CN109112435A - A kind of transformation toughening ZrCu base amorphous composite material and preparation method thereof - Google Patents
A kind of transformation toughening ZrCu base amorphous composite material and preparation method thereof Download PDFInfo
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- CN109112435A CN109112435A CN201810986788.6A CN201810986788A CN109112435A CN 109112435 A CN109112435 A CN 109112435A CN 201810986788 A CN201810986788 A CN 201810986788A CN 109112435 A CN109112435 A CN 109112435A
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 230000009466 transformation Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010891 electric arc Methods 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000005482 strain hardening Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000004807 localization Effects 0.000 abstract description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 229910008008 ZrCo Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical group [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention discloses a kind of transformation toughening ZrCu base amorphous composite material and preparation method thereof, and the atomic ratio of the composite material is Zr50Cu50‑xCox, x is 10 ~ 30；Preparation method is according to Zr50Cu50‑xCoxIngredient is carried out, each multicomponent metallic is placed in arc-melting furnace and carries out melting, after alloy pig is cooling, alloy pig is overturn, is re-melted, repeats to obtain master alloy at least 4 times, after master alloy remelting, by copper mold at blocky Zr50Cu50‑xCoxAmorphous composite material.The material not only has the excellent mechanical property of amorphous itself, such as high breaking strength, big elastic limit etc., and the defects of overcoming inductile caused by brittleness caused by shear band height localization and strain softening, not only there is good plasticity during deformation at room temperature, and show microcosmic work hardening capacity.
Description
Technical field
The present invention relates to a kind of transformation toughening ZrCu base amorphous composite materials and preparation method thereof, belong to amorphous composite material
Preparation technical field.
Background technique
Bulk metallic glass (BMG) is due to becoming structure, function is answered with big elastic limit, high intensity and corrosion resistance
With the ideal chose of material, but since the plastic deformation of glassy metal is realized by height localized shear deformation, fracture
Before the shear band quantity that can start it is extremely limited, the catastrophic brittleness section without macroscopic view plastic deformation can occur at room temperature for BMG
It splits, if the plasticity of ZrCu base noncrystal alloy is about between 0.5-0.7%.Therefore, brittleness at room temperature problem has been developed as BMG
The important bottleneck of material application.
To improve brittleness at room temperature and the room temperature softening when deformation of bulk amorphous alloy material, there are two types of improve non-gold to close at present
The method of golden plasticity, first is that compound second phase improves its plasticity in bulk amorphous alloy, another kind is to pass through addition element
Amorphous composite material is obtained to generate interior raw phase, and is had made some progress.The prior art also has by closing to bulk glass
ZrC, WC, SiC, the Second Phase Particles such as W, to make the plasticity of amorphous alloy composite material make moderate progress, still are introduced in gold
The not big variation of its intensity.
Summary of the invention
The technical problem to be solved by the present invention is to improve the brittleness at room temperature when deformation of ZrCu base lump non-crystalline alloy material
Soften with room temperature, by adding Co element in ZrCu base lump non-crystalline alloy, ZrCu base amorphous is closed in rapid solidification
Can produce B2(CsCl structure in gold) CuZr phase and CoZr phase, and then shear band fast propagation can be inhibited in glass matrix simultaneously
Promote the value-added nano-micrometre grade of multiple shear bands, the ZrCu based alloy with interior raw B2 CuZr phase and CoZr phase shows excellent
Different compression plasticity, high intensity and good work hardening capacity.
The purpose of the present invention is to provide a kind of transformation toughening ZrCu base amorphous composite material, the atomic ratios of the composite material
For Zr50Cu50-xCox, the value range of x is 10 ~ 30.
Another object of the present invention is to provide the preparation methods of the transformation toughening ZrCu base amorphous composite material, specifically
Are as follows: according to Zr50Cu50-xCoxIngredient is carried out, each multicomponent metallic is placed in arc-melting furnace and carries out melting, it is cold to alloy pig
But after, alloy pig is overturn, is re-melted, repeats to obtain master alloy at least 4 times, after master alloy remelting, passes through copper mold
Rodlike Zr is cast in suction50Cu50-xCoxAmorphous composite material.
The purity of each multicomponent metallic raw material used in the present invention is greater than 99.99%.
Preferably, electric arc furnaces is evacuated to vacuum degree 5*10 in fusion process of the present invention-5Pa, then filling purity again is
99.9999% Ar gas is to an atmospheric pressure.
The principle of the present invention: the present invention in ZrCu amorphous alloy by adding suitable Co element, thus at room temperature
Stable B2 CuZr phase and CoZr phase are obtained, and has the generation of B19 ' CuZr phase and B33 CoZr phase when deformation occurs, from
And " phase-change induced plastic " (TRIP) effect is introduced into amorphous composite material, amorphous ZrCu base matrix can be effectively compensated for
Strain softening.Both phase transition obtain to overcome amorphous alloy brittleness at room temperature and strain softening to provide new thinking
Stretching plastic and work hardening capacity greatly is obtained, the potential structure application of amorphous alloy is greatly improved.
Beneficial effects of the present invention: the present invention utilizes Zr made from quick setting method50Cu50-xCoxAmorphous composite material,
The material not only has excellent mechanical property of amorphous itself, such as high breaking strength, big elastic limit etc., Er Qieke
The defects of having taken inductile caused by brittleness caused by shear band height localization and strain softening, during deformation at room temperature not
Only there is good plasticity, and show microcosmic work hardening capacity.
Detailed description of the invention
Fig. 1 is Zr50Cu25Co25The light microscopic figure (OM) of amorphous composite material；
Fig. 2 is Zr50Cu25Co25The XRD diffraction pattern of amorphous composite material deformation front and back；
Fig. 3 is Zr50Cu25Co25The room temperature mechanics compression stress strain curve figure of amorphous composite material；
Fig. 4 is Zr50Cu25Co25Amorphous composite material compresses profile scanning figure.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
The preparation method of transformation toughening ZrCu base amorphous composite material described in the embodiment of the present invention, specifically: according to
Zr50Cu50-xCoxIngredient is carried out, each multicomponent metallic is placed in clean water cold crucible, electric arc furnaces is evacuated to vacuum degree 5*10- 5Then Pa fills the Ar gas that purity is 99.9999% to an atmospheric pressure again；It opens electric arc furnaces and is heated to prepared alloy melting point
More than, after alloy pig is cooling, alloy pig is overturn, is re-melted, is at least repeated 4 times to guarantee that alloy is uniformly mixed
To master alloy；After master alloy remelting, by copper mold at blocky Zr50Cu50-xCoxA length of 70mm of amorphous composite material,
Diameter is 2mm.
The selection of raw material:
Table 1 prepares the purity (%) that master alloy ingot selects metal constituent element
The performance of the different atomic ratio respective materials of table 2
By embodiment 1 ~ 7 it can be seen that increasing with Co content, ZrCuCo alloy first increases before deformation, when Co content reaches
Reach highest when to 25at%, then hardness slowly reduces again, this is because the B2 generated when Co content reaches 25at%
(Cu/Co) Zr phase content highest.After deformation occurs, its intensity has increase after generating processing hardening.Compression strength and compression
Rate has increase, because the B2 ZrCu phase transition of generation is B19 ' phase, and the B2 ZrCo phase generated turns in ZrCuCo alloy
Become B33 phase, " deformation induced trans- formation " has occurred then " phase transformation causes plasticity ".
Below with Zr50Cu25Co25Micro-structure diagram is combined to carry out analytic explanation for amorphous composite material:
Fig. 1 is Zr50Cu25Co25It is non-can clearly to find out that crystal phase is embedded in by figure for the light microscopic figure (OM) of amorphous composite material
In crystal phase.
Fig. 2 is Zr50Cu25Co25The XRD diffraction pattern of amorphous composite material, it is main before deformation occurs as seen from the figure
To be mutually B2 CuZr phase and CoZr phase, and there is B19 ' CuZr phase to generate after deformation with B33 CoZr phase, this illustrates in deformation
The generation of deformation induced trans- formation has occurred in the process: B2 CuZr phase transition is B19 ' CuZr phase；B2 CoZr phase transition is B33
CoZr phase.
Fig. 3 is Zr50Cu25Co25The room temperature mechanics compression stress strain curve figure of amorphous composite material, as seen from the figure
The compressive strength of the alloy is 2.3 GPa, and compression ratio is 18.3 %, hence it is evident that is higher than amorphous alloy, this is because compressing
Deformation has occurred in deformation process and causes phase transformation, and then phase-change induced plastic improves.And intensity raising is since crystal phase is being sent out
Processing hardening phenomenon is generated in raw deformation process.
Fig. 4 is Zr50Cu25Co25Amorphous composite material compresses profile scanning figure, as can be seen from Figure in Zr50Cu25Co25
There are three types of pattern, train of thought shape regions, molten drop shape regional peace skating area domain for the compression section of sample.What amorphous alloy occurred when being broken
Train of thought shape style and molten drop shape structure feature can be explained with " free volume+adiabatic heating " model.The process of room temperature compression
It is the ever-increasing process of free volume in shear band, when moment fracture occurs for material, the elastic strain stored in alloy is strained
It can be released in the environment of insulation, a large amount of heat can not distribute in time, be driven in entire shear band in a very short period of time
Temperature increases rapidly, and the raising of temperature causes the reduction of alloy viscosity, and leaves train of thought shape style and molten drop in fracture surface
The viscous rheology characteristic of shape structure；Smooth region is the feature that crystal phase is broken, and these crystal phases should be B19 ' CuZr
Phase and B33 CoZr phase.
Claims (3)
1. a kind of transformation toughening ZrCu base amorphous composite material, it is characterised in that: the atomic ratio of the composite material is Zr50Cu50- xCox, x is 10 ~ 30.
2. the preparation method of transformation toughening ZrCu base amorphous composite material described in claim 1, it is characterised in that: according to
Zr50Cu50-xCoxIngredient is carried out, each multicomponent metallic is placed in arc-melting furnace and carries out melting, it, will after alloy pig is cooling
Alloy pig is overturn, and is re-melted, and repeats to obtain master alloy at least 4 times, blocking by copper mold after master alloy remelting
Shape Zr50Cu50-xCoxAmorphous composite material.
3. the preparation method of transformation toughening ZrCu base amorphous composite material according to claim 2, it is characterised in that: melting
Electric arc furnaces is evacuated to vacuum degree 5*10 in journey-5Then Pa fills the Ar gas that purity is 99.9999% to an atmospheric pressure again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810986788.6A CN109112435A (en) | 2018-08-28 | 2018-08-28 | A kind of transformation toughening ZrCu base amorphous composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810986788.6A CN109112435A (en) | 2018-08-28 | 2018-08-28 | A kind of transformation toughening ZrCu base amorphous composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110195173A (en) * | 2019-06-06 | 2019-09-03 | 浙江大学 | A kind of hydrogen isotope storage alloy and preparation method thereof |
| CN114318179A (en) * | 2020-10-09 | 2022-04-12 | 华中科技大学 | Preparation method of high-strength super-toughness amorphous alloy composite material with bionic structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4135924A (en) * | 1977-08-09 | 1979-01-23 | Allied Chemical Corporation | Filaments of zirconium-copper glassy alloys containing transition metal elements |
| JP5685761B2 (en) * | 2011-01-31 | 2015-03-18 | 株式会社真壁技研 | Zr-based metallic glass alloy containing no Cu |
| CN105401105A (en) * | 2015-11-17 | 2016-03-16 | 山东大学（威海） | High-strength high-plasticity Cu-Zr-Zn amorphous composite and preparation method |
-
2018
- 2018-08-28 CN CN201810986788.6A patent/CN109112435A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4135924A (en) * | 1977-08-09 | 1979-01-23 | Allied Chemical Corporation | Filaments of zirconium-copper glassy alloys containing transition metal elements |
| JP5685761B2 (en) * | 2011-01-31 | 2015-03-18 | 株式会社真壁技研 | Zr-based metallic glass alloy containing no Cu |
| CN105401105A (en) * | 2015-11-17 | 2016-03-16 | 山东大学（威海） | High-strength high-plasticity Cu-Zr-Zn amorphous composite and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| F.A. JAVID 等: ""Martensitic transformation and thermal cycling effect in Cu–Co–Zr alloys"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| S. PAULY等: ""Microstructural Evolution and Mechanical Behaviour of Metastable CueZreCo Alloys"", 《JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110195173A (en) * | 2019-06-06 | 2019-09-03 | 浙江大学 | A kind of hydrogen isotope storage alloy and preparation method thereof |
| CN114318179A (en) * | 2020-10-09 | 2022-04-12 | 华中科技大学 | Preparation method of high-strength super-toughness amorphous alloy composite material with bionic structure |
| CN114318179B (en) * | 2020-10-09 | 2022-12-09 | 华中科技大学 | Preparation method of high-strength super-toughness amorphous alloy composite material with bionic structure |
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Application publication date: 20190101 |