CN102978541B - 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 PDFInfo
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- CN102978541B CN102978541B CN201210539119.7A CN201210539119A CN102978541B CN 102978541 B CN102978541 B CN 102978541B CN 201210539119 A CN201210539119 A CN 201210539119A CN 102978541 B CN102978541 B CN 102978541B
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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
Technical field
The present invention relates to Ti base amorphous composite field, be specially composition of a kind of shape memory crystalline phase activeness and quietness Ti base amorphous composite and preparation method thereof.
Background technology
The titanium-based amorphous advantage with the wear resistance and corrosion resistance and biocompatibility etc. that density is low, intensity is high, good, has very large application prospect in space flight and aviation, machinery, building, the energy and biomedicine etc.But, because non-crystaline amorphous metal atomic arrangement presents longrange disorder, shot-range ordered structure, the work hardening mechanisms such as the dislocation of conventional crystalline metallic substance and slippage are lacked during distortion, height localization shearing behavior make its temperature-room type plasticity and fracture toughness property low, limit non-crystaline amorphous metal as the widespread use of structured material in engineering.In recent years, there has been proposed the multiple method toughness reinforcing to non-crystaline amorphous metal, wherein introducing second-phase can select according to various performance index, and BMG based composite material structure and performance have designability, is a kind of effective BMG method for toughening.
As 2008, W. L. Johnson seminar is by adjustment alloying constituent and Semi-solid Material Processing, the matrix material that the β phase dendrite with remarkable plasticity is toughness reinforcing is developed in titanium-based amorphous alloy system, 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 reaches the indication range of traditional metal materials, but still shows strain softening after its distortion surrender, engineering is promoted and receives a definite limitation.
Summary of the invention
the object of this invention is to provide oneshape 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 is composited with the supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi that can produce deformation induced trans-formation.
shapethe preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite, the steps include:
(1) prepare burden:
By (the Ti shown in claim 1
0.50ni
0.50-ym
y)
100-xcu
xnominal composition takes each component;
(2) melting system (Ti
0.50ni
0.50-ym
y)
100-xcu
xmother alloy:
The desired raw material that step (1) claims is put into vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares amorphous composite sample:
By (Ti prepared by step (2)
0.50ni
0.50-ym
y)
100-xcu
xwater-cooled suspension smelting crucible remelting put into by mother alloy, regulates the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa;
Under induction voltage 5 ~ 10kV after smelting time 1 ~ 3min, by negative pressure copper mold casting, bar is cast in mother alloy suction.
The present invention compared with prior art, there is remarkable advantage: the matrix material invented is using Ti base noncrystal alloy as body material, compared to single-phase non-crystaline amorphous metal and in the past in raw Ti base amorphous composite, matrix situ is separated out has deformation induced trans-formation character shape memory crystalline phase as tough phase, reach the object significantly improving intensity and plasticity, and show strong work hardening.
Accompanying drawing explanation
Fig. 1 is the as cast condition XRD figure of the Ti base amorphous composite of diameter 3mm, and Fig. 2 is XRD figure after the 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 is composited with the supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi that can produce deformation induced trans-formation.
shapethe preparation method of shape memory crystalline phase highly malleablized Ti base amorphous composite, the steps include:
(1) prepare burden:
By (the Ti shown in claim 1
0.50ni
0.50-ym
y)
100-xcu
xnominal composition takes each component;
(2) melting system (Ti
0.50ni
0.50-ym
y)
100-xcu
xmother alloy:
The desired raw material that step (1) claims is put into vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares amorphous composite sample:
By (Ti prepared by step (2)
0.50ni
0.50-ym
y)
100-xcu
xwater-cooled suspension smelting crucible remelting put into by mother alloy, regulates the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa;
Under induction voltage 5 ~ 10kV after smelting time 1 ~ 3min, by negative pressure copper mold casting, bar is cast in 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 to be greater than Ti and Cu of 99.99%, Zr and Al of 99.9%, prepare the raw material of certain mass by atomic percent after, put into vacuum high-frequency electromagnetic induction heating furnace, regulate the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa melting, alloy pig melt back at least three times.Again mother alloy is put into water-cooled suspension smelting crucible remelting, regulate the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa.Under induction voltage 5 ~ 10kV after smelting time 1 ~ 3min, by negative pressure copper mold casting, diameter 3mm bar is cast in mother alloy suction.
Fig. 1 is the as cast condition XRD figure of inhaling casting sample, except typical amorphous diffuse scattering peak, also has bright and sharp crystalline diffraction peak to be superimposed upon on diffuse scattering peak, shows that sample is the composite structure of Crystal and glass.The predominant crystal of separating out is B2-TiNi, Pearson symbol is mutually cP2 (ClCs), lattice constant a
0=0.301nm is supercooled austenite phase; B19 '-TiNi phase detected, crystal parameters a simultaneously
0=0.2892, b
0=0.4108, c
0=0.4646, β=97.78
ofor martensitic phase, the speed of cooling high due to copper mold is present in as-cast structure soon.
Fig. 2 is for inhaling the rear XRD figure of casting sample stress loading fracture, and except typical amorphous diffuse scattering peak, predominant crystal phase the B19 '-TiNi phase of precipitation, compared with before fracture, stress loading rear section austenite is to martensitic transformation, and martensite amount of precipitation obviously increases.
Fig. 3 be inhale casting sample room temperature stress under compression strain curve, this alloy compression yield strength be 1384MPa, breaking tenacity is 2256MPa, and compressive strain is 12.2%, and shows strong work hardening.
Embodiment 2:
Adopt the preparation method identical with embodiment 1, the composition of Ti base amorphous composite alloy is:
Atomic percent is (Ti
0.5ni
0.48zr
0.02)
80cu
20,
As shown in Figure 1, the as-cast structure inhaling casting sample is amorphous matrix composite, and separating out predominant crystal is supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi mutually.
As shown in Figure 2, compared with before fracture, stress loading rear section austenite is to martensitic transformation, and martensite amount of precipitation obviously increases.
As Fig. 3, this alloy compression yield strength be 1295MPa, breaking tenacity is 2360MPa, and compressive strain is 11.6%, and shows strong work hardening.
Embodiment 3:
Adopt the preparation method identical with embodiment 1, the composition of Ti base amorphous composite alloy is:
Atomic percent is (Ti
0.5ni
0.48co
0.02)
80cu
20,
As shown in Figure 1, the as-cast structure inhaling casting sample is amorphous matrix composite, and separating out predominant crystal is supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi mutually.
Compared with before fracture, stress loading rear section austenite is to martensitic transformation, and martensite amount of precipitation obviously increases.
As shown in Figure 3, this alloy compression yield strength be 1504MPa, breaking tenacity is 2582MPa, and plastix strain is 15%, and shows strong work hardening.
Claims (1)
1. a preparation method for shape memory crystalline phase highly malleablized Ti base amorphous composite, the steps include:
(1) prepare burden:
By atomic percentage, the composition of described Ti base amorphous composite is: (Ti
0.50ni
0.50-ym
y)
100-xcu
x, wherein: M is Co or Zr element, x=5 ~ 33, y=0 ~ 0.25 takes each component;
(2) melting system (Ti
0.50ni
0.50-ym
y)
100-xcu
xmother alloy:
The desired raw material that step (1) claims is put into vacuum high-frequency electromagnetic induction heating furnace;
Regulate the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa melting, alloy pig melt back at least three times;
(3) copper mold casting prepares amorphous composite sample:
By (Ti prepared by step (2)
0.50ni
0.50-ym
y)
100-xcu
xwater-cooled suspension smelting crucible remelting put into by mother alloy, regulates the vacuum tightness 2 × 10 of vacuum magnetic suspension smelting furnace
-3~ 5 × 10
-3pa, then fills vacuum tightness to 0.1 × 10 that high-purity argon gas makes vacuum chamber
-3~ 0.8 × 10
-3pa;
(4) under induction voltage 5 ~ 10kV, after smelting time 1 ~ 3min, by negative pressure copper mold casting, bar is cast in mother alloy suction;
Described shape memory crystalline phase highly malleablized Ti base amorphous composite is that Ti base noncrystal alloy and the supercooled austenite phase B2-TiNi that can produce deformation induced trans-formation and martensitic phase B19 '-TiNi are composited; In preparation method, by doping and the composition adjustment acquisition different volumes mark supercooled austenite phase B2-TiNi and martensitic phase B19 '-TiNi of alloy, and there is strong amorphous formation ability; The compression yield strength of described matrix material is 1000 ~ 1800MPa, and breaking tenacity is 1400 ~ 2800MPa, and compressive strain is 10% ~ 20%, and shows strong work hardening.
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| 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 |
| CN105296800B (en) * | 2014-08-01 | 2018-07-24 | 中国石油大学(北京) | A kind of TiNiCuNb memorial alloys and preparation method thereof |
| CN104789910B (en) * | 2015-03-06 | 2017-01-25 | 张临财 | Ti-based amorphous alloy and method for making bone drill from the same |
| CN105177470B (en) * | 2015-06-05 | 2017-04-19 | 北方民族大学 | Titanium-based amorphous fiber and preparation method thereof |
| KR101752976B1 (en) * | 2015-10-07 | 2017-07-11 | 서울대학교산학협력단 | Fabricating method for metallic glass composite with controlling work hardening capacity and composites fabricated by the method |
| CN114109752B (en) * | 2021-11-08 | 2023-07-28 | 上海交通大学 | Shape memory alloy driving element |
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Effective date of registration: 20170526 Address after: 730050 Lanzhou City, Gansu Province Lan Ping, No. 287 Patentee after: Lanzhou Polytechnic Alloy Powder Co.,Ltd. Address before: 730050 Lanzhou City, Gansu Province Lan Ping, No. 287 Patentee before: Lanzhou University Of Technology |