CN102899592B - Plastic zirconium-based metal glass and preparation method thereof - Google Patents
Plastic zirconium-based metal glass and preparation method thereof Download PDFInfo
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- CN102899592B CN102899592B CN201210401806.2A CN201210401806A CN102899592B CN 102899592 B CN102899592 B CN 102899592B CN 201210401806 A CN201210401806 A CN 201210401806A CN 102899592 B CN102899592 B CN 102899592B
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Abstract
The invention discloses plastic zirconium-based metal glass and a preparation method thereof. The component atom percentage expression of zirconium-based metal glass is Zr<a>Ti<b>Cu<c>Ni<d>Be<e>, wherein a is more than or equal to 46 and is less than or equal to 50, b is more than or equal to 14 and is less than or equal to 18, c is more than or equal to 9 and is less than or equal to 11, d is more than or equal to 7 and is less than or equal to 9, e is more than or equal to 16 and is less than or equal to 19, and a+b+c+d+e=100. The preparation method of the plastic zirconium-based metal glass comprises the following steps of: selecting a block metal glass alloy system, and designing alloy components according to a phase selection principle and in combination with binary alloy phase diagrams; melting the raw materials for preparing the alloy into mother alloy by adopting an electric arc melting method; and re-melting the mother alloy and conducting copper-mold gravity casting to obtain the plastic zirconium-based metal glass. The plastic zirconium-based metal glass provided by the invention not only has high strength and excellent plasticity, but also has very high glass formation ability.
Description
Technical field
The invention belongs to metal-base composites technology, particularly a kind of plasticity zirconium-based metallic glass 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 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, 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, the second-phase that domestic and international researchist has introduced varying strength and Young's modulus in metallic glass is prepared BMG matrix material, utilize second-phase to hinder the slippage of single shear zone, and by generation, bifurcated and the deflection of many shear zones and macroscopical plasticity of burying in oblivion to improve material.Wherein the most representative work is that U.S. Johnson research group in 2000 by adding Nb alloy element in Zr-Ti-Cu-Ni-Be alloy system, the BMG matrix material of preparing the plasticising of micron-scale β-Zr (Ti) solid solution phase, its breaking strain can reach 8.26%.Microtexture control aspect, the people such as Chen Guang are by carrying out spheroidizing to dentrite β-Zr (Ti) phase sosoloid, the fracture plasticity of BMG matrix material has been brought up to the method for dentrite nodularization in 20%(bulk metallic glass composite, number of patent application is 200610085409.3).
Although raw sosoloid plasticising BMG matrix material plasticization effect is remarkable in above-mentioned as cast condition, because the intensity of plasticity solid solution phase is far below metallic glass matrix, so cause composite material strength significantly to decline.
Summary of the invention
The object of the invention is to by suitable Composition Design, take common metallic element as constituent element, develop the plasticity zirconium-based metallic glass with strong glass forming ability high-strength and high ductility.
The technical solution that realizes the object of the invention is: a kind of plasticity zirconium-based metallic glass, its alloying element atomic percent expression formula is: Zr
ati
bcu
cni
dbe
e, 46≤a≤50 wherein, 14≤b≤18,9≤c≤11,7≤d≤9,16≤e≤19, a+b+c+d+e=100.
Prepare an above-mentioned plasticity zirconium-based metallic glass process, comprise the following steps:
The first step: choose block metal glass alloy system, according to selecting mutually principle, in conjunction with binary alloy phase diagram, design and adjust alloying constituent Zr
ati
bcu
cni
dbe
e, 46≤a≤50 wherein, 14≤b≤18,9≤c≤11,7≤d≤9,16≤e≤19, a+b+c+d+e=100;
Second step: adopt the method for arc melting, alloy raw material is smelted into mother alloy;
The 3rd step: mother alloy refuse, copper mold gravitational casting obtains plasticity zirconium-based metallic glass.
The purity of the alloy constituent element described in the first step is greater than 99.5%.
The compression plasticity maximum of the plasticity zirconium-based metallic glass described in the 3rd step can reach 10%.
Plasticity zirconium-based metallic glass described in the 3rd step is full non-crystal structure, and its maximum diameter is 35mm.
The present invention compared with prior art, its remarkable advantage: (1) zirconium-based metallic glass of the present invention has excellent comprehensive mechanical property, and its room temperature compressive strength has reached 1900MPa, and plastix strain has also surpassed 8%; (2) zirconium-based metallic glass of the present invention has very strong glass forming ability, adopts water cooled copper mould gravitational casting can prepare the full amorphous coupon of 35mm diameter.
Accompanying drawing explanation
Fig. 1 is plasticity zirconium-based metallic glass preparation schema of the present invention.
Fig. 2 is embodiment 1 plasticity zirconium-based metallic glass metallographic structure and XRD figure (a is micro-organization chart, and b is XRD figure).
Fig. 3 is embodiment 1 plasticity zirconium-based metallic glass chamber temperature and pressure contracting graphic representation.
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, in conjunction with binary alloy phase diagram, carries out design of alloy.Particularly, be exactly by adjusting the relative proportion of alloy element Zr, Ti, Cu, Ni, Be, obtaining required alloy component range, Zr
ati
bcu
cni
dbe
e(atomic percent) represent, 46≤a≤50 wherein, 14≤b≤18,9≤c≤11,7≤d≤9,16≤e≤19, a+b+c+d+e=100.
(2) mother alloy melting:
According to the atomic percent between the resulting different-alloy element of (1) Composition Design, converse mass percent, adopt 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 mother alloy remelting, by copper mold gravitational casting or blow and cast shape, its shape and size can design the inner chamber of copper mold as required.
(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 mechanical property sign, to determine the alloying constituent with best comprehensive mechanical property.
Below in conjunction with specific embodiment, 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
48.7ti
16.3cu
9.7ni
7.8be
17.5(atomic percent).
Table 1 is prepared master alloy ingot and is selected 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 buckle ingot with non-consumable arc-melting furnace, its specific procedure is as follows:
A, the surperficial mechanical grinding of raw metal is removed after surperficial oxide skin, according to the composition proportion material designing, got the raw materials ready; Weight according to every ingot 80g left and right is put into the material preparing 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, argon pressure scope is 0.4 ~ 0.6MPa;
B, before founding master alloy ingot, by the Ti ingot melting for air-breathing 2 ~ 3 times;
C, multi-pass master alloy melting ingot: adopt non-consumable tungsten electrode first by Zr, Ti, Cu, Ni, Be alloying element together melting 2 ~ 3 times, and apply function composite by electromagnetic stirring, the mother alloy button ingot that obtains mixing.The electric current adopting 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 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 (a) is the 35mm diameter Zr that adopts above-mentioned processing condition to prepare
48.7ti
16.3cu
9.7ni
7.8be
17.5the microtexture of alloy.Visible, it is undistinguishable full non-crystal structure.XRD(Fig. 2 (b)) further confirmed its diffuse scattering feature.
Fig. 3 is plasticity zirconium-based metallic glass strain-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 plasticity zirconium fund glass fracture strength has reached 1900MPa, and compression plasticity has surpassed 8%.
Fact proved, this plasticity zirconium fund glass not only has strong glass forming ability, also has high strength and excellent plasticity, has realized the good combination of intensity and plasticity.
embodiment 2
Adopt the method identical with embodiment 1, alloying constituent is: Zr
50ti
18cu
9ni
7be
16, prepared the full amorphous coupon of 25mm diameter, breaking tenacity has reached 1980MPa, and compression plasticity has reached 5%.
embodiment 3
Adopt the method identical with embodiment 1, alloying constituent is: Zr
46ti
14cu
11ni
9be
20, prepared the full amorphous coupon of 30mm diameter, breaking tenacity has surpassed 1800MPa, and compression plasticity has reached 10%.
Claims (7)
1. a plasticity zirconium-based metallic glass, is characterized in that described zirconium-based metallic glass is full non-crystal structure, and metallic glass alloys element atom percentage expression formula is: Zr
ati
bcu
cni
dbe
e, 46≤a≤50 wherein, 14≤b≤18,9≤c≤11,7≤d≤9,16≤e≤19, a+b+c+d+e=100.
2. plasticity zirconium-based metallic glass according to claim 1, is characterized in that the compression plasticity maximum of described zirconium-based metallic glass reaches 10%.
3. a method of preparing above-mentioned plasticity zirconium-based metallic glass, is characterized in that said method comprising the steps of:
The first step: choose block metal glass alloy system, according to selecting mutually principle, in conjunction with binary alloy phase diagram, design and adjust alloying constituent Zr
ati
bcu
cni
dbe
e, 46≤a≤50 wherein, 14≤b≤18,9≤c≤11,7≤d≤9,16≤e≤19, a+b+c+d+e=100;
Second step: adopt the method for arc melting, alloy raw material is smelted into mother alloy;
The 3rd step: mother alloy refuse, copper mold gravitational casting obtains plasticity zirconium-based metallic glass.
4. the method for preparing plasticity zirconium-based metallic glass according to claim 3, is characterized in that the purity of the alloy constituent element described in the first step is greater than 99.5%.
5. the method for preparing plasticity zirconium-based metallic glass according to claim 3, the electric current adopting while it is characterized in that melting in second step is 500 ~ 650A, the voltage that induction stirring adopts is 1 ~ 3V.
6. the method for preparing plasticity zirconium-based metallic glass according to claim 3, is characterized in that the plasticity zirconium-based metallic glass described in the 3rd step is full non-crystal structure, and its maximum diameter is 35mm.
7. the method for preparing plasticity zirconium-based metallic glass according to claim 3, is characterized in that the compression plasticity maximum of the plasticity zirconium-based metallic glass described in the 3rd step can reach 10%.
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| CN104419879B (en) * | 2013-09-06 | 2016-09-21 | 南京理工大学 | A kind of zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region |
| CN108265238B (en) * | 2016-12-30 | 2020-01-24 | 南京理工大学 | Zirconium-based metallic glass endogenetic composite material and tissue thinning method thereof |
| CN107841692B (en) * | 2017-11-13 | 2019-06-07 | 东莞宜安科技股份有限公司 | A method of β type amorphous situ composite material is prepared using iteration thought |
| CN108063269B (en) * | 2017-12-29 | 2018-12-07 | 成都新柯力化工科技有限公司 | It is a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method |
| CN115948706B (en) * | 2023-03-13 | 2023-05-12 | 松诺盟科技有限公司 | Amorphous alloy high-pressure common rail pipe forging process, common rail pipe and high-pressure common rail system |
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| CN102181809A (en) * | 2011-04-21 | 2011-09-14 | 南京理工大学 | Large-size metallic glass composite material with tensile ductility and preparation method thereof |
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| CN102181809A (en) * | 2011-04-21 | 2011-09-14 | 南京理工大学 | Large-size metallic glass composite material with tensile ductility and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Zr-Ti-Cu-Ni-Be大块非晶合金等温晶化过程相分离研究;沈军等;《稀有金属材料工程》;20041231;第33卷(第12期);1257-1260 * |
| 沈军等.Zr-Ti-Cu-Ni-Be大块非晶合金等温晶化过程相分离研究.《稀有金属材料工程》.2004,第33卷(第12期),1257-1260. |
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