CN102978541A - Shape-memory crystalline-phase strengthened and toughened Ti-base amorphous composite material and preparation method thereof - Google Patents

Shape-memory crystalline-phase strengthened and toughened Ti-base amorphous composite material and preparation method thereof Download PDF

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CN102978541A
CN102978541A CN2012105391197A CN201210539119A CN102978541A CN 102978541 A CN102978541 A CN 102978541A CN 2012105391197 A CN2012105391197 A CN 2012105391197A CN 201210539119 A CN201210539119 A CN 201210539119A CN 102978541 A CN102978541 A CN 102978541A
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amorphous composite
shape memory
base amorphous
vacuum
phase
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CN102978541B (en
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赵燕春
寇生中
袁小鹏
李春燕
蒲永亮
李超
蒋维科
徐娇
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Lanzhou Polytechnic Alloy Powder Co.,Ltd.
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Lanzhou University of Technology
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Abstract

The invention relates to a shape-memory crystalline-phase toughened Ti-base amorphous composite material and a preparation method thereof. On the basis of atomic percents, the composition of the composite material is (Ti0.50Ni0.50-yMy)100-xCux, wherein M is one or more of Fe, Co, Nb, Al, Zr and Si, x is 5-33, and y is 0-0.25. The material has certain shape memory effect and high amorphous formation capacity. A plastic phase-overcooling austenite phase precipitated from the amorphous base in situ is used for toughening; and the overcooling austenite in the shape memory alloy is subjected to thermoelastic martensitic phase transformation under the induction of deformation, so that the amorphous body is subjected to work hardening and thus is strengthened. The composite material has excellent comprehensive mechanical properties: the compressive yield strength is 1000-1800 MPa, the fracture strength is 1400-2800 MPa, and the plastic deformation is 10-20%; and the composite material has strong work hardening property.

Description

Shape memory crystalline phase highly malleablized Ti base amorphous composite and preparation method thereof
Technical field
[0001] the present invention relates to Ti base amorphous composite field, be specially a kind of shape memory crystalline phase and strengthen composition of toughness reinforcing Ti base amorphous composite and preparation method thereof.
Background technology
Titanium-based amorphous advantage with density is low, intensity is high, good wear resistance and corrosion resistance and biocompatibility etc. has very large application prospect in space flight and aviation, machinery, building, the energy and the aspect such as biomedical.But, because the non-crystaline amorphous metal atomic arrangement presents unordered, the shot-range ordered structure of long-range, lack the work hardening mechanisms such as the dislocation of conventional crystalline metal material and slippage during distortion, the shearing behavior of height localization has limited non-crystaline amorphous metal as the widespread use of structured material in engineering so that its temperature-room type plasticity and fracture toughness property are low.In recent years, people have proposed the multiple method toughness reinforcing to non-crystaline amorphous metal, wherein introduce second-phase and can select according to various performance index, and BMG based composite material structure and performance have designability, are a kind of effective BMG method for toughening.
Such as 2008, W. L. Johnson seminar processes by adjusting alloying constituent and semi-solid state, in titanium-based amorphous alloy system, develop the toughness reinforcing matrix material of β phase dendrite with remarkable plasticity, its room temperature tensile total deformation rate is respectively 10.8% and 13.1%, relative reduction in area is respectively 50% and 46%, the plasticity and toughness index of this material has reached the indication range of traditional metal materials, but still shows strain softening after its distortion surrender, has been subject to certain limitation so that engineering is promoted.
Summary of the invention
The purpose of this invention is to provide a kind ofShape memory crystalline phase highly malleablized Ti base amorphous composite and preparation method thereof.
The present invention isShape memory crystalline phase highly malleablized Ti base amorphous composite and preparation method thereof, shape memory crystalline phase highly malleablized Ti base amorphous composite, Ti base noncrystal alloy and the supercooled austenite that can produce deformation induced phase transformation mutually B2-TiNi and martensitic phase B19 '-TiNi are composited.
ShapeThe preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite the steps include:
(1) batching:
By (the Ti shown in the claim 1 0.50Ni 0.50-yM y) 100-xCu xNominal composition takes by weighing each component;
(2) melting system (Ti 0.50Ni 0.50-yM y) 100-xCu xMother alloy:
With step (1) claim desired raw material put into the vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3The Pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares the amorphous composite sample:
(Ti with step (2) preparation 0.50Ni 0.50-yM y) 100-xCu xMother alloy is put into the water-cooled suspension smelting crucible remelting, regulates the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3Pa;
Behind smelting time 1 ~ 3min under induction voltage 5 ~ 10kV, by the negative pressure copper mold casting bar is cast in the mother alloy suction.
The present invention compared with prior art, remarkable advantage is arranged: the matrix material of inventing with the Ti base noncrystal alloy as body material, than single-phase non-crystaline amorphous metal and interior living Ti base amorphous composite in the past, the matrix situ is separated out has deformation induced phase transition property shape memory crystalline phase as tough phase, reach the purpose that significantly improves intensity and plasticity, and show strong work hardening.
Description of drawings
Fig. 1 is the as cast condition XRD figure of the Ti base amorphous composite of diameter 3mm, and Fig. 2 is the rear XRD figure of Ti base amorphous composite stress loading fracture of diameter 3mm, and Fig. 3 is the room temperature stress under compression strain curve of the Ti base amorphous composite of diameter 3mm.
Embodiment
The present invention isShape memory crystalline phase highly malleablized Ti base amorphous composite and preparation method thereof, shape memory crystalline phase highly malleablized Ti base amorphous composite, Ti base noncrystal alloy and the supercooled austenite that can produce deformation induced phase transformation mutually B2-TiNi and martensitic phase B19 '-TiNi are composited.
ShapeThe preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite the steps include:
(1) batching:
By (the Ti shown in the claim 1 0.50Ni 0.50-yM y) 100-xCu xNominal composition takes by weighing each component;
(2) melting system (Ti 0.50Ni 0.50-yM y) 100-xCu xMother alloy:
With step (1) claim desired raw material put into the vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3The Pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares the amorphous composite sample:
(Ti with step (2) preparation 0.50Ni 0.50-yM y) 100-xCu xMother alloy is put into the water-cooled suspension smelting crucible remelting, regulates the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3Pa;
Behind smelting time 1 ~ 3min under induction voltage 5 ~ 10kV, by the negative pressure copper mold casting bar is cast in the mother alloy suction.
Below by specific embodiment in detail the present invention is described in detail.
Embodiment 1:
The composition of Ti base amorphous composite is (Ti 0.5Ni 0.5) 80Cu 20, select purity greater than 99.99% Ti and Cu, 99.9% Zr and Al, prepare the raw material of certain mass by atomic percent after, put into the vacuum high-frequency electromagnetic induction heating furnace, regulate the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3The Pa melting, alloy pig melt back at least three times.Again mother alloy is put into the water-cooled suspension smelting crucible remelting, regulated the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3Pa.Behind smelting time 1 ~ 3min under induction voltage 5 ~ 10kV, by the negative pressure copper mold casting diameter 3mm bar is cast in the mother alloy suction.
Fig. 1 except typical amorphous diffuse scattering peak, also has bright and sharp crystalline diffraction peak to be superimposed upon on the diffuse scattering peak for inhaling the as cast condition XRD figure of casting sample, shows that sample is the composite structure of Crystal and glass.The main crystal of separating out is B2-TiNi mutually, and the Pearson symbol is cP2 (ClCs), lattice constant a 0=0.301nm is the supercooled austenite phase; Detect simultaneously B19 '-TiNi phase, crystal parameters a 0=0.2892, b 0=0.4108, c 0=0.4646, β=97.78 oBe martensitic phase, because the high speed of cooling of copper mold is present in the as-cast structure soon.
Fig. 2 is for inhaling XRD figure after the fracture of casting sample stress loading, and except typical amorphous diffuse scattering peak, the main crystal phase B19 ' that separates out-TiNi phase and compares before the fracture, and stress loading rear section austenite is to martensitic transformation, and the martensite amount of separating out obviously increases.
Fig. 3 is for inhaling the room temperature stress under compression strain curve of casting sample, this alloy compression yield strength be 1384MPa, breaking tenacity is 2256MPa, compressive strain is 12.2%, and shows strong work hardening.
Embodiment 2:
Adopt the preparation method identical with embodiment 1, the composition of the basic amorphous composite alloy of Ti is:
Atomic percent is (Ti 0.5Ni 0.48Zr 0.02) 80Cu 20,
As shown in Figure 1, the as-cast structure of inhaling the casting sample is the amorphous matrix composite, separates out main crystal and is mutually supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi.
As shown in Figure 2, with the fracture before compare, stress loading rear section austenite is to martensitic transformation, the martensite amount of separating out obviously increases.
Such as Fig. 3, this alloy compression yield strength be 1295MPa, breaking tenacity is 2360MPa, compressive strain is 11.6%, and shows strong work hardening.
Embodiment 3:
Adopt the preparation method identical with embodiment 1, the composition of the basic amorphous composite alloy of Ti is:
Atomic percent is (Ti 0.5Ni 0.48Co 0.02) 80Cu 20,
As shown in Figure 1, the as-cast structure of inhaling the casting sample is the amorphous matrix composite, separates out main crystal and is mutually supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi.
With the fracture before compare, stress loading rear section austenite is to martensitic transformation, the martensite amount of separating out obviously increases.
As shown in Figure 3, this alloy compression yield strength be 1504MPa, breaking tenacity is 2582MPa, plastix strain is 15%, and shows strong work hardening.

Claims (5)

1. shape memory crystalline phase highly malleablized Ti base amorphous composite is characterized in that: this matrix material is the Ti base noncrystal alloy and B2-TiNi and martensitic phase B19 '-TiNi's supercooled austenite that can produce deformation induced phase transformation are composited mutually.
2. shape memory crystalline phase highly malleablized Ti according to claim 1 base amorphous composite, it is characterized in that: doping and composition adjustment by alloy obtain different volumes mark supercooled austenite mutually B2-TiNi and martensitic phase B19 '-TiNi, and have strong amorphous formation ability.
3. shape memory crystalline phase highly malleablized Ti according to claim 1 base amorphous composite, it is characterized in that: by atomic percent, the composition of described Ti base amorphous composite is: (Ti 0.50Ni 0.50-yM y) 100-xCu x, wherein: M is one or several of Fe, Co, Nb, Al, Zr, Si element, x=5 ~ 33, y=0 ~ 0.25.
4. shape memory crystalline phase highly malleablized Ti according to claim 1 base amorphous composite, it is characterized in that: the compression yield strength of matrix material is 1000 ~ 1800MPa, breaking tenacity is 1400 ~ 2800MPa, and compressive strain is 10% ~ 20%, and shows strong work hardening.
5. the preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite the steps include:
(1) batching:
By (the Ti shown in the claim 1 0.50Ni 0.50-yM y) 100-xCu xNominal composition takes by weighing each component;
(2) melting system (Ti 0.50Ni 0.50-yM y) 100-xCu xMother alloy:
With step (1) claim desired raw material put into the vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3The Pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares the amorphous composite sample:
(Ti with step (2) preparation 0.50Ni 0.50-yM y) 100-xCu xMother alloy is put into the water-cooled suspension smelting crucible remelting, regulates the vacuum tightness 2 * 10 of vacuum magnetic suspension smelting furnace -3～5 * 10 -3Then Pa fills high-purity argon gas and makes the vacuum tightness to 0.1 of vacuum chamber * 10 -3～0.8 * 10 -3Pa;
Behind smelting time 1 ~ 3min under induction voltage 5 ~ 10kV, by the negative pressure copper mold casting bar is cast in the mother alloy suction.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103361501A (en) * 2013-07-18 2013-10-23 兰州理工大学 Preparation method of shape-memory crystalline-phase strengthened and roughened Ti-based amorphous composite material
CN104789910A (en) * 2015-03-06 2015-07-22 张临财 Ti-based amorphous alloy and method for making bone drill from the same
CN105177470A (en) * 2015-06-05 2015-12-23 北方民族大学 Titanium-based amorphous fiber and preparation method thereof
CN105296800A (en) * 2014-08-01 2016-02-03 中国石油大学(北京) TiNiCuNb memory alloy and preparation method thereof
US20190062884A1 (en) * 2015-10-07 2019-02-28 Seoul National University R&Db Foundation Metallic glass composites with controllable work-hardening capacity
CN114109752A (en) * 2021-11-08 2022-03-01 上海交通大学 Shape memory alloy driving element

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103361501A (en) * 2013-07-18 2013-10-23 兰州理工大学 Preparation method of shape-memory crystalline-phase strengthened and roughened Ti-based amorphous composite material
CN103361501B (en) * 2013-07-18 2015-08-05 兰州理工大学 The preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite
CN105296800A (en) * 2014-08-01 2016-02-03 中国石油大学(北京) TiNiCuNb memory alloy and preparation method thereof
CN104789910A (en) * 2015-03-06 2015-07-22 张临财 Ti-based amorphous alloy and method for making bone drill from the same
CN104789910B (en) * 2015-03-06 2017-01-25 张临财 Ti-based amorphous alloy and method for making bone drill from the same
CN105177470A (en) * 2015-06-05 2015-12-23 北方民族大学 Titanium-based amorphous fiber and preparation method thereof
US20190062884A1 (en) * 2015-10-07 2019-02-28 Seoul National University R&Db Foundation Metallic glass composites with controllable work-hardening capacity
US10895005B2 (en) 2015-10-07 2021-01-19 Seoul National University R & Db Foundation Metallic glass composites with controllable work-hardening capacity
CN114109752A (en) * 2021-11-08 2022-03-01 上海交通大学 Shape memory alloy driving element
CN114109752B (en) * 2021-11-08 2023-07-28 上海交通大学 Shape memory alloy driving element

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Address after: 730050 Lanzhou City, Gansu Province Lan Ping, No. 287

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Address before: 730050 Lanzhou City, Gansu Province Lan Ping, No. 287

Patentee before: Lanzhou University Of Technology