CN106756646B - A kind of Strengthening and Toughening metal glass composite material and preparation method thereof - Google Patents
A kind of Strengthening and Toughening metal glass composite material and preparation method thereof Download PDFInfo
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- CN106756646B CN106756646B CN201611007102.1A CN201611007102A CN106756646B CN 106756646 B CN106756646 B CN 106756646B CN 201611007102 A CN201611007102 A CN 201611007102A CN 106756646 B CN106756646 B CN 106756646B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
Abstract
The invention discloses a kind of Strengthening and Toughening metal glass composite materials and preparation method thereof, and preparation method is as follows：（1）SelectionβZr/ metal glass composite materials orβTi/ metal glass composite materials are basic alloy；（2）Add 0.5 2%（Weight percent）Zirconium oxide or titanium dioxide powder；（3）Base alloy is broken into powder, and the zirconium oxide or titanium dioxide powder that add are uniformly mixed, is put into sensing in crucible and is heated to melting, and implement rapid sequential solidification, and then obtain the metal glass composite material with core-shell structure precipitated phase.The present invention is prepared for the large scale metal glass composite material of high-strength and high ductility, which has significant work hardening capacity and excellent tensile strength and plasticity.
Description
Technical field
The invention belongs to metal-base composites technical fields, and in particular to a kind of glassy metal composite wood of high-strength and high ductility
Material and preparation method thereof.
Background technology
Block metal glass (BMG) has high intensity, high rigidity, low elasticity modulus and big elastic strain limit etc. one
Series is different from the excellent mechanical performance of traditional crystal alloy so that it is considered as the structural material of great potential.It is however, high
The shearing behavior of degree localization causes BMG material in the case of unapparent room temperature macroscopic view plastic deformation, with catastrophic failure
Calamitous fracture occurs for mode, this seriously restricts large-scale applications of the BMG as advanced configuration material in engineering.Cause
This, brittleness at room temperature problem has been developed as the important bottleneck of BMG material application.
To improve the brittleness at room temperature of BMG material, Johnson research groups of U.S. first passage is in Zr-Ti-Cu- within 2000
Nb alloy elements are added in Ni-Be alloy systems, prepare the BMG composite woods of micron-scale β-Zr (Ti) solid solution phase plasticising
Material, stretching plastic strain reach 3%.Then, Chen Guang et al. is by carrying out at nodularization dendrite β-Zr (Ti) phases solid solution
Reason, more than 6% is increased to by the stretching plastic of BMG composite materials（Large scale metal glass composite material with stretching plastic and
Preparation method, number of patent application 201110099685.6）.But the acquisition of the plasticity of above-mentioned metal glass composite material, greatly
Amplitude reduction intensity.
Invention content
The purpose of the present invention is to provide a kind of metal glass composite material intensity, with excellent stretching plastic and by force
Degree.
The Strengthening and Toughening metal glass composite material of the present invention, selectionβ- Zr/ metal glass composite materials orβ- Ti/ metal glass
Glass composite material is basic alloy, and typical alloy system is Zr-Ti-Nb-Cu-Ni-Be and Ti-Zr-V-Cu-Be.Addition
Zirconium oxide or titanium dioxide powder regulate and control metal glass composite material microstructure, obtain and sink with core-shell structure as presoma
The high-strength and high ductility metal glass composite material of shallow lake phase.
The weight of the addition precursor powder is 0.5-2%, and the granularity of powder is 1-15 μm.
The invention also discloses the preparation method of the Strengthening and Toughening metal glass composite material, specific preparation processes
For：
The first step：It is matched according to the predetermined ingredient of base alloy, non-consumable is used first under argon atmosphere
Arc melting is uniform；
Second step：Base alloy is broken into powder, and adds corresponding zirconium oxide or titanium dioxide powder is uniformly mixed, is put
Enter in graphite crucible, sensing heating, using the High temperature diffusion of oxygen element, makes the zirconium oxide or titania precursor of addition to 2000 DEG C
It is dystectic that body powder is changed into elevated oxygen levelα- Zr orα- Ti phases, and regulate and control to be precipitated by soaking timeα- Zr orα- Ti is dissolved
The size of body phase.
Third walks：Using apparatus for directional solidification, implement rapid sequential solidification under 4mm/s withdrawing rates, in process of setting,
First it is precipitatedα- Zr orα- Ti will be used as forming core core, promoteβ- Zr orβThe precipitation of-Ti, and then obtain and sink with core-shell structure
Shallow lake phase（α-Zr/β- Zr orα-Ti/β-Ti）Metal glass composite material.The room temperature tensile of the metal glass composite material is bent
Take intensity >=1350MPa, stretching plastic >=5%.
Compared with prior art, the present invention its remarkable advantage：Zirconium oxide or titanium dioxide powder are added as presoma, in height
Oxygen element diffusion transformation is temperature downα- Zr orα- Ti so as to be used as forming core core, in subsequent process of setting, is formedα-Zr/β- Zr orα-Ti/β- Ti core-shell structures improve composite material strength, are combined so as to fulfill the strong modeling of metal glass composite material,
Prepare the metal glass composite material of high-strength and high ductility.
Description of the drawings
Fig. 1 is the flow chart of metal glass composite material preparation method of the present invention.
Fig. 2 is macroscopical sample drawing of 1 metal glass composite material of the embodiment of the present invention.
Fig. 3 is the micro-structure diagram of 1 metal glass composite material of the embodiment of the present invention.
Fig. 4 is the XRD diffraction patterns of 1 metal glass composite material of the embodiment of the present invention.
Fig. 5 is the room temperature tensile load-deformation curve of 1 metal glass composite material of the embodiment of the present invention.
Specific embodiment
With reference to Fig. 1, Strengthening and Toughening metal glass composite material of the present invention, selectionβ- Zr/ metal glass composite materials orβ-Ti/
Metal glass composite material is basic alloy, and typical alloy system is Zr-Ti-Nb-Cu-Ni-Be and Ti-Zr-V-Cu-
Be.The content for adding zirconium oxide or titanium dioxide powder presoma is 0.5-2%（Weight percent）, the granularity of powder is 1-15 μ
m。
The preparation method of the Strengthening and Toughening metal glass composite material, specific preparation process are：
The first step：It chooses purity and is more than 99.5% alloying element, matched according to the predetermined ingredient of base alloy, first
It is uniform using non-consumable arc furnace melting under argon atmosphere；
Second step：Base alloy is broken into powder, and adds corresponding zirconium oxide or titanium dioxide powder is uniformly mixed, is put
Enter in graphite crucible, sensing heating, using the High temperature diffusion of oxygen element, makes the zirconium oxide or titania precursor of addition to 2000 DEG C
It is dystectic that body powder is changed into elevated oxygen levelα- Zr orα- Ti phases, and regulate and control to be precipitated by soaking timeα- Zr orα- Ti is dissolved
The size of body phase.
Third walks：Using apparatus for directional solidification, implement rapid sequential solidification under 4mm/s withdrawing rates, in process of setting,
First it is precipitatedα- Zr orα- Ti will be used as forming core core, promoteβ- Zr orβThe precipitation of-Ti, and then obtain and sink with core-shell structure
Shallow lake phase（α-Zr/β- Zr orα-Ti/β-Ti）Metal glass composite material.
The specific implementation process of the present invention is as follows：
(1) selection and design of base alloy system and ingredient：
Selection can be formed firstβ- Zr orβThe metal glass composite material of-Ti forms system, such as：Zr-Ti-Nb-Cu-Ni-
Be and Ti-Zr-V-Cu-Be etc., specific ingredient can be selected and designed according to patent ZL201110099685.6；Its main feature is that
The alloy system and ingredient of selection can be precipitated during solidificationβ- Zr orβ- Ti solid solution phases.
(2) base alloy melting：
According to（1）Obtained alloying component, by raw material of the purity more than 99.5% using non-under argon atmosphere
Consumable electroarc furnace melting is uniform.
(3) oxide adds：
It will（2）The base alloy of gained is broken into powder, then adds corresponding zirconium oxide or titanium dioxide powder is uniformly mixed,
It is put into graphite crucible, graphite crucible is placed in vacuum induction melting furnace, be evacuated to 2 × 10-3After Pa, sensing heating is extremely
2000 DEG C, using the High temperature diffusion of oxygen element, the zirconium oxide or titania precursor body powder for making addition are changed into elevated oxygen level, height
Fusing pointα- Zr orα- Ti phases, and regulate and control to be precipitated by soaking timeα- Zr orαThe size of-Ti solid solution phases.
(4) rapid sequential solidifies：
Alloy in molten state is immersed into the extremely strong Ga-In-Sn liquid of cooling capacity with crucible with the withdrawing rate of 4mm/s
In state alloy, rapid sequential solidification is realized.
(5) structure and performance characterization：
Microstructure characterization is carried out, and further carry out mechanics to it to the composite material of preparation using XRD, DSC and SEM
Performance characterization, to determine the composite material microstructure with best comprehensive mechanical property and its corresponding preparation technology parameter.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
(1) selection of raw material
The present invention prepares the purity such as table 1 of each metal constituent element of base alloy selection, alloying component Zr60Ti14.6Nb5.4C
u5.6Ni4.4Be10(atomic percent).Zirconium oxide powder of the presoma of addition for 15 μm of granularities.
Table 1 prepares the purity (%) that base alloy selects metal constituent element
(2) preparation of base alloy
Under high-purity argon gas protective condition, master alloy is melted with non-consumable arc-melting furnace and buckles ingot, specific procedure is as follows：
A, it is standby according to designed composition proportion material after the surface mechanical grinding of raw metal being removed the oxide skin on surface
Material；The material prepared is put into the water jacketed copper crucible in smelting furnace according to the weight of every ingot 80g or so, bell is covered and is evacuated to
2×10-3Pa；The high-purity argon gas of a certain amount of pressure is filled with into stove（99.99%）, argon pressure ranging from 0.4 ~ 0.6MPa.
B, multi-pass melting base alloy：Using non-consumable arc furnace by Zr, Nb high-melting-point constituent element in function composite by electromagnetic stirring
Under melt 2 ~ 3 times together, then by all alloying components together melting 3 ~ 4 times, obtain uniformly mixed base alloy.During melting
The electric current used is 500 ~ 650A, and the voltage that electromagnetic agitation uses is 1 ~ 3V.
(3) oxide adds
Base alloy is broken into essence into particle, then pulverize using sledgehammer, adds in the zirconia powder of 1% weight percent
End is uniformly mixed, and is fitted into the graphite crucible of internal diameter 26mm, 2 millimeters of wall thickness after cleaning, drying, graphite crucible is in advance at 200 DEG C
It is 1 hour dry in baking oven.Graphite crucible is put into vacuum induction melting furnace, is evacuated to 2 × 10-3Then Pa is initially added into
20 minutes are kept the temperature to 2000 DEG C.
(4) rapid sequential solidifies
Alloy in molten state with crucible is immersed with the withdrawing rate of 4mm/s in Ga-In-Sn liquid alloys, is realized
Rapid sequential solidifies.
(5) structure and performance characterization
Fig. 2 is the metal glass composite material sample of a diameter of 26mm prepared by above-mentioned technique.Fig. 3 and 4 is composite wood
The microscopic structure and XRD spectrum of material, it show composite material be byα-Zr/β- Zr core-shell structures precipitated phase and glassy metal base
Body forms.
Fig. 5 is the tensile stress-strain curve of a diameter of 3mm composite materials of gauge length, it can be seen that has shell-nuclear compounded material
The tensile yield strength of material and plastic strain respectively reach 1440MPa and 6.8%, far above not adding zirconium oxide
Zr60Ti14.6Nb5.4Cu5.6Ni4.4Be10Alloy.
It is above-mentioned it turns out that, compared to existing metal glass composite material and its technique, the present invention utilizes oxide precursor
Metal glass composite material prepared by body has novel core-shell structure precipitated phase, and the intensity of composite material is greatly improved,
Realize the good combination of intensity and plasticity.
Embodiment 2
Using method same as Example 1, base alloy ingredient is Zr60Ti14.6Nb5.4Cu5.6Ni4.4Be10(atom hundred
Divide ratio), addition 0.5%（Weight percent）10 μm of granularities titanium dioxide powder.The room temperature tensile surrender of the composite material is strong
Degree and plastic strain respectively reach 1350MPa and 7.3%.
Embodiment 3
Using method same as Example 1, base alloy ingredient is Zr60Ti14.6Nb5.4Cu5.6Ni4.4Be10(atom hundred
Divide ratio), addition 2%（Weight percent）5 μm of granularities titanium dioxide powder.The room temperature tensile yield strength of the composite material
1530MPa and 5.1% are respectively reached with plastic strain.
Embodiment 4
Using method same as Example 1, base alloy ingredient is Ti62Zr15V10Cu4Be9(atomic percent), addition
1%（Weight percent）The titanium dioxide powder of 15 μm of granularities.The room temperature tensile yield strength of the composite material and plastic strain point
1400MPa and 6.7% are not reached.
Embodiment 5
Using method same as Example 1, base alloy ingredient is Ti62Zr15V10Cu4Be9(atomic percent), adds
Add 0.5%（Weight percent）The Zirconium oxide powder of 10 μm of granularities.The room temperature tensile yield strength and plasticity of the composite material should
Change respectively reaches 1370MPa and 8.6%.
Embodiment 6
Using method same as Example 1, base alloy ingredient is Ti62Zr15V10Cu4Be9(atomic percent), adds
Add 2%（Weight percent）The Zirconium oxide powder of 1 μm of granularity.The room temperature tensile yield strength of the composite material and plastic strain
Respectively reach 1550MPa and 5.3%.
Claims (3)
1. a kind of preparation method of Strengthening and Toughening metal glass composite material, which is characterized in that including：
The first step：It is matched according to the predetermined ingredient of base alloy, non-consumable electric arc is used first under argon atmosphere
Stove melting is uniform；The base alloy system is Zr-Ti-Nb-Cu-Ni-Be and Ti-Zr-V-Cu-Be；
Second step：Base alloy is broken into powder, and adds zirconium oxide or oxygen that corresponding weight percentage is 0.5-2%
Change titanium powder to be uniformly mixed, be put into graphite crucible, sensing heating regulates and controls solid solution is precipitated to 2000 DEG C, and by soaking time
The size of phase；
Third walks：Using apparatus for directional solidification, implement rapid sequential solidification under 4mm/s withdrawing rates, in process of setting, first analyse
Go outα- Zr orα- Ti will be used as forming core core, promoteβ- Zr orβThe precipitation of-Ti, and then obtain with core-shell structure precipitated phase
Metal glass composite material.
2. the preparation method of Strengthening and Toughening metal glass composite material according to claim 1, it is characterised in that：The metal
Room temperature tensile yield strength >=1350MPa of glass composite material, stretching plastic >=5%.
3. the preparation method of Strengthening and Toughening metal glass composite material according to claim 1, it is characterised in that：The oxidation
The granularity of zirconium or titanium dioxide powder is 1-15 μm.
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| JP2002105609A (en) * | 2000-09-26 | 2002-04-10 | Japan Science & Technology Corp | High hydrogen storage alloy and its manufacturing method |
| 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 |
| CN105886965A (en) * | 2016-05-06 | 2016-08-24 | 西北工业大学 | Element N and O co-doped ti-based amorphous composite and preparation method thereof |
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2016
- 2016-11-16 CN CN201611007102.1A patent/CN106756646B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105609A (en) * | 2000-09-26 | 2002-04-10 | Japan Science & Technology Corp | High hydrogen storage alloy and its manufacturing method |
| 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 |
| CN105886965A (en) * | 2016-05-06 | 2016-08-24 | 西北工业大学 | Element N and O co-doped ti-based amorphous composite and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Microstructure and Fracture Behavior of Zr55Cu30A110Ni5 Bulk Metallic Glass and Its Composites Containing ZrO2;Chu Zhenhua et al.;《Rare Metal Materials and Engineering》;20110531;第40卷(第5期);第766-767页 * |
| ZrO2增强Zr基大块非晶复合材料制备工艺探索及其力学性能研究;张鉴;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090915(第9期);第23-25页 * |
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