CN102912260B - Endogenic intermetallic compound metal glass composite material and preparation method thereof - Google Patents
Endogenic intermetallic compound metal glass composite material and preparation method thereof Download PDFInfo
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- CN102912260B CN102912260B CN201210401586.3A CN201210401586A CN102912260B CN 102912260 B CN102912260 B CN 102912260B CN 201210401586 A CN201210401586 A CN 201210401586A CN 102912260 B CN102912260 B CN 102912260B
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Abstract
The invention discloses an endogenic intermetallic compound metal glass composite material and a preparation method thereof. According to the invention, an atomic percent expression of components of the alloy is ZraTibCucNidBee, wherein a is not less than 30 and not more than 39, b is not less than 10 and not more than 12, c is not less than 6 and not more than 9, d is not less than 4 and not more than 8, e is not less than 32 and not more than 50, and a+b+c+d+e=100. A method for preparing the endogenic intermetallic compound metal glass composite material comprises the following steps of: selecting a block metal glass alloy system, and adjusting alloy components according to a phase selection principle so as to separate out an intermetallic compound phase in a condensation process; smelting the alloy components obtained in the first step to a mother alloy according to an electric arc smelting method; remelting the mother alloy, and carrying out gravity casting and copper mold suction cast so as to obtain a section bar; placing the section bar into a processed crucible, adopting induction smelting to a molten state, thermally insulating and quickly condensing in sequence so as to an as-cast endogenic composite material, wherein a second phase of the intermetallic compound is uniformly distributed on a metal glass substrate. According to the invention, the high intensity and the high hardness of the block metal glass are kept, and the room-temperature plasticity is greatly improved.
Description
Technical field
The invention belongs to metal-base composites technology, particularly a kind of interior raw intermetallic compound metal glass 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 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, within 2000, Johnson research group of U.S. first passage adds 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 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 more than 6% (have large size metal glass composite material of stretching plastic and preparation method thereof, number of patent application is 201110099685.6).
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, therefore cause composite material strength significantly to decline.
Summary of the invention
The object of the present invention is to provide a kind of novel interior raw intermetallic compound metal glass composite material.The constructional feature of this matrix material is taking BMG as matrix, in as cast condition, gives birth to intermetallic compound (IMC) as second-phase.This matrix material, in ensureing the high-yield strength of metallic glass, can significantly improve its brittleness at room temperature.
The technical solution that realizes the object of the invention is: raw intermetallic compound metal glass composite material in a kind of, its alloying constituent atomic percent expression formula is: Zr
ati
bcu
cni
dbe
e, wherein 30≤a≤39,10≤b≤12,6≤c≤9,4≤d≤8,32≤e≤50, a+b+c+d+e=100.Metal glass composite material prepared by this composition is even dispersion distribution rigid brittle second-phase ZrBe on its glass basis
2.
Prepare an above-mentioned interior raw intermetallic compound metal glass composite material method, comprise the following steps:
The first step: choose block metal glass alloy system, according to selecting mutually principle, adjust alloying constituent Zr
ati
bcu
cni
dbe
e, wherein 30≤a≤39,10≤b≤12,6≤c≤9,4≤d≤8,32≤e≤50, a+b+c+d+e=100, make its can first precipitating metal in process of setting between Compound Phase ZrBe
2;
Second step: adopt the method for arc melting, the alloying constituent that the first step is obtained is smelted into mother alloy;
The 3rd step: mother alloy refuse, copper mold is made section bar;
The 4th step: again section bar is put into the crucible of handling well, adopt induction melting to molten state, after insulation, adopt rapid sequential solidifying process, thereby prepare the matrix material of raw intermetallic compound in the as cast condition that is uniformly distributed different volumes mark on block metal glass matrix.
Alloy constituent element purity described in the first step is greater than 99.5%.
The withdrawing rate of the rapid sequential solidifying process described in the 4th step is 0.83-5mm/s.
The present invention compared with prior art, its remarkable advantage: (1) keeps existing BMG high strength.Prior art be mostly there is certain plasticity interior raw solid solution phase (as β-Zr (Ti) phase) as plasticising second-phase, but the intensity of solid solution phase (800 ~ 950MPa) compared with metallic glass (1800MPa), its intensity is low more than 50%.The composite material strength that obtained is like this starkly lower than original metal glass, and along with the volume fraction of solid solution phase increases, the intensity of matrix material can further decline.The present invention adopts the intermetallic compound of rigid brittle as second-phase, and this has high intensity mutually (as ZrBe
2the intensity >1400MPa of phase), close to block metal glass.The intermetallic compound of low volume fraction can not cause obvious impact for the intensity of final matrix material.For the lower block metal glass of some intensity (Mg-BMG etc.), intermetallic compound even can play the effect of chilled glass matrix.(2) plasticity of raising material.Although the matrix phase of institute's invention matrix material and second-phase is single-phase while existing, all shows room temperature macroscopic view fragility, the matrix material being made up of them but has significant compression plasticity.Because the brittleness at room temperature of BMG material is because the localization of shear zone causes, and in each shear zone, plastix strain is very large, and the application utilizes intermetallic compound (IMC) fully to excite the plasticity of BMG matrix phase own.In the time of stress application load, the intermetallic compound of hard has hindered the rapid expansion of single shear zone, excites the generation of many shear zones.Shear zone is blocked by intermetallic compound in expansion process, is forced to stop or walks around IMC particle.Intermetallic compound is of a size of micron-scale magnitude and has substantially exceeded the shear band spacing of block metal glass matrix, can effectively to shear zone, expansion hinders.Therefore,, although intermetallic compound is high-intensity hard phase, the bulk metallic glass in situ composite material that we obtain still has good plasticity.
Brief description of the drawings
Fig. 1 is raw intermetallic compound metal glass composite material preparation flow figure in the present invention.
Fig. 2 is embodiment 1IMC/BMG matrix material micro-structure diagram (a is micro-organization chart, and b is XRD figure).
Fig. 3 is the room temperature compression curve figure of embodiment 1IMC/BMG matrix 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, in conjunction with the forming core growth rhythm of intermetallic compound, carries out design of alloy.Particularly, choose block metal glass Zr
41.2ti
13.8cu
12.5ni
10be
22.5, by adjusting the relative proportion of alloy element Zr, Ti, Cu, Ni, Be, make it near ZrBe
2, obtain required alloy component range, Zr
ati
bcu
cni
dbe
e(atomic percent), wherein 30≤a≤39,10≤b≤12,6≤c≤9,4≤d≤8,32≤e≤50, a+b+c+d+e=100.
(2) mother alloy melting:
Atomic percent between the different-alloy element obtaining according to (1) Composition Design converses mass percent, adopts 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 or blow and cast required section bar, its shape and size can design the inner chamber of copper mold as required.
(4) rapid sequential solidifies
The section bar that copper mold is shaped is put into and the plumbago crucible of handling well, after vacuumizing, is filled with high-purity argon gas, carries out induction heating and makes alloy molten, after insulation, immerses in the extremely strong Ga-In-Sn liquid alloy of cooling power with different withdrawing rates.
(5) 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 matrix material of preparation, and further it is carried out to mechanical property sign, to determine matrix material microtexture and the corresponding preparation technology parameter thereof 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
39ti
12cu
9ni
8be
32(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, got the raw materials ready according to the composition proportion material designing; The water jacketed copper crucible of according to the weight of every ingot 80g left and right, the material preparing being put into 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 when 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) rapid sequential solidifies
The section bar that copper mold is shaped is put into and the plumbago crucible of handling well, after vacuumizing, is filled with high-purity argon gas, and induction heating to 900 DEG C is incubated after ten minutes and immerses in the extremely strong Ga-In-Sn liquid alloy of cooling power with 0.83mm/s withdrawing rate.
(5) structure and performance characterization
Fig. 2 (a) is the Zr that adopts above-mentioned processing condition (5mm diameter, 0.83mm/s withdrawing rate) to prepare
39ti
12cu
9ni
8be
32the microtexture of alloy.Visible, it is uniform-distribution with the phase of needle-like on noncrystal substrate, by XRD analysis (Fig. 2 (b)), finds that this needle-like is ZrBe mutually
2structure, its volume fraction is about 40%.
Fig. 3 is zirconium-based metallic glass situ composite material stress-strain curve, and experiment condition is: sample is 3 × 6mm column sample, and experimental temperature is room temperature (25 DEG C), and compressive strain speed is 2 × 10
-4s
-1.Mechanical experimental results shows: prepared fracture of composite materials intensity exceedes 1900MPa, and compression plasticity reaches 3.2%.
Fact proved, than Single Phase Metal glass and plasticity solid solution phase metal glass composite material in the past, in as cast condition, raw intermetallic compound is ensureing that as the metal glass composite material of second-phase on the basis of breaking tenacity, plasticity is significantly improved, and has realized the good combination of intensity and plasticity.
embodiment 2
Adopt the method identical with embodiment 1, alloying constituent is: Zr
36.5ti
11.2cu
8.5ni
6.8be
37.0.Under 2mm/s withdrawing rate, prepare raw intermetallic compound/bulk metal glass composite material sample in the bar-shaped as cast condition of diameter 5mm.
embodiment 3
Adopt the method identical with embodiment 1, alloying constituent is: Zr
33.5ti
10.8cu
6.4ni
5.3be
44.0.Under 5mm/s withdrawing rate, prepare raw intermetallic compound/bulk metal glass composite material sample in the bar-shaped as cast condition of diameter 8mm.
embodiment 4
Adopt the method identical with embodiment 1, alloying constituent is: Zr
30ti
10cu
6ni
4be
50.Under 5mm/s withdrawing rate, prepare raw intermetallic compound/bulk metal glass composite material sample in the bar-shaped as cast condition of diameter 8mm.
Claims (4)
1. a raw intermetallic compound metal glass composite material in, is characterized in that described matrix material alloying constituent atomic percent expression formula is: Zr
ati
bcu
cni
dbe
e, wherein 30≤a≤39,10≤b≤12,6≤c≤9,4≤d≤8,32≤e≤50, a+b+c+d+e=100, metal glass composite material prepared by described alloying constituent is even dispersion distribution rigid brittle second-phase ZrBe on its glass basis
2.
2. prepare a method for interior raw intermetallic compound metal glass composite material as claimed in claim 1, it is characterized in that said method comprising the steps of:
The first step: choose block metal glass alloy system, according to selecting mutually principle, adjust alloying constituent Zr
ati
bcu
cni
dbe
e, wherein 30≤a≤39,10≤b≤12,6≤c≤9,4≤d≤8,32≤e≤50, a+b+c+d+e=100, make its can first precipitating metal in process of setting between Compound Phase ZrBe
2;
Second step: adopt the method for arc melting, the alloying constituent that the first step is obtained is smelted into mother alloy;
The 3rd step: mother alloy refuse, copper mold is made section bar;
The 4th step: again section bar is put into the crucible of handling well, adopt induction melting to molten state, after insulation, under 0.83-5mm/s withdrawing rate, adopt rapid sequential solidifying process, thereby prepare the matrix material of raw intermetallic compound in the as cast condition that is uniformly distributed different volumes mark on block metal glass matrix.
3. the method for raw intermetallic compound metal glass composite material in preparation according to claim 2, is characterized in that the alloy constituent element purity described in the first step is greater than 99.5%.
4. the method for raw intermetallic compound metal glass composite material in preparation according to claim 2, 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.
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| CN1122148A (en) * | 1993-04-07 | 1996-05-08 | 加利福尼亚技术学院 | Formation of beryllium containing metallic glasses |
| CN101050491A (en) * | 2007-03-16 | 2007-10-10 | 北京科技大学 | Method for preparing porous blocks of metallic glass by electrochemical eroding metal fibers |
| CN101440465A (en) * | 2007-11-20 | 2009-05-27 | 比亚迪股份有限公司 | Zirconium based amorphous alloy and manufacture method thereof |
| CN101629252A (en) * | 2008-07-14 | 2010-01-20 | 南京理工大学 | Plastic bulk metallic glass in situ composite material and method for preparing same |
| 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 |
| WO2011159596A1 (en) * | 2010-06-14 | 2011-12-22 | Crucible Intellectual Property, Llc | Tin-containing amorphous alloy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762502A (en) * | 1993-08-19 | 1995-03-07 | Takeshi Masumoto | Amorphous zirconium alloy having wide region of supercooled liquid |
-
2012
- 2012-10-19 CN CN201210401586.3A patent/CN102912260B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122148A (en) * | 1993-04-07 | 1996-05-08 | 加利福尼亚技术学院 | Formation of beryllium containing metallic glasses |
| CN101050491A (en) * | 2007-03-16 | 2007-10-10 | 北京科技大学 | Method for preparing porous blocks of metallic glass by electrochemical eroding metal fibers |
| CN101440465A (en) * | 2007-11-20 | 2009-05-27 | 比亚迪股份有限公司 | Zirconium based amorphous alloy and manufacture method thereof |
| CN101629252A (en) * | 2008-07-14 | 2010-01-20 | 南京理工大学 | Plastic bulk metallic glass in situ composite material and method for preparing same |
| WO2011159596A1 (en) * | 2010-06-14 | 2011-12-22 | Crucible Intellectual Property, Llc | Tin-containing amorphous alloy |
| 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 (1)
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