CN108504966A - A kind of cobalt-base body amorphous alloy and preparation method thereof - Google Patents
A kind of cobalt-base body amorphous alloy and preparation method thereof Download PDFInfo
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- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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Abstract
The present invention relates to a kind of cobalt-base body amorphous alloys and preparation method thereof in non-crystaline amorphous metal field.Its block amorphous alloy ingredient is Cox‑Moy‑Bz, x, y, z is atomic percent, wherein 59≤x≤67,17≤y≤28,11≤z≤19, and x+y+z=100, such as Co64Mo22B14, Co59Mo28B13Deng.The block amorphous alloy has the characteristics that superhigh intensity, high amorphous formation ability, good thermal stability, corrosion resistance and soft magnet performance, and without elements such as rare precious metal Ta, Nb, manufacturing cost is cheap, is suitable for the application fields such as high tensile metal structural member, corrosion-proof wear coating, magnetic elements.
Description
Technical field
The present invention is to belong to amorphous alloy material field, relates generally to a kind of new ternary cobalt-base body amorphous alloy and its system
Preparation Method.Particularly point out is a kind of superhigh intensity, high amorphous formation ability, excellent corrosion resistance and good soft magnet performance
Ternary block amorphous alloy.
Background technology
Non-crystaline amorphous metal is because of its atomic arrangement longrange disorder, the unique texture of shortrange order so that non-crystaline amorphous metal has high
Intensity and hardness, good wearability and processing performance and excellent corrosion resistance.It is generally that amorphous three-dimensional dimension is big
It is known as block amorphous alloy in 1mm, in numerous block amorphous alloys, cobalt-base body amorphous alloy possesses higher intensity, good
Good corrosion resistance and soft magnet performance.However, the cobalt base amorphous alloy Forming ability of early-stage development is relatively low, product master
To exist in the form of strip, filiform etc..Until 2000, Co is developed in Inoue etc.40Fe22Nb6Zr2B30The block of diameter 1mm
After non-crystaline amorphous metal（Materials Transactions Jim. 2000, 41 (9) :1256-1262）, it is non-to realize cobalt-based
The breakthrough of peritectic alloy existence form, into bulk amorphous alloy ranks.Then, micro- Er is introduced into Men in 2006 et al.
In cobalt base amorphous alloy, the Co that critical dimension is up to 10mm is developed48Cr15Mo14C15B6Er2Block amorphous alloy (Journal
of Matreials Research. 2006, 21 (4) :958-961), it is opened for the research of cobalt-base body amorphous alloy
The new situation.
In order to further increase cobalt-base body amorphous mechanical property, it is non-that Zhang Tao in 2011 has developed Co-Ta-B blocks
Crystal system（Journal of Materials Research. 2011, 26 (16) :2072-2079）, fracture strength height
Up to 6GPa, but its plasticity only has 0.5%, seriously limits its engineer application and further development.2012, Shen Baolong et al. was opened
Send out (Co1-xFex)68B21.9Si5.1Nb5（Intermetallics. 23 (2012) 63-67）Non-crystaline amorphous metal, temperature-room type plasticity
Certain promotion has been obtained, 1.3% plastic strain is reached.However, the intensity of such alloy but integrally reduces.It continues thereafter with out
Co-Nb-B non-crystaline amorphous metal systems are sent out（Journal of Non-Crystalline Solids. 386 (2014) 121–
123）, maximum intensity has reached 5200MPa, and has very high amorphous formation ability, and critical dimension reaches 2mm, plasticity
Also it is greatly improved.However, often contain rare precious metal, such as Ta, Nb in developed cobalt-base body amorphous alloy at present, this
Its development space and application space are limited to a certain extent.Therefore, development of high strength, low cost and good corrosion resistance is had both
With the cobalt-base body amorphous alloy material of soft magnet performance, there is important theoretical research value and practical application meaning.
Invention content
In view of this, it is an object of the invention to：（1）There is provided a kind of strong cobalt-base body amorphous alloy of completely new ternary superelevation and
Preparation method；（2）There is superhigh intensity, high amorphous formation energy by cobalt-base body amorphous alloy material prepared by the method
The advantages that power, excellent corrosion resistance and good soft magnet performance；(3) current high-strength cobalt-base body amorphous alloy body is not contained
The rare precious metals such as common Ta, Nb in system, develop a kind of cobalt-base body amorphous alloy system that cost is more cheap.
In order to achieve the above objectives, the present invention provides the following technical solutions：
A kind of cobalt-base body amorphous alloy, which is characterized in that the cobalt-base body amorphous ingredient Cox-Moy-BzIn system, x,
Y, z is atomic percent, 59≤x≤67,17≤y≤28,11≤z≤19.The cobalt-base body amorphous alloy is by single
Amorphous phase is formed, and cut off diameter is 1 ~ 2mm；The fracture strength of the cobalt-base body amorphous alloy be 4.8GPa ~
5.4GPa, plastic deformation amount are 4%；Corrosion electric current density of the cobalt-base body amorphous alloy in 3.5%NaCl solution be
3.94μA/cm2~7.55μA/cm2；The glass transformation temperature of the cobalt-base body amorphous alloy is 818 ~ 847K.
According to the preparation method of above-mentioned cobalt-base body amorphous alloy, comprise the following steps：
（1）Tri- kinds of high-purity raw materials of Co, Mo, B, and gold of polishing are weighed according to the ingredient of above-mentioned cobalt-base body amorphous alloy
Belong to Co and metal Mo surface scales, ensures that each material purity need to be higher than 99.9%.
（2）Prepared raw material is put into vacuum arc furnace ignition first；Then 4 × 10 are evacuated to-3Pa is hereinafter, be re-filled with
0.05MPa argon gas continues to be evacuated to 4 × 10-3Pa or less is re-filled with 0.2MPa argon gas；Then the argon for being 99.999% in purity
Melting five to seven times under gas shielded atmosphere so that alloying component is uniform, obtains master alloy ingot；It is finally that master alloy ingot is completely molten
Change, the lining bar of cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology.
Further, step（1）The purity of tri- kinds of high-purity raw materials of Co, Mo, B is all higher than 99.9%.
Further, step（2）The sample that cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology
Stick.
The beneficial effects of the present invention are：It is the fracture strength of critical dimension, 4.8GPa ~ 5.4MPa with 1 ~ 2mm, good
Temperature-room type plasticity, high glass transformation temperature；In addition, in mass fraction is 3.5%NaCl solution, low corrosion current is shown as
Density and wide passivation section, have good corrosion resistance；Without containing normal in current high-strength cobalt-base body amorphous alloy system
The rare precious metals such as Nb, Ta, Cox-Moy-BzCost is more cheap；The block amorphous alloy for preparing the present invention uses vacuum electric
The smelting technology of arc stove, then block amorphous alloy lining bar is prepared with water cooled copper mould flash set technology, preparation process is simple.
Description of the drawings
In order to keep the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides following attached drawing and carries out
Explanation：
Fig. 1 is the Co of embodiment 164Mo22B14The XRD spectrum of block amorphous alloy.
Fig. 2 is the Co of embodiment 164Mo22B14The compression stress strain curve figure of block amorphous alloy
Fig. 3 is the Co of embodiment 164Mo22B14Block amorphous alloy dynamic potential polarization curve.
Fig. 4 is the Co of embodiment 259Mo28B13The XRD spectrum of block amorphous alloy.
Fig. 5 is the Co of embodiment 259Mo28B13Block amorphous alloy dynamic potential polarization curve.
Fig. 6 is the Co of embodiment 359Mo24B17、Co60Mo26B14、Co65Mo24B11Block amorphous alloy DTA figures.
Specific implementation mode
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
Embodiment 1
Prepare Co64Mo22B14Bulk amorphous alloy
（1）According to Co64Mo22B14The ingredient of cobalt-base body amorphous alloy weighs tri- kinds of high-purity raw materials of Co, Mo, B, and beats
Metal Co and metal Mo surface scales are ground, ensures that each material purity need to be higher than 99.9%.
（2）Prepared raw material is put into vacuum arc furnace ignition first；Then 4 × 10 are evacuated to-3Pa is hereinafter, be re-filled with
0.05MPa argon gas continues to be evacuated to 4 × 10-3Pa or less is re-filled with 0.2MPa argon gas；Then the argon for being 99.999% in purity
Melting five to seven times under gas shielded atmosphere so that alloying component is uniform, obtains master alloy ingot；It is finally that master alloy ingot is completely molten
Change, the lining bar of cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology.
By Co made from embodiment 164Mo22B14Block amorphous alloy bar is analyzed through X-ray diffraction (XRD), such as Fig. 1 institutes
The Co shown64Mo22B14Block amorphous alloy XRD spectrum, result shows as the typical diffusing scattering peak packet of non-crystalline material in figure, without bright
Aobvious crystal peak can illustrate the ingredient by single amorphous phase composition in XRD accuracy ratings, and amorphous formation critical dimension is
Diameter 2mm.
By Co made from embodiment 164Mo22B14Block amorphous alloy bar carries out Compressive Mechanical experimental analysis, such as Fig. 2 institutes
Show Co64Mo22B14Block amorphous alloy compression stress strain curve, the results showed that Co64Mo22B14The fracture of block amorphous alloy is strong
Degree is 5250MPa, and plastic strain is about 4%.
By Co made from embodiment 164Mo22B14Block amorphous alloy bar is in the NaCl solution that mass fraction is 3.5%
Carry out electrochemistry experiment, Co as shown in Figure 364Mo22B14The dynamic potential polarization curve figure of block amorphous alloy, the results showed that,
Co64Mo22B14Block amorphous alloy has apparent passivation region, belongs to homogeneous corrosion, corrosion electric current density is about 7.55 μ A/
cm2。
Embodiment 2
Prepare Co59Mo28B13Bulk amorphous alloy
（1）According to Co59Mo28B13The ingredient of cobalt-base body amorphous alloy weighs tri- kinds of high-purity raw materials of Co, Mo, B, and beats
Metal Co and metal Mo surface scales are ground, ensures that each material purity need to be higher than 99.9%.
（2）Prepared raw material is put into vacuum arc furnace ignition first；Then 4 × 10 are evacuated to-3Pa is hereinafter, be re-filled with
0.05MPa argon gas continues to be evacuated to 4 × 10-3Pa or less is re-filled with 0.2MPa argon gas；Then the argon for being 99.999% in purity
Melting five to seven times under gas shielded atmosphere so that alloying component is uniform, obtains master alloy ingot；It is finally that master alloy ingot is completely molten
Change, the lining bar of cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology.
By Co made from embodiment 259Mo28B13Block amorphous alloy bar is analyzed through X-ray diffraction (XRD), such as Fig. 4 institutes
Show Co59Mo28B13The XRD spectrum of block amorphous alloy, result shows as the typical diffusing scattering peak packet of non-crystalline material in figure, wherein
There is not apparent crystal peak, can illustrate the ingredient by single amorphous phase composition, maximum amorphous in XRD accuracy ratings
Formation size is diameter 1.5mm.
By Co made from embodiment 259Mo28B13Block amorphous alloy bar is in the NaCl solution that mass fraction is 3.5%
Carry out electrochemistry experiment, Co as shown in Figure 559Mo28B13The dynamic potential polarization curve figure of block amorphous alloy, the results showed that,
Co59Mo28B13Apparent passivation section is presented in block amorphous alloy, belongs to typical homogeneous corrosion, corrosion electric current density is about
3.94μA/cm2。
Embodiment 3
Prepare Co59Mo24B17、Co60Mo26B14、Co65Mo24B11Block amorphous alloy
（1）According to Co59Mo24B17、Co60Mo26B14、Co65Mo24B11The ingredient of cobalt-base body amorphous alloy weighs Co, Mo, B tri-
Kind high-purity raw material, and polish metal Co and metal Mo surface scales ensure that each material purity need to be higher than 99.9%.
（2）Prepared raw material is put into vacuum arc furnace ignition first；Then 4 × 10 are evacuated to-3Pa is hereinafter, be re-filled with
0.05MPa argon gas continues to be evacuated to 4 × 10-3Pa or less is re-filled with 0.2MPa argon gas；Then the argon for being 99.999% in purity
Melting five to seven times under gas shielded atmosphere so that alloying component is uniform, obtains master alloy ingot；It is finally that master alloy ingot is completely molten
Change, the lining bar of cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology.
By the Co of diameter 1mm made from embodiment 359Mo24B17、Co60Mo26B14、Co65Mo24B11Three kinds of non-crystaline amorphous metals carry out
DTA is analyzed, Co as shown in Figure 659Mo24B17、Co60Mo26B14、Co65Mo24B11Block amorphous alloy DTA curve, the results showed that, it should
It is 818 ~ 847K that serial cobalt-base body amorphous alloy, which has significant glass transition and crystallization phenomenon, glass transformation temperature Tg,
Crystallization initial temperature Tx is 911 ~ 920K, has high thermal stability.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (4)
1. a kind of cobalt-base body amorphous alloy, which is characterized in that the cobalt-base body amorphous alloy ingredient Cox-Moy-BzSystem
In, x, y, z is atomic percent, wherein 59≤x≤67,17≤y≤28,11≤z≤19；The cobalt-base body amorphous conjunction
Gold is made of single amorphous phase, the critical a diameter of 1 ~ 2mm of amorphous formation；The fracture of the cobalt-base body amorphous alloy
Intensity is 4.8GPa ~ 5.4GPa, and plastic deformation amount is 4%；Corruption of the cobalt-base body amorphous alloy in 3.5%NaCl solution
Erosion current density is 3.94 μ A/cm2~7.55μA/cm2；The glass transformation temperature of the cobalt-base body amorphous alloy be 818 ~
847K。
2. the preparation method of cobalt-base body amorphous alloy according to claim 1, which is characterized in that include the following steps：
（1）The ingredient of cobalt-base body amorphous alloy described in accordance with the claim 1 weighs tri- kinds of high-purity raw materials of Co, Mo, B,
And polish metal Co and metal Mo surface scales ensure that metal Co, metal Mo, simple substance B purity are higher than 99.9%；
（2）Prepared raw material is put into vacuum arc furnace ignition first；Then 4 × 10 are evacuated to-3Pa is hereinafter, be re-filled with
0.05MPa argon gas continues to be evacuated to 4 × 10-3Pa or less is re-filled with 0.2MPa argon gas；Then the argon for being 99.999% in purity
Melting five to seven times under gas shielded atmosphere so that alloying component is uniform, obtains master alloy ingot；It is finally that master alloy ingot is completely molten
Change, the lining bar of cobalt-base body amorphous alloy is obtained by water cooled copper mould flash set technology.
3. a kind of preparation method of cobalt-base body amorphous alloy according to claim 2, which is characterized in that step（1）Institute
The purity for the tri- kinds of high-purity raw materials of Co, Mo, B stated is above 99.9%.
4. a kind of preparation method of cobalt-base body amorphous alloy according to claim 2, which is characterized in that step（2）Institute
That states obtains the lining bar of cobalt-base body amorphous alloy by water cooled copper mould flash set technology.
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| CN109355601A (en) * | 2018-12-27 | 2019-02-19 | 西南大学 | A kind of cobalt-base body amorphous alloy and preparation method thereof |
| CN113122784A (en) * | 2021-04-19 | 2021-07-16 | 西南大学 | Molybdenum-based bulk amorphous alloy and preparation method thereof |
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| CN113122784A (en) * | 2021-04-19 | 2021-07-16 | 西南大学 | Molybdenum-based bulk amorphous alloy and preparation method thereof |
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