline amorphous metal, is to be main component with the gadolinium, adds other alloying element, and it forms available following formulate:
Gd aAl bNi cCu d
Wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20, and a+b+c+d=100.
The purity of described Gd, Al, Ni and Cu element is not less than 99.5% (weight percent).
Described gadolinium-based bulk non-crystaline amorphous metal comprises at least 50% volume percent amorphous phase, and size is not less than 1 millimeter in each dimension.
Gadolinium-based bulk non-crystaline amorphous metal provided by the invention also comprises transiting group metal elements M, the available following formulate of the composition of alloy:
Gd aAl bNi cCu dM e
Wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20,0＜e≤15, and a+b+c+d+e=100.
Described transiting group metal elements M is Sc, Nb, Ti, Cr, Mn, Fe, Co, Y, La, Pr, Nd or Hf.The purity of described transiting group metal elements M is not less than 99.5% (weight percent).
The invention provides a kind of preparation method of above-mentioned gadolinium-based bulk non-crystaline amorphous metal, comprise the steps:
1) in the electric arc furnace of the argon atmospher that titanium adsorbs, by needed atom proportioning said components Gd, Cu, Ni and Al are mixed, melting obtains mother alloy ingot after the cooling;
2) use conventional permanent mold casting method, the mother alloy ingot refuse with step 1) makes utilizes the absorbing and casting device in the electric arc furnace, and the melt suction water cooled copper mould with mother alloy obtains gadolinium-based bulk non-crystaline amorphous metal Gd aAl bNi cCu d
The preparation method of above-mentioned gadolinium-based bulk non-crystaline amorphous metal provided by the invention also comprises: in step 1) with the transiting group metal elements M of needed atom proportioning with Gd, Al, Cu and Ni melting.
Described transiting group metal elements M is Sc, Nb, Ti, Cr, Mn, Fe, Co, Y, La, Pr, Nd or Hf.
Gadolinium-based bulk non-crystaline amorphous metal provided by the invention has high glass forming ability, and its crystallization temperature is about 450～580K, and glass transformation temperature is about 500～550K, and the width of supercooling liquid phase region is between 25～75K.
Gadolinium-based bulk non-crystaline amorphous metal provided by the invention is compared with existing non-crystaline amorphous metal, and its advantage is:
1, the critical cooling rate of this gadolinium-based bulk non-crystaline amorphous metal is low, and rate of cooling (Rc) can reach 10 2The order of magnitude of K/s, 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 1.5mm;
2, cost is low.China's rare earth resources is abundant, and the preparation of rare earth gadolinium is simple, so be a kind of large block amorphous system that is well suited for the china natural resources characteristics.
Description of drawings
Fig. 1 is the non-crystaline amorphous metal Gd of the embodiment of the invention 1 60Cu 20Al 10Ni 10X-ray diffraction analysis spectrum;
Fig. 2 is the non-crystaline amorphous metal Gd of the embodiment of the invention 1 60Cu 20Al 10Ni 10DSC and DTA graphic representation.
Embodiment
Embodiment 1, Gd 60Cu 20Al 10Ni 10The preparation of bulk amorphous alloys
Use purity is that the molar weight ratio more than 99.9% is 60: 20: 10: 10 Gd, Cu, Al and Ni prepare the gadolinium-based bulk non-crystaline amorphous metal, at first four kinds of components are prepared in proportion back melting in the electric arc furnace of the argon atmospher of titanium absorption, mix, obtain the mother alloy ingot of Gd-Cu-Al-Ni quad alloy after the cooling; Use conventional metal mould cast method then, with this ingot casting refuse, utilize the absorbing and casting device in the electric arc furnace, the mother alloy melt is sucked water cooled copper mould, obtaining composition is Gd 60Cu 20Al 10Ni 10, diameter is the block amorphous alloy of 1.5mm.
X-ray diffraction as shown in Figure 1 (XRD) proves that this alloy is amorphous completely.Heat analysis (DSC) figure as shown in Figure 2, its second-order transition temperature (T g), crystallization begins temperature (T x), cross width (the Δ T=T between the cold-zone x-T g) be respectively 481K, 514K and 33K.In addition, this alloy also has higher reduction glass temperature (T Rg) and vitrifying index (γ), they are respectively 0.55 and 0.366.T RgUsually can be used for judging the glass forming ability of non-crystaline amorphous metal with γ, therefore Gd as can be known 60Al 10Ni 10Cu 20Non-crystaline amorphous metal has bigger glass forming ability.
Embodiment 2～19
Prepare the gadolinium-based bulk non-crystaline amorphous metal of various proportionings by the method for embodiment 1, it is formed and thermal physical property parameter is listed in table 1.
The composition of table 1, gadolinium-based bulk non-crystaline amorphous metal and thermal physical property parameter
Embodiment Alloying constituent T g (K) T x (K) ΔT (K) T m (K) T l (K) T rg γ
1 Gd 60Cu 20Al 10Ni 10 481 514 33 880 925 0.55 0.366
2 Gd 60Cu 10Al 10Ni 10Fe 10 498 538 39 897 931 0.567 0.340
3 Gd 60Cu 15Al 5Ni 10Fe 10 520 557 37 910 945 0.571 0.380
4 Gd 60Al 15Ni 15Cu 10 477 516 39 871 913 0.547 0.371
5 Gd 65Al 10Ni 10Cu 10Nb 5 488 523 35 869 907 0.562 0.375
6 Gd 60Al 10Ni 10Cu 10Sc 10 505 549 44 870 905 0.580 0.389
7 Gd 60Al 10Ni 10Cu 15Ti 5 491 529 38 877 911 0.560 0.377
8 Gd 60Al 10Ni 12Cu 16Cr 2 514 551 37 892 930 0.576 0.382
9 Gd 58Al 10Ni 12Cu 15Mn 5 501 543 42 901 942 0.556 0.376
10 Gd 61Al 10Ni 12.5Cu 15.5Fe 1 491 527 36 892 933 0.55 0.370
11 Gd 62Al 10Ni 12.5Cu 15.5Co 1 475 511 36 877 922 0.542 0.366
12 Gd 57Al 10Ni 12.5Cu 15.5Y 5 501 535 34 899 944 0.557 0.370
13 Gd 60Al 10Ni 12.5Cu 15.5Nb 2 511 549 38 907 951 0.563 0.376
14 Gd 57Al 10Ni 12.5Cu 15.5La 5 477 511 34 878 921 0.543 0.366
15 Gd 57Al 10Ni 12.5Cu 15.5Pr 5 486 521 35 889 933 0.547 0.367
16 Gd 57Al 10Ni 12.5Cu 15.5Nd 5 521 561 40 893 936 0.583 0.385
17 Gd 57Al 10Ni 12.5Cu 15.5Hf 5 469 502 33 864 910 0.543 0.364
18 Gd 80Al 10Ni 5Cu 5 489 526 37 892 922 0.548 0.373
19 Gd 50Al 20Ni 20Cu 10 483 502 29 866 900 0.558 0.363
Annotate: 1) T wherein Rg=T g/ T m, γ=T x/ (T g+ T l), D cBe the critical size under this experiment condition.
2) in the table during each composition sample measurement used heating rate be 10K/min.
The desired gadolinium of gadolinium-based bulk non-crystaline amorphous metal provided by the invention is industrial starting material, and its purity is 99.5%, and by contrast, its cost is lower than other precious metal-based.And China is rare earth big country, and the Mineral resources that contain gadolinium are very abundant, so development gadolinium-based bulk non-crystaline amorphous metal is very suitable for the china natural resources characteristics.Because the gadolinium element has special electronic structure, its compound has peculiar magnetic and magneto-optical property, be widely used in preparing functional materials, and gadolinium base noncrystal alloy structure is different from crystalline structure, therefore has the potential application prospect.

Claims (10)

1, a kind of gadolinium-based bulk non-crystaline amorphous metal is characterized in that: this alloy is to be main component with the gadolinium, shown in its formula composed as follows:
Gd aAl bNi cCu d
Wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20, and a+b+c+d=100.
2, gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 1 is characterized in that, the purity of described Gd, Al, Ni and Cu element all is not less than 99.5wt%.
3, gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 1 is characterized in that, described gadolinium-based bulk non-crystaline amorphous metal comprises at least 50% volume percent amorphous phase.
4, as claim 1,2 or 3 described gadolinium-based bulk non-crystaline amorphous metals, it is characterized in that described gadolinium-based bulk non-crystaline amorphous metal also comprises transiting group metal elements M, shown in the formula composed as follows of alloy:
Gd aAl bNi cCu dM e
Wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20,0＜e≤15, and a+b+c+d+e=100.
5, gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 4 is characterized in that, described transiting group metal elements M is Sc, Nb, Ti, Cr, Mn, Fe, Co, Y, La, Pr, Nd or Hf.
6, gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 4 is characterized in that, the purity of described transiting group metal elements M is not less than 99.5wt%.
7, the preparation method of the described gadolinium-based bulk non-crystaline amorphous metal of a kind of claim 1 is characterized in that comprising the steps:
According to Gd aAl bNi cCu d, the ratio of wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20, and a+b+c+d=100 is prepared raw material;
1) in the electric arc furnace of the argon atmospher that titanium adsorbs, by needed atom proportioning the Gd in the above-mentioned component, Al, Cu and Ni are mixed, melting obtains mother alloy ingot after the cooling;
2) inhale casting: use conventional permanent mold casting method, the mother alloy ingot refuse with step 1) makes utilizes the absorbing and casting device in the electric arc furnace, and the melt suction water cooled copper mould with mother alloy obtains the gadolinium-based bulk non-crystaline amorphous metal.
8, the preparation method of gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 7 is characterized in that: described preparation method also comprises:
According to Gd aAl bNi cCu dM e, the ratio of wherein 50≤a≤80,5≤b≤20,5≤c≤20,5≤d≤20,0＜e≤15, and a+b+c+d+e=100 is prepared raw material;
In step 1) with the transiting group metal elements M of needed atom proportioning with Gd, Al, Cu and Ni melting.
9, the preparation method of gadolinium-based bulk non-crystaline amorphous metal as claimed in claim 8 is characterized in that, described transiting group metal elements M is Sc, Nb, Ti, Cr, Mn, Fe, Co, Y, La, Pr, Nd or Hf.
10, as claim 7,8 or 9 described gadolinium-based bulk non-crystaline amorphous metals, it is characterized in that the purity of described Gd, Al, Ni, Cu element and transiting group metal elements M all is not less than 99.5wt%.
CNB2004100307656A 2004-04-02 2004-04-02 Gadolinium-base block amorphous alloy and its preparing method Expired - Fee Related CN1294289C (en)

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CN100453687C (en) * 2005-12-14 2009-01-21 中国科学院物理研究所 Nickle-based block metal glass and its production
CN102290183A (en) * 2011-05-04 2011-12-21 上海大学 Fe-based bulk permanent magnet alloy with excellent coercive force and preparation method thereof
CN116445833A (en) * 2021-12-21 2023-07-18 东莞市逸昊金属材料科技有限公司 Amorphous alloy, alloy preparation method and alloy part
CN116926394B (en) * 2023-09-18 2023-12-08 有研资源环境技术研究院(北京)有限公司 Gadolinium-niobium alloy belt with high neutron absorptivity, and preparation method and application thereof

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CN1332261A (en) * 2001-07-12 2002-01-23 四川大学 Magnetic rare earth-gadolinium refrigerating alloy

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CN1332261A (en) * 2001-07-12 2002-01-23 四川大学 Magnetic rare earth-gadolinium refrigerating alloy

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