CN102888572B - Zirconium-based metallic glass multi-phase composite material and preparation method thereof - Google Patents
Zirconium-based metallic glass multi-phase composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a zirconium-based metallic glass multi-phase composite material and a preparation method thereof. The atom percentage expression formula of the zirconium-based metallic glass multi-phase composite material is as follows: ZraTibCucNisBee, wherein 52<=a<=70, 17<=b<=22, 2<=c<=9, 2<=d<=7, 4<=e<=15, and a+b+c+d+e=100. The preparation method of the zirconium-based metallic glass multi-phase composite material comprises the following steps: selecting a block metallic glass alloy system; according to a phase selection principle, adjusting the components of alloy so that a second phase solid solution of zirconium is separated out at first in the solidification process of the alloy, and a high-hardness third phase is separated out in the subsequent cooling process of the second phase solid solution; melting the alloy components obtained from the first step to form mother alloy by using an electric arc melting method; and melting the mother alloy repeatedly, carrying out gravity casting in a copper-formed mold to obtain the metallic glass multi-phase composite material. According to the invention, the zirconium-based metallic glass multi-phase composite material is high in strength and realizes the good combination of strength and plasticity while the plasticity of the metallic glass is improved.
Description
Technical field
The invention belongs to the metal-base composites technology, particularly a kind of zirconium-based metallic glass heterogeneous composite material and preparation method thereof.
Background technology
Block metal glass (BMG) is although material has high breaking tenacity and hardness and high elastic strain limit, but because the viscous deformation of Single Phase Metal glass is to realize by the height localized shear deformation, the shear zone quantity that can start before fracture is very limited, and the calamitous brittle rupture without macroscopical viscous deformation at room temperature can occur BMG.Therefore, the brittleness at room temperature problem has developed into the important bottleneck of BMG material application.
For improving the brittleness at room temperature of BMG material, within 2000, U.S. Johnson research group first passage adds the Nb alloy element in the Zr-Ti-Cu-Ni-Be alloy system, prepare the BMG matrix material of micron-scale β-Zr (Ti) solid solution phase plasticising, its stretching plastic strain reaches 3%.Subsequently, the people such as Chen Guang are by carrying out spheroidizing to dentrite β-Zr (Ti) phase sosoloid, the stretching plastic of BMG matrix material is brought up to (have large size metal glass composite material of stretching plastic and preparation method thereof, number of patent application is 201110099685.6) more than 6%.
Although it is remarkable to give birth to sosoloid plasticising BMG matrix material plasticization effect in above-mentioned as cast condition, due to the intensity of plasticity solid solution phase, far below the metallic glass matrix, so cause composite material strength significantly to descend.
Summary of the invention
The object of the present invention is to provide a kind of new type zirconium-based metallic glass heterogeneous composite material.The constructional feature of this matrix material is to take BMG as matrix, separates out in as cast condition and gives birth to the sosoloid second-phase, and separate out the third phase of the high rigidity tiny, that disperse distributes in the sosoloid second-phase, thereby produce precipitation strength.When this matrix material is given birth to sosoloid plasticising BMG matrix material plasticization effect within keeping in the past as cast condition, significantly improve the intensity of matrix material.
The technical solution that realizes the object of the invention is: a kind of zirconium-based metallic glass heterogeneous composite material, the atomic percent expression formula of its alloying constituent is: Zr
ati
bcu
cni
dbe
e, 52≤a≤70,17≤b≤22,2≤c≤9,2≤d≤7,4≤e≤15 wherein, a+b+c+d+e=100.The metal glass composite material of this composition has heterogeneous composite structure, is uniform-distribution with sosoloid second-phase β-Zr on its metallic glass matrix, and is settled out the third phase ω-Zr of the high rigidity tiny, that disperse distributes in the sosoloid second-phase.
A kind of method for preparing above-mentioned zirconium-based metallic glass heterogeneous composite material comprises the following steps:
The first step: choose block metal glass, according to selecting mutually principle, adjust alloying constituent Zr
ati
bcu
cni
dbe
e, 52≤a≤70,17≤b≤22 wherein, 2≤c≤9,2≤d≤7,4≤e≤15, a+b+c+d+e=100, make it in process of setting, can first separate out the sosoloid second-phase of zirconium, and the sosoloid second-phase is separated out the third phase of high rigidity in subsequent cooling process;
Second step: adopt the method for arc melting, alloy raw material is smelted into to mother alloy;
The 3rd step: the mother alloy refuse, the copper mold gravitational casting obtains zirconium-based metallic glass heterogeneous composite material.
Each constituent element purity of alloy described in the first step is greater than 99.5%.
The compression plasticity maximum of the zirconium-based metallic glass heterogeneous composite material described in the 3rd step reaches 10%.
Compared with prior art, its remarkable advantage: the present invention has developed a kind of new type zirconium-based metallic glass heterogeneous composite material first in the present invention.This matrix material has unique constructional feature, and it separates out in as cast condition and gives birth to the sosoloid second-phase on the block metal glass matrix, and separates out the third phase of the high rigidity tiny, that disperse distributes in the sosoloid second-phase, thereby produces precipitation strength.Therefore, when this matrix material is given birth to sosoloid plasticising BMG matrix material plasticization effect within keeping general as cast condition, increased substantially the intensity of matrix material.In addition, this matrix material is along with β-Zr phase and ω-Zr phase separates out, and the residue alloy melt has very strong glass forming ability, can obtain the zirconium-based metallic glass heterogeneous composite material of maximum diameter 35mm.
The accompanying drawing explanation
Fig. 1 is to be zirconium-based metallic glass heterogeneous composite material preparation flow figure of the present invention.
Fig. 2 is embodiment 1 zirconium-based metallic glass heterogeneous composite material microstructure and XRD figure spectrum (a is micro-organization chart, and b is the XRD figure spectrum).
Fig. 3 is the room temperature compression curve of embodiment 1 zirconium-based metallic glass heterogeneous composite material.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail
(1) design of alloy:
Selection has the Zr-Ti-Cu-Ni-Be alloy system of good glass forming ability (GFA), according to selecting mutually principle, binary alloy phase diagram, and the stability of phase is analyzed, thereby is determined alloying constituent, obtains required alloy component range, Zr
ati
bcu
cni
dbe
e(atomic percent), 52≤a≤70,17≤b≤22,2≤c≤9,2≤d≤7,4≤e≤15 wherein, a+b+c+d+e=100.
(2) mother alloy melting:
Converse mass percent according to the atomic percent between the resulting different-alloy element of (1) Composition Design, adopt the high pure metal constituent element to configure required alloy.Under the protection of high-purity Ar gas, utilize melting Ti or Zr pure metal to remove residual oxygen in chamber, adopt water jacketed copper crucible non-consumable arc melting equipment to found mother alloy.Mother alloy repeatedly carries out the mother alloy button ingot of induction stirring to obtain mixing when melting.
(3) forming materials:
By after the mother alloy remelting, by the copper mold gravitational casting or blow and cast shape, its shape and size can be as required designed the inner chamber of copper mold.
(4) structural characterization:
Utilize X-ray diffractometer (XRD), differential scanning calorimeter (DSC), opticmicroscope (OM) and scanning electron microscope (SEM) etc. to carry out Microstructure characterization to the alloy of preparation, and further it is carried out to the mechanical property sign, to determine the alloying constituent with best comprehensive mechanical property.
Below in conjunction with specific embodiments and the drawings, the invention will be further described.
embodiment 1
(1) raw-material selecting
The present invention prepares the purity of each metal constituent element that master alloy ingot selects as table 1, and alloying constituent is Zr
60ti
20cu
5.6ni
4.4be
10(atomic percent).
Table 1 prepares master alloy ingot and selects the purity of metal constituent element (%)
| Alloying element | Zr | Ti | Cu | Ni | Be |
| Purity/% | 99.95 | 99.95 | 99.99 | 99.99 | 99.5 |
(2) preparation of master alloy ingot
Under, high-purity argon gas protective condition air-breathing at Ti, found mother alloy with the non-consumable arc-melting furnace and buckle ingot, its specific procedure is as follows:
A, the surperficial mechanical grinding of raw metal is removed to surperficial oxide skin after, according to the composition proportion material designed, get the raw materials ready; Weight according to every ingot 80g left and right is put into the material prepared the water jacketed copper crucible of smelting furnace, covers bell and is evacuated to 2 * 10
-3pa; To the high-purity argon gas (99.99%) that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.4 ~ 0.6MPa;
B, before founding master alloy ingot, will be for air-breathing Ti ingot melting 2 ~ 3 times;
C, multi-pass master alloy melting ingot: adopt the non-consumable tungsten electrode first by Zr, Ti, Cu, Ni, Be alloying element melting together 2 ~ 3 times, and apply function composite by electromagnetic stirring, the mother alloy button ingot that obtains mixing.The electric current adopted during melting is 500 ~ 650A, and the voltage that induction stirring adopts is 1 ~ 3V.
(3) forming materials
Mother alloy button ingot is placed in to the shaping system that water jacketed copper crucible and water cooled copper mould are combined closely.System is evacuated to 4 ~ 5 * 10
-4pa; After the electric-arc heating remelting, under rare gas element (99.999% the high-purity argon) protective atmosphere of 0.6MPa, rely on self gravitation to inject water cooled copper mould, prepare the bar-shaped sample of required diameter.
(4) structure and performance characterization
Fig. 2 is the 35mm diameter Zr that adopts above-mentioned processing condition to prepare
60ti
20cu
5.6ni
4.4be
10the microtexture of alloy and XRD figure spectrum, can find out, the structure of this matrix material is: be uniform-distribution with the β of 10～30 μ m-Zr phase on the block metal glass matrix, and β-Zr mutually in the even dispersion tiny ω-Zr particle that distributing.
Fig. 3 is zirconium-based metallic glass heterogeneous composite material room temperature compressive stress strain curve, and experiment condition is: sample is 3 * 6mm column sample, and experimental temperature is room temperature (25 ℃), and compressive strain speed is 2 * 10
-4s
-1.Mechanical experimental results shows: prepared matrix material yield strength has reached 1450MPa, and compression plasticity has surpassed 10%.
Fact proved, gave birth to solid solution phase plasticising metal glass composite material in the past, zirconium-based metallic glass heterogeneous composite material, on the basis that has kept good plasticity, significantly improves the intensity of material, has realized the good combination of intensity and plasticity.
embodiment 2
Adopt the method identical with embodiment 1, alloying constituent is Zr
56.3ti
18.7cu
6.9ni
5.6be
12.5, having prepared the zirconium-based metallic glass heterogeneous composite material of 25mm diameter, yield strength has reached 1580MPa, and compression plasticity has reached 8%.
embodiment 3
Adopt the method identical with embodiment 1, alloying constituent is Zr
52ti
17cu
9ni
7be
15, having prepared the zirconium-based metallic glass heterogeneous composite material of 30mm diameter, yield strength has surpassed 1650MPa, and compression plasticity has reached 6%.
Adopt the method identical with embodiment 1, alloying constituent is Zr
70ti
22cu
2ni
2be
4, having prepared the zirconium-based metallic glass heterogeneous composite material of 30mm diameter, yield strength has surpassed 1350MPa, and compression plasticity has reached 10%.
Claims (9)
1. a zirconium-based metallic glass heterogeneous composite material, is characterized in that the atomic percent expression formula of the alloying constituent of described matrix material is: Zr
ati
bcu
cni
dbe
e, 52≤a≤70,17≤b≤22,2≤c≤9,2≤d≤7,4≤e≤15 wherein, a+b+c+d+e=100.
2. zirconium-based metallic glass heterogeneous composite material according to claim 1, the matrix material that it is characterized in that described composition has heterogeneous composite structure, be uniform-distribution with sosoloid second-phase β-Zr on its metallic glass matrix, and be settled out the third phase ω-Zr of the high rigidity tiny, that disperse distributes in the sosoloid second-phase.
3. zirconium-based metallic glass heterogeneous composite material according to claim 1, the maximum diameter that it is characterized in that described matrix material is 35mm.
4. zirconium-based metallic glass heterogeneous composite material according to claim 1, is characterized in that the compression plasticity maximum of described matrix material reaches 10%.
5. a method for preparing zirconium-based metallic glass heterogeneous composite material is characterized in that said method comprising the steps of:
The first step: choose block metal glass, according to selecting mutually principle, adjust alloying constituent Zr
ati
bcu
cni
dbe
e, 52≤a≤70,17≤b≤22 wherein, 2≤c≤9,2≤d≤7,4≤e≤15, a+b+c+d+e=100, make its sosoloid second-phase β-Zr that can first separate out zirconium in process of setting, and the sosoloid second-phase is separated out the third phase ω-Zr of high rigidity in subsequent cooling process;
Second step: adopt the method for arc melting, alloy raw material is smelted into to mother alloy;
The 3rd step: the mother alloy refuse, the copper mold gravitational casting obtains zirconium-based metallic glass heterogeneous composite material.
6. the method for preparing zirconium-based metallic glass heterogeneous composite material according to claim 5, is characterized in that each constituent element purity of the alloy described in the first step is greater than 99.5%.
7. the method for preparing zirconium-based metallic glass heterogeneous composite material according to claim 5, the electric current adopted while it is characterized in that melting described in second step is 500～650A, the voltage that induction stirring adopts is 1～3V.
8. the method for preparing zirconium-based metallic glass heterogeneous composite material according to claim 5, is characterized in that the maximum diameter of the zirconium-based metallic glass heterogeneous composite material described in the 3rd step is 35mm.
9. the method for preparing zirconium-based metallic glass heterogeneous composite material according to claim 5, is characterized in that the compression plasticity maximum of the zirconium-based metallic glass heterogeneous composite material described in the 3rd step reaches 10%.
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| JPH0762502A (en) * | 1993-08-19 | 1995-03-07 | Takeshi Masumoto | Amorphous zirconium alloy having wide region of supercooled liquid |
| JP2002544386A (en) * | 1999-04-30 | 2002-12-24 | カリフォルニア・インスティテュート・オブ・テクノロジー | In-situ formed ductile metal / bulk metallic glass matrix composite formed by concentration distribution |
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