CN101161851A - Zr-Al-Co-RE-Cu amorphous alloy - Google Patents

Zr-Al-Co-RE-Cu amorphous alloy Download PDF

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CN101161851A
CN101161851A CNA2007101785697A CN200710178569A CN101161851A CN 101161851 A CN101161851 A CN 101161851A CN A2007101785697 A CNA2007101785697 A CN A2007101785697A CN 200710178569 A CN200710178569 A CN 200710178569A CN 101161851 A CN101161851 A CN 101161851A
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amorphous metal
crystaline amorphous
alloy
smelting
crystaline
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张涛
郭瑶峰
逄淑杰
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Beihang University
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Beihang University
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Abstract

The invention discloses a Zr-Al-Co-RE-Cu amorphous alloy. The composition of the alloy is Zr49Al20Co25-xRE6Cux, wherein, x equals 1 to 8 at percent, and RE is ER or Y of lanthanon. The alloy reduces the content of the element of Co by adding the element of Cu, which effectively improves the mechanical property of the Zr-Al-Co-RE-Er amorphous alloy. The lanthanon RE adopts the element of Y in the Zr-Al-Co-RE-Cu amorphous alloy, which effectively increases the amorphous forming ability of the Zr-Al-Co-RE-Er alloy. The Zr-Al-Co-RE-Cu amorphous alloy of the invention has strong amorphous forming ability, good inoxidability, and high rupture strength and plasticity.

Description

A kind of Zr-Al-Co-RE-Cu non-crystaline amorphous metal
Technical field
The present invention relates to a kind of zirconium-base amorphous alloy, more particularly, be meant a kind of Zr-Al-Co-RE-Cu non-crystaline amorphous metal.
Background technology
Block amorphous alloy is because of its unique microtexture, have crystal alloy incomparable performance, as high strength, high rigidity, snappiness, high fracture toughness property and corrosion-resistant, wear resistance, thereby have huge potential application foreground.Zirconium-base amorphous alloy has the potential using value owing to have high amorphous formation ability, big sub-cooled liquid temperature interval, low Young's modulus and superior corrosion resistance energy aspect bio-medical material.Typical zirconium-base amorphous alloy system has Zr-Ti-Cu-Ni-Be, Zr-Al-Ni-Cu-RE (rare earth), Zr-Al-Ni-Cu etc.These non-crystaline amorphous metals all have higher amorphous formation ability, its critical size reaches tens even tens millimeters, but their breaking tenacity is lower, and all contains high bio-toxicity element Ni, Be mostly, has limited their application on bio-medical material greatly.Therefore, developing that breaking tenacity height, viscous deformation are good, excellent anti-corrosion performance and do not contain the block zirconium-base amorphous alloy material of high bio-toxicity element Ni, Be, has been zirconium-base amorphous inexorable trend that can the widespread use development.
A kind of Zr is disclosed in publication number CN101003884A 55-x-Al 20-Co 25-Er xZirconium-base amorphous alloy, this alloy are during as bio-medical material, and the erosion resistance under its room temperature awaits improving.
Summary of the invention
The purpose of this invention is to provide a kind of Zr-Al-Co-RE-Cu non-crystaline amorphous metal, this alloy has improved the mechanical property of Zr-Al-Co-Er non-crystaline amorphous metal effectively by adding the content that Cu unit usually reduces the Co element.Adopt Y element in Zr-Al-Co-RE-Cu non-crystaline amorphous metal middle-weight rare earths elements RE, improved the amorphous formation ability of Zr-Al-Co-Er alloy effectively.The Zr-Al-Co-RE-Cu non-crystaline amorphous metal that the present invention makes has high amorphous formation ability, good corrosion resistance energy, and higher breaking tenacity and plasticity.
Zr-Al-Co-RE-Cu amorphous alloy component expression formula of the present invention is Zr 49Al 20Co 25-xRE 6Cu x, wherein x=1～8at%, and RE is Er or the Y in the rare earth element.
The characteristics of Zr-Al-Co-RE-Cu non-crystaline amorphous metal of the present invention: the interpolation of Cu element makes the further diversification of alloy of the present invention, has suppressed the crystallization of alloy melt in process of setting.The interpolation of rare earth element er or Y and Cu element makes that element atom size difference is more remarkable in this non-crystaline amorphous metal, and the atomic radius of alloy constituent element is followed successively by Y (1.80 )＞Er (1.757 )＞Zr (1.58 )＞Al (1.43 )＞Co (1.28 )＞Cu (1.27 ); Simultaneously, containing in the alloy of rare earth element er or Y and Cu has increased Er-Al, Er-Co, Y-Al, Y-Co, Y-Cu and the Zr-Cu atom pairs with bigger negative enthalpy of mixing again, enthalpy of mixing is respectively-38kJ ,-24kJ ,-38kJ ,-22KJ ,-22KJ and-23kJ.According to the composition experience criterion of the alloy with high amorphous formation ability, the Zr-Al-Co-RE-Cu alloy that is obtained forms finer and close unordered packed structures easily, improves the solid-liquid phase interface energy of alloy, thereby suppresses the forming core of crystalline state phase.In addition, the unordered packed structures of this densification makes alloy at supercooled liquid very big viscosity be arranged, and has increased the difficulty of constituent element atom long-range diffusion, thereby has suppressed crystallization, has improved amorphous formation ability.
Description of drawings
Fig. 1 is Zr 49Al 20Co 25-xEr 6Cu xNon-crystaline amorphous metal is at 1N H 2SO 4Anodic polarization curves in the solution.
Fig. 2 is Zr 49Al 20Co 25-xEr 6Cu xThe anodic polarization curves of non-crystaline amorphous metal in 3%NaCl solution.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Zr-Al-Co-RE-Cu amorphous alloy component expression formula of the present invention is Zr 49Al 20Co 25-xRE 6Cu x, wherein x=1～8at%, and RE is Er or the Y in the rare earth element.
Zr-Al-Co-RE-Cu non-crystaline amorphous metal of the present invention is prepared from by following method:
Step 1, take by weighing each element
The quality that calculates each associated element by required atomic percent takes by weighing;
Step 2, melting system Zr-Al-Co-RE-Cu mother alloy
With step 1 claim desired raw material put into vacuum smelting furnace, regulate suction to 5 * 10 -3Pa charges into argon shield gas, argon pressure is 0.05MPa; Melting is 3～5 times under 1000～1600 ℃ of conditions of smelting temperature, takes out the Zr-Al-Co-RE-Cu mother alloy behind the furnace cooling;
Step 3, system Zr-Al-Co-RE-Cu non-crystaline amorphous metal bar
The 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 argon shield gas, argon pressure is 0.05MPa; Behind 1100～1500 ℃ of smelting temperatures, smelting time 2～5min, spurt in the copper mold, and make Zr-Al-Co-RE-Cu non-crystaline amorphous metal bar with the copper mold cooling.
The performance test of Zr-Al-Co-RE-Cu non-crystaline amorphous metal:
(1) the Zr-Al-Co-RE-Cu non-crystaline amorphous metal that will adopt aforesaid method to make adopts Sans-MTS equipment to compress Mechanics Performance Testing.
(2) the Zr-Al-Co-RE-Cu non-crystaline amorphous metal that will adopt aforesaid method to make adopts the HXZ-1000 hardness-testing device to measure vickers microhardness, and load is 50g, and the loading time is 10s.
(3) the Zr-Al-Co-RE-Cu non-crystaline amorphous metal that will adopt aforesaid method to make adopts VersaStatII electrochemical workstation and three-electrode system to study it at 1N H 2SO 4, the corrosion behavior in the 3%NaCl solution, as counter electrode, reference electrode is a saturated calomel electrode with Pt.Place solution to treat that open circuit potential stablizes (after about 20 minutes) in sample, measure anodic polarization curves, potential scanning speed is 50mV/min.
Embodiment 1:System Zr 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal
Step 1: press Zr 49Al 20Co 23Er 6Cu 2The chemical ingredients proportioning is prepared burden
Mol ratio according to Zr: Al: Co: Er: Cu is 49: 20: 23: 6: 2 proportional meter is calculated the quality of each associated element, employing purity is 99.9% Zr, 99.9% Al, 99.9% Co, 99.9% rare earth element er and 99.9% Cu prepare burden;
Step 2: preparation Zr 49Al 20Co 23Er 6Cu 2Mother alloy
The batching of step 1 is put into vacuum smelting furnace (a day new skill is ground the New-ADR05 model vacuum smelting furnace of production);
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas;
After 1100 ℃ of following meltings of smelting temperature 3 times, take out;
Step 3: preparation Zr 49Al 20Co 23Er 6Cu 2The non-crystaline amorphous metal bar
The Zr that step 2 is made 49Al 20Co 23Er 6Cu 2Mother alloy is put into the induction furnace (a day new skill is ground the New-A 05 model induction furnace of production) of quick solidification apparatus;
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas;
Behind 1100 ℃ of following smelting time 2min of smelting temperature, spurt in the copper mold (selecting the internal recess diameter respectively is the mould of 2～6mm), with making Zr after the copper mold cooling 49Al 20Co 23Er 6Cu 2The non-crystaline amorphous metal bar.
(1) Zr that makes 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal intercepting φ 2mm * 4mm adopts Sans-MTS equipment to compress Mechanics Performance Testing: the plastix strain (ε of non-crystaline amorphous metal p) be 1.5%, yield strength (σ y) be 1880MPa, compressed rupture strength (σ f) be 1950MPa.
(2) Zr that makes 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal adopts the HXZ-1000 hardness-testing device to measure vickers microhardness (H v) be 662.
(3) Zr that makes 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal adopts VersaStat II electrochemical workstation and three-electrode system to study it at 1N H 2SO 4, the corrosion behavior in the 3%NaCl solution, as counter electrode, reference electrode is a saturated calomel electrode with Pt.Place solution to treat that open circuit potential stablizes (after about 20 minutes) in sample, measure anodic polarization curves, potential scanning speed is 50mV/min.Referring to Fig. 1, shown in Figure 2, record Zr 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal is at 1N H 2SO 4Be about 3 * 10 respectively with the passivation current density in the 3%NaCl solution -2A/m 2, 1 * 10 -2A/m 2
The Zr that adopts the method identical to make with embodiment 1 49Al 20Co 25Er 6Non-crystaline amorphous metal, its plastix strain (ε p) be 0, compressed rupture strength (σ f) be 1770 MPa; Vickers microhardness (H v) be 536; At 1N H 2SO 4Be respectively 4.0 * 10 with the passivation current density in the 3%NaCl solution -2A/m 2, 2.0 * 10 -2A/m 2
The comparison of through performance test helps the improvement of mechanical property and the raising of corrosion resistance nature with the Co element of proper C u element substitution Zr-Al-Co-Er alloy.
Embodiment 2:System Zr 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal
Step 1: press Zr 49Al 20Co 17Er 6Cu 8The chemical ingredients proportioning is prepared burden.
Mol ratio according to Zr: Al: Co: Er: Cu is 49: 20: 17: 6: 8 proportional meter is calculated the quality of each associated element, employing purity is 99.9% Zr, 99.9% Al, 99.9% Co, 99.9% rare earth element er and 99.9% Cu prepare burden.
Step 2: preparation Zr 49Al 20Co 17Er 6Cu 8Mother alloy.
The batching of step 1 is put into vacuum smelting furnace;
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas;
Behind 3 times furnace cooling of 1300 ℃ of following meltings of smelting temperature, take out;
Step 3: preparation Zr 49Al 20Co 17Er 6Cu 8The non-crystaline amorphous metal bar.
The Zr that step 2 is made 49Al 20Co 17Er 6Cu 8Mother alloy is put into the induction furnace of quick solidification apparatus,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas;
Under 1300 ℃ of smelting temperatures, spurt in the copper mold behind the smelting time 2min, with making Zr after the copper mold cooling 49Al 20Co 17Er 6Cu 8The non-crystaline amorphous metal bar.
(1) Zr that makes 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal intercepting φ 2mm * 4mm adopts Sans-MTS equipment to compress Mechanics Performance Testing: the plastix strain (ε of non-crystaline amorphous metal p) be 0.5%, yield strength (σ y) be 1750MPa, compressed rupture strength (σ f) be 1780MPa.
(2) Zr that makes 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal adopts the HXZ-1000 hardness-testing device to measure vickers microhardness (H v) be 568.
(3) Zr that makes 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal adopts VersaStat II electrochemical workstation and three-electrode system to study it at 1N H 2SO 4, the corrosion behavior in the 3%NaCl solution, as counter electrode, reference electrode is a saturated calomel electrode with Pt.Place solution to treat that open circuit potential stablizes (after about 20 minutes) in sample, measure anodic polarization curves, potential scanning speed is 50mV/min.Referring to Fig. 1, shown in Figure 2, record Zr 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal is at 1N H 2SO 4Be about 2 * 10 respectively with the passivation current density in the 3%NaCl solution -2A/m 2, 1 * 10 -2A/m 2
Embodiment 3:System Zr 49Al 20Co 23Y 6Cu 2Non-crystaline amorphous metal
Step 1: press Zr 49Al 20Co 23Y 6Cu 2The chemical ingredients proportioning is prepared burden
Mol ratio according to Zr: Al: Co: Y: Cu is 49: 20: 23: 6: 2 proportional meter is calculated the quality of each associated element, employing purity is 99.9% Zr, 99.9% Al, 99.9% Co, 99.9% rare earth element y and 99.9% Cu prepare burden.
Step 2: preparation Zr 49Al 20Co 23Y 6Cu 2Mother alloy
The batching of step 1 is put into vacuum smelting furnace;
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas;
Behind 4 times furnace cooling of 1150 ℃ of following meltings of smelting temperature, take out;
Step 3: preparation Zr 49Al 20Co 23Y 6Cu 2The non-crystaline amorphous metal bar
The Zr that step 2 is made 49Al 20Co 23Y 6Cu 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;
Behind 1150 ℃ of following smelting time 5min of smelting temperature, spurt in the copper mold, with making Zr after the copper mold cooling 49Al 20Co 23Y 6Cu 2The non-crystaline amorphous metal bar.
(1) Zr that makes 49Al 20Co 23Y 6Cu 2Non-crystaline amorphous metal intercepting φ 2mm * 4mm adopts Sans-MTS equipment to compress Mechanics Performance Testing: the plastix strain (ε of non-crystaline amorphous metal p) be 0.9%, yield strength (σ y) be 1810MPa, compressed rupture strength (σ f) be 1910MPa.
(2) Zr that makes 49Al 20Co 23Y 6Cu 2Non-crystaline amorphous metal adopts the HXZ-1000 hardness-testing device to measure vickers microhardness (H v) be 656.
Adopt the preparation method identical, make the Zr of different Cu content with embodiment 1 49Al 20Co 25-xRE 6Cu xNon-crystaline amorphous metal, its performance is shown in Table 1:
Alloying constituent d c (mm) T g(℃) T x (℃) ΔT x (℃) σ y(MPa) σ f (MPa) ε p (％)
Zr 49Al 20Co 21Er 6Cu 4 5 447 505 58 1850 1910 0.8
Zr 49Al 20Co 19Er 6Cu 6 5 447 503 56 1770 1810 0.5
Zr 49Al 20Co 20Er 6Cu 5 4 445 505 60 1810 1900 0.9
Zr 49Al 20Co 24Y 6Cu 1 5 447 508 61 1790 1880 0.5
Zr 49Al 20Co 21Y 6Cu 4 6 452 507 55 1870 1900 0.8
Zr 49Al 20Co 19Y 6Cu 6 6 457 522 65 1850 1870 0.5
Zr 49Al 20Co 17Y 6Cu 8 6 437 502 65 1790 1850 0.5
Annotate: d cExpression amorphous alloy rod critical diameter; T gThe expression second-order transition temperature; T xThe expression Tc; Δ T xExpression supercooled liquid interval, and Δ T x=T x-T gσ yThe expression yield strength; σ fThe expression breaking tenacity; ε pThe expression amount of plastic deformation.
The interpolation of Cu element makes the further diversification of alloy of the present invention in the Zr-Al-Co-RE-Cu non-crystaline amorphous metal of the present invention, has suppressed the crystallization of alloy melt in process of setting.The interpolation of rare earth element er or Y and Cu element makes that element atom size difference is more remarkable in this non-crystaline amorphous metal, and the atomic radius of alloy constituent element is followed successively by Y (1.80 )＞Er (1.757 )＞Zr (1.58 )＞Al (1.43 )＞Co (1.28 )＞Cu (1.27 ); Simultaneously, containing in the alloy of rare earth element er or Y and Cu has increased Er-Al, Er-Co, Y-Al, Y-Co, Y-Cu and the Zr-Cu atom pairs with bigger negative enthalpy of mixing again, enthalpy of mixing is respectively-38kJ ,-24kJ ,-38kJ ,-22kJ ,-22kJ and-23kJ.According to the composition experience criterion of the alloy with high amorphous formation ability, the Zr-Al-Co-RE-Cu alloy that is obtained forms finer and close unordered packed structures easily, improves the solid-liquid phase interface energy of alloy, thereby suppresses the forming core of crystalline state phase.In addition, the unordered packed structures of this densification makes alloy at supercooled liquid very big viscosity be arranged, and has increased the difficulty of constituent element atom long-range diffusion, thereby has suppressed crystallization, has improved amorphous formation ability.

Claims (6)

1. Zr-Al-Co-RE-Cu non-crystaline amorphous metal is characterized in that:
Alloying constituent is Zr 49Al 20Co 25-xRE 6Cu x, wherein x=1～8 at%, and RE are Er or the Y in the rare earth element.
2. Zr-Al-Co-RE-Cu non-crystaline amorphous metal according to claim 1 is characterized in that: Zr is arranged 49Al 20Co 23Er 6Cu 2Non-crystaline amorphous metal, Zr 49Al 20Co 20Er 6Cu 5Non-crystaline amorphous metal, Zr 49Al 20Co 17Er 6Cu 8Non-crystaline amorphous metal, Zr 49Al 20Co 23Y 6Cu 2Non-crystaline amorphous metal or Zr 49Al 20Co 21Y 6Cu 4Non-crystaline amorphous metal.
3. Zr-Al-Co-RE-Cu non-crystaline amorphous metal according to claim 1 is characterized in that: the plastix strain (ε of non-crystaline amorphous metal p) be 0.5～1.5%, yield strength (σ y) be 1750～1900 MPa, compressed rupture strength (σ f) be 1750～2000MPa.
4. Zr-Al-Co-RE-Cu non-crystaline amorphous metal according to claim 1 is characterized in that: vickers microhardness (H v) be 565～670.
5. Zr-Al-Co-Er-Cu non-crystaline amorphous metal according to claim 1 is characterized in that: at 1N H 2S0 4Be respectively 2.0 * 10 with the passivation current density in the 3%NaCl solution -2～4.0 * 10 -2A/m 2, 7.0 * 10 -3～2.5 * 10 -2A/m 2
6. method for preparing Zr-Al-Co-RE-Cu non-crystaline amorphous metal as claimed in claim 1 is characterized in that the following step is arranged:
Step 1, take by weighing each element
The quality that calculates each associated element by required atomic percent takes by weighing;
Step 2, melting prepare the Zr-Al-Co-RE-Cu mother alloy
With step 1 claim desired raw material put into vacuum smelting furnace, regulate suction to 5 * 10 -3Pa charges into argon shield gas, argon pressure is 0.05MPa; Melting is 3～5 times under 1000～1600 ℃ of conditions of smelting temperature, takes out the Zr-Al-Co-RE-Cu mother alloy behind the furnace cooling;
Step 3, system Zr-Al-Co-RE-Cu non-crystaline amorphous metal bar
The 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 argon shield gas, argon pressure is 0.05MPa; Behind 1100～1500 ℃ of smelting temperatures, smelting time 2～5min, spurt in the copper mold, and make Zr-Al-Co-RE-Cu non-crystaline amorphous metal bar with the copper mold cooling.
CNA2007101785697A 2007-11-30 2007-11-30 Zr-Al-Co-RE-Cu amorphous alloy Pending CN101161851A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103695814A (en) * 2012-12-31 2014-04-02 比亚迪股份有限公司 Zirconium based amorphous alloy and preparation method thereof
WO2015096479A1 (en) * 2013-12-26 2015-07-02 深圳市比亚迪汽车研发有限公司 Zirconium-based amorphous alloy and preparation method therefor
CN107058912A (en) * 2017-03-30 2017-08-18 福建工程学院 Zr base block amorphous alloys containing precious metal element and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103695814A (en) * 2012-12-31 2014-04-02 比亚迪股份有限公司 Zirconium based amorphous alloy and preparation method thereof
CN103695814B (en) * 2012-12-31 2016-01-13 比亚迪股份有限公司 Zirconium-base amorphous alloy and preparation method thereof
WO2015096479A1 (en) * 2013-12-26 2015-07-02 深圳市比亚迪汽车研发有限公司 Zirconium-based amorphous alloy and preparation method therefor
CN107058912A (en) * 2017-03-30 2017-08-18 福建工程学院 Zr base block amorphous alloys containing precious metal element and preparation method thereof

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