CN100447287C - New type zirconium-based amorphous alloy - Google Patents

New type zirconium-based amorphous alloy Download PDF

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Publication number
CN100447287C
CN100447287C CNB2007100634505A CN200710063450A CN100447287C CN 100447287 C CN100447287 C CN 100447287C CN B2007100634505 A CNB2007100634505 A CN B2007100634505A CN 200710063450 A CN200710063450 A CN 200710063450A CN 100447287 C CN100447287 C CN 100447287C
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alloy
metal bar
amorphous alloy
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amorphous metal
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CN101012534A (en
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张涛
傅军英
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Shenzhen xinkailai Technology Co.,Ltd.
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

Abstract

The invention discloses a zirconium-based non-crystal alloy, whose chemical formula is Zr50-xAl10Cu40REx, wherein RE is Y, La, Ce, Nd, Sm, Gd, Dy, Ho, Er, Tm, Lu and X (0<X<=10); when x is 2, 3, RE is Y, Er, Gd, Dy and Lu.

Description

A kind of Zirconium based amorphous alloy
Technical field
The present invention relates to amorphous alloy, particularly a kind of Zirconium based amorphous alloy.
Background technology
By the amorphous alloy of alloy from the preparation of the method for gaseous state or liquid rapid solidification, do not have the long-range atomic ordered, and has special amorphous structure, thereby make amorphous alloy have crystal alloy incomparable mechanical property, as high strength, high rigidity, snappiness, high fracture toughness property and anti-corrosion, wear resistance, has huge potential application foreground at space flight, aviation field and biomedical sector.The Zr base amorphous alloy has been successfully used to prepare golf club head, tennis racket and space flight solar wind collector and some other products with its high amorphous formation ability, good performance.Typical system has Zr-Ti-Ni-Cu-Be (A.Pekerand W.L.Johnson, Appl.Phys.Lett.63,2342 (1993) .), Zr-Al-Ni-Cu-RE (J.Luo, H.P.Duan, C.L.Ma, S.J.Pang and T.Zhang, Mater.Trans.JIM, 47 (2006), p.1), Zr-Cu-Ni-Al-Ti (X.H.Lin, W.L.Johnson, andW.K.Rhim, Mater.Trans., JIM 38,473 (1997) .), Zr-Al-Ni-Cu amorphous alloys such as (T.Zhang, A.Inoue and T.Masumoto:Mater.Trans.JIM 32 (1991) 1005-1010).These amorphous alloys all have higher amorphous formation ability, and critical size reaches tens even tens millimeters.
Up to now, in the block zirconium-base amorphous alloy of in world's research range, having developed, have in the alloy of high amorphous formation ability and all contain Ni, Be etc. mostly to the deleterious element of organism, this has just limited its application on biomaterial and medical device greatly.Therefore, exploitation had not only had high amorphous formation ability but also had not contained the alloy material of Ni, Be element, had been the inexorable trend of zirconium-base amorphous development that can widespread use.
Summary of the invention
One of purpose of the present invention provide a kind of can form large block amorphous, have a higher breaking tenacity and not containing again to the deleterious element Ni of biology, Be and amorphous alloy with good anti-corrosion, be specially: a kind of Zirconium based amorphous alloy is characterized in that the expression formula of alloying constituent is:
Zr 50-xAl 10Cu 40RE x, atom number %,
Wherein RE represents Y or La or Ce or Nd or Sm or Gd or Dy or Ho or Er or Tm or Lu;
X：0＜X≤10；
Wherein x is 2 or 3 according to qualifications; RE is Y or Er or Gd or Dy or Lu.
Unless it is clearly refer else, used herein: omnipotent test machine (mechanical testing system) hereinafter to be referred as having following implication: MTS; d c: the non-crystaline amorphous metal critical diameter; Tg: glass transformation temperature; Tx: Tc; Δ Tx: the interval Δ Tx of supercooled liquid (=Tx-Tg); σ y: yield strength; σ f: breaking tenacity; ε p: amount of plastic deformation; Φ: the diameter of amorphous alloy rod.
Realize technical scheme of the present invention:
Is the Metal Melting of certain ingredients proportioning mother alloy earlier, will be cast into metal die after the mother alloy remelting then and be frozen into amorphous alloy.Be specially:
Amorphous alloy of the present invention is prepared from by following method:
Step 1, take by weighing each element
Calculating each associated element wt by required atom number takes by weighing;
Step 2, melting system Zr-Al-Cu-RE mother alloy
The described batching that step 1 takes by weighing is put into vacuum smelting furnace, regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then; Regulate electric current 20A, 1000 ℃ of smelting temperatures; Take out the Zr-Al-Cu-RE mother alloy behind the smelting time 5-10min behind the furnace cooling;
Step 3, system Zr-Al-Cu-RE non-crystaline amorphous metal bar
The Zr-Al-Cu-RE mother alloy that step 2 is made is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then; Regulate electric current 2-10A, temperature sensor 700-1000 ℃;
Spray into behind the smelting time 2-5min (selecting the internal recess diameter respectively is the mould of 2～20mm) in the copper mold, with making Zr-Al-Cu-RE non-crystaline amorphous metal bar after the copper mold cooling.
Zr-Al-Cu-RE non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm with making tests its compression mechanical property, and the compression mechanical property of material adopts the MTS testing of equipment.
In the Zr-Al-Cu system, add rare earth element and can play and stablize the effect that liquid phase and oxygen uptake suppress heterogeneous forming core, can reduce its fusing point significantly, shortening fusing point T lWith glass transformation temperature T gBetween distance, make metal liquid in process of cooling, can keep the supercooled liquid state to pass through T fast lWith T gBetween temperature province, avoid crystallization, thereby make alloy have high glass forming ability and good thermostability.
Table 1 shows the thermodynamic property and the mechanical property of the part amorphous alloy rod of being cast.The supercooled liquid of Zr base amorphous alloy of the present invention has higher thermostability, the interval Δ Tx of supercooled liquid (=Tx-Tg)＞70K, critical size Φ＞the 15mm of the amorphous alloy that forms, the wideest Δ Tx is 124K, the compressed rupture strength of described alloy can reach more than the 2265MPa, the compressive plastic deformation amount can reach more than 2.3%, do not contain organism harmful element Ni and Be, have simultaneously high strength and high tenacity again, be easy to produce, can be widely used in making various structured materials, sports equipment, biomaterial and medical device.
The thermodynamic property and the mechanical property of the part amorphous alloy rod that table 1 is cast
Alloy d c/mm Tg Tx ΔTx σ y(MPa) σ f ε
(K) (K) (K) (MPa) (％)
Zr 50Al 10Cu 40 Zr 48Al 10Cu 40Y 2 Zr 49Al 10Cu 40Y 1 Zr 47Al 10Cu 40Y 3 Zr 46Al 10Cu 40Y 4 Zr 45Al 10Cu 40Y 5 Zr 48Al 10Cu 40La 2 Zr 48Al 10Cu 40Ce 2 Zr 48Al 10Cu 40Er 2 Zr 48Al 10Cu 40Dy 2 Zr 49Al 10Cu 40Dy 1 Zr 47Al 10Cu 40Dy 3 Zr 46Al 10Cu 40Dy 4 Zr 48Al 10Cu 40Gd 2 Zr 48Al 10Cu 40Sm 2 5 12 8 15 12 10 - - 10 10 8 15 15 12 - 675 644 668 677 661 662 673 668 652 646 668 664 773 768 770 767 763 762 763 753 761 767 770 751 98 124 102 90 102 100 90 85 109 121 102 87 1901 1841 1819 1869 1636 1584 1740 1710 1648 1711 1794 1685 1676 1814 1688 1919 1961 1888 1982 1755 1795 1892 1953 1879 1757 1723 1876 1887 0 2.3 1.2 1 1.1 0.9 0.9 0.85 0.2 0.13 0.14 0 1.6
Zr 48Al 10Cu 40Tm 2 Zr 48Al 10Cu 40Nd 2 Zr 48Al 10Cu 40Lu 2 - - 8 689 613 674 759 715 765 70 102 91 1487 1806 2070 1558 1836 2265 0.3 0 0.5
The present invention is further illustrated below by embodiment, but the present invention is not limited only to these embodiment.
Embodiment
Embodiment 1
Preparation Zr 47Al 10Cu 40Y 3The non-crystaline amorphous metal bar
Step 1: press Zr 47Al 10Cu 40Y 3The chemical ingredients proportioning is prepared burden;
Adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Cu and 99.9% rare earths material Y, be 47: 10: 40 according to the mol ratio of Zr: Al: Cu: Y: 3 ratio is prepared burden.
Step 2: system Zr 47Al 10Cu 40Y 3Mother alloy
The described batching that step 1 makes is put into vacuum smelting furnace,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1000 ℃ of smelting temperatures;
Take out Zr behind the furnace cooling behind the smelting time 5-10min 47Al 10Cu 40Y 3Mother alloy;
Step 3: system Zr 47Al 10Cu 40Y 3The non-crystaline amorphous metal bar
The described Zr that step 2 is made 47Al 10Cu 40Y 3Mother alloy is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then; Regulate electric current 2A, 850 ℃ of temperature sensors;
Spray into behind the smelting time 2-5min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～20mm), with making Zr after the copper mold cooling 47Al 10Cu 40Y 3The non-crystaline amorphous metal bar.This Zr 47Al 10Cu 40Y 3The maximum critical size of alloy is 15mm; With the Zr that makes 47Al 10Cu 40Y 3Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1869MPa, and breaking tenacity is 1982MPa, and amount of plastic deformation is 1%, and other performances are as shown in table 1.
Embodiment 2
Preparation Zr 48Al 10Cu 40Y 2The non-crystaline amorphous metal bar
Step 1: press Zr 48Al 10Cu 40Y 2The chemical ingredients proportioning is prepared burden.
Mol ratio according to Zr: Al: Cu: Y is 48: 10: 40: 2 proportional meter is calculated each associated element wt, and adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Cu and 99.9% rare earths material Y prepare burden.
Step 2: system Zr 48Al 10Cu 40Y 2Mother alloy
The batching of step 1 is put into vacuum smelting furnace; Successively vacuumize, regulate suction to 5 * 10 with mechanical pump and diffusion pump -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1000 ℃ of smelting temperatures; Take out Zr behind the furnace cooling behind the smelting time 5-10min 48Al 10Cu 40Y 2Mother alloy;
Step 3: system Zr 48Al 10Cu 40Y 2The non-crystaline amorphous metal bar
The Zr that step 2 is made 48Al 10Cu 40Y 2Mother alloy is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into argon shield gas, and argon pressure is 0.05MPa; Regulate electric current 2A, 860 ℃ of temperature sensors; Spurt into behind the smelting time 2-5min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～15mm), with making Zr after the copper mold cooling 48Al 10Cu 40Y 2The non-crystaline amorphous metal bar.This Zr 48Al 10Cu 40Y 2The maximum critical size of alloy is 12mm; With the Zr that makes 48Al 10Cu 40Y 2Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1841MPa, and breaking tenacity is 1961MPa, and amount of plastic deformation is 2.3%, and other performances are as shown in table 1.
Embodiment 3
Preparation Zr 47Al 10Cu 40Dy 3The non-crystaline amorphous metal bar
Step 1: press Zr 47Al 10Cu 40Dy 3The chemical ingredients proportioning is prepared burden
Adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Cu and 99.9% rare earths material Dy, be 47: 10: 40 according to the mol ratio of Zr: Al: Cu: Dy: 3 ratio is prepared burden.
Step 2: system Zr 47Al 10Cu 40Dy 3Mother alloy
The batching that step 1 makes is put into vacuum smelting furnace, regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1000 ℃ of smelting temperatures;
Take out Zr behind the furnace cooling behind the smelting time 5-10min 47Al 10Cu 40Dy 3Mother alloy;
Step 3: system Zr 47Al 10Cu 40Dy 3The non-crystaline amorphous metal bar
The described Zr that step 2 is made 47Al 10Cu 40Dy 3Mother alloy is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then; Regulate electric current 2A, 850 ℃ of temperature sensors;
Be injected into behind the smelting time 2-5min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～20mm), with making Zr after the copper mold cooling 47Al 10Cu 40Dy 3The non-crystaline amorphous metal bar.This Zr 47Al 10Cu 40Dy 3The maximum critical size of alloy is 15mm; With the Zr that makes 47Al 10Cu 40Dy 3Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1685MPa, and breaking tenacity is 1757MPa, and amount of plastic deformation is 0.13%, and other performances are as shown in table 1.
Embodiment 4
Preparation Zr 48Al 10Cu 40Lu 2The non-crystaline amorphous metal bar
Step 1: press Zr 48Al 10Cu 40Lu 2The chemical ingredients proportioning is prepared burden
Adopting purity is the Al of 99.9% Zr.99.9% and 99.9% Cu, and 99.9% Lu is 48: 10: 40 according to the mol ratio of Zr: Al: Cu: Lu: 2 ratio is prepared burden.
Step 2: system Zr 48Al 10Cu 40Lu 2Mother alloy
The described batching that step 1 makes is put into vacuum smelting furnace,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1000 ℃ of temperature sensors;
Take out Zr behind the furnace cooling behind the smelting time 5-10min 48Al 10Cu 40Lu 2Mother alloy;
Step 3: system Zr 48Al 10Cu 40Lu 2The non-crystaline amorphous metal bar
The described Zr that step 2 is made 48Al 10Cu 40Lu 2Mother alloy is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then; Regulate electric current 2A, 840 ℃ of temperature sensors;
Spray into behind the smelting time 2-5min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～10mm), with making Zr after the copper mold cooling 48Al 10Cu 40Lu 2The non-crystaline amorphous metal bar.This Zr 48Al 10Cu 40Lu 2The maximum critical size of alloy is 8mm; With the Zr that makes 48Al 10Cu 40Lu 2Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 2070MPa, and breaking tenacity is 2265MPa, and amount of plastic deformation is 0.5%, and other performances are as shown in table 1.
Embodiment 5
Preparation Zr 45Al 10Cu 40Y 5The non-crystaline amorphous metal bar:
Step 1: press Zr 45Al 10Cu 40Y 5The chemical ingredients proportioning is prepared burden.
Mol ratio according to Zr: Al: Cu: Y is 45: 10: 40: 5 proportional meter is calculated each associated element wt, and adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Cu and 99.9% rare earths material Y prepare burden.
Step 2: system Zr 45Al 10Cu 40Y 5Mother alloy.
The batching of step 1 is put into vacuum smelting furnace; Successively vacuumize, regulate suction to 5 * 10 with mechanical pump and diffusion pump -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1000 ℃ of smelting temperatures; Take out Zr behind the furnace cooling behind the smelting time 5-10min 45Al 10Cu 40Y 5Mother alloy;
Step 3: system Zr 45Al 10Cu 40Y 5The non-crystaline amorphous metal bar.
The Zr that step 2 is made 45Al 10Cu 40Y 5Mother alloy is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into argon shield gas, and argon pressure is 0.05MPa; Regulate electric current 2A, 860 ℃ of temperature sensors; Spurt into behind the smelting time 2-5min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～15mm), with making Zr after the copper mold cooling 45Al 10Cu 40Y 5The non-crystaline amorphous metal bar.This Zr 45Al 10Cu 40Y 5The maximum critical size of alloy is 10mm; With the Zr that makes 48Al 10Cu 40Y 2Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1584MPa, and breaking tenacity is 1789MPa, and amount of plastic deformation is 0.9%, and other performances are as shown in table 1.

Claims (3)

1, a kind of Zirconium based amorphous alloy is characterized in that the expression formula of alloying constituent is: Zr 50-xAl 10Cu 40RE x, atom number %, wherein: RE represents Y or La or Ce or Nd or Sm or Gd or Dy or Ho or Er or Tm or Lu; X is 0＜X≤10.
2, a kind of Zirconium based amorphous alloy as claimed in claim 1, wherein x is 2 or 3.
3, a kind of Zirconium based amorphous alloy as claimed in claim 1, wherein RE is Y or Er or Gd or Dy or Lu.
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CN102517525A (en) * 2011-12-31 2012-06-27 北京航空航天大学 Copper mould casting and ironing combined method for preparing corrosion-resistant Zr-based amorphous alloy
CN102965599A (en) * 2012-11-26 2013-03-13 华为技术有限公司 Zirconium-based amorphous alloy
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CN103484800B (en) * 2013-09-10 2015-12-09 黄利敏 A kind of zirconium-base amorphous alloy and preparation method thereof
CN104561842B (en) * 2013-10-28 2017-08-22 比亚迪股份有限公司 A kind of zirconium-base amorphous alloy and preparation method thereof
CN106947925A (en) * 2017-03-22 2017-07-14 中国科学院金属研究所 A kind of Zr base block amorphous alloys and its preparation method and application
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