CN103290341B - Anti-corrosion block rare earth-based metal glass and annealing method thereof - Google Patents
Anti-corrosion block rare earth-based metal glass and annealing method thereof Download PDFInfo
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- CN103290341B CN103290341B CN201310208651.5A CN201310208651A CN103290341B CN 103290341 B CN103290341 B CN 103290341B CN 201310208651 A CN201310208651 A CN 201310208651A CN 103290341 B CN103290341 B CN 103290341B
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Abstract
The invention relates to anti-corrosion block rare earth-based metal glass and an annealing method thereof, belonging to the technical field of preparation of amorphous alloy materials. Specific to the problem of poor crystallization resistance of the existing metal glass, the invention provides an anti-corrosion block rare earth-based metal glass with good crystallization resistance; and the composition is CexLayPrzSmsGdtComAln, wherein x, y, z, s, t, m and n represent the atom percentage content; x is 29.31%, y is 21.83%, z is 3.53%, s is 7.08%, t is 3.25%, m is 25% and n is 10%. The anti-corrosion block rare earth-based metal glass provided by the invention is a single amorphous phase and has strong amorphous forming ability; the anti-corrosion block rare earth-based metal glass after annealing treatment is still in an amorphous state; the corrosion resistance is obviously enhanced by 49.5%; and the hardness is remarkably improved.
Description
Technical field
The present invention relates to a kind of corrosion block rare earth based metallic glass and method for annealing thereof, belong to the preparing technical field of amorphous alloy material.
Background technology
Non-crystaline amorphous metal refers to that similar is in the metal or alloy without solid form of glass, has the metastable structure feature of short range order, longrange disorder, is a kind of new metallic material.Different from traditional metallic substance, the arrangement of its interior atoms presents the confusing state being similar to glass, therefore is referred to as metallic glass again.Not having dislocation in amorphous alloy, do not have phase boundary, is therefore the solid without lattice defect.Non-crystaline amorphous metal has high strength, high tenacity, good abrasion resistance, erosion resistance and desirable magnetics etc., has caused the extensive concern of material circle.
Block rare earth based metallic glass not only has high amorphous formation ability and unique physics, chemistry, mechanical characteristic, and due to the special property of rare earth element, the peculiar physicals that rare earth based metallic glass also has some other metallic glasss not possess, as magnetothermal effect, magneto-optic effect, heavy fermion behavior.This becomes the material that Material Field has theoretical investigation and using value very much.For many years, the raising of glass forming ability and the research of alloy property improvement are key content studied for design and Development of Novel block metal glass.
CN1952201A discloses a kind of mixed rare earths-based amorphous metal plastic, and it consists of:
dal
ecu
fz
g, wherein, 55≤d≤75,5≤e≤25,10≤f≤30,0.1≤g≤10, and meet d+e+f+g=100; The mixing system of the low-purity that described R is 22.3 % by weight La, 57.1 % by weight Ce, the impurity of 4.2 % by weight Pr, 15.4 % by weight Nd and 1 % by weight forms; Described Z is selected from the arbitrary element in Fe, Co, Ni, Zn, Hf, Mg, Mo, Nb, Sc, Ta, Ti, W, Y, Zr, Bi and Sn.But these amorphous metal plastics are made up of four kinds of (race) metallic elements, and only contain the amorphous phase of more than 50%, its amorphous formation ability is weak.
Patent CN101200778A discloses a kind of bulk rare-earth based amorphous alloy; Its composition is Re
aal
bm
cn
d, wherein 40≤a≤90,5≤b≤30,1≤c≤40,0.1≤d≤10 and a+b+c+d=100; Wherein, rare earth element Re is La, Ce, Pr, Nd, Sm, Eu), two or more mixing in Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; N is the mixing of one or more in Y, Hf, Nb; M is the mixing of one or more in Si, P, S, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, As, Zr, Mo, Pd, Ag.This rare-earth-base amorphous alloy contains N, and N is the mixing of one or more in Y, Hf, Nb; If not containing its comparative example 1 and 2 of N(), prepared alloy is then incomplete non-crystalline state.
The performance of structural relaxation on metallic glass extensively thinking at present to a certain degree has and affects significantly.But existing rare-earth-base amorphous alloy, after annealed process, its non-crystal structure becomes crystalline structure, and namely opposing crystallization ability is weak.The present invention develops just under such theoretical background.
Summary of the invention
For the problem that existing metallic glass opposing crystallization ability is weak; The invention provides a kind of the opposing crystallization ability, the corrosion block rare earth based metallic glass that have had.
The present invention is achieved through the following technical solutions:
1, a kind of corrosion block rare earth based metallic glass, it consists of Ce
xla
ypr
zsm
sgd
tco
mal
n, wherein, x, y, z, s, t, m, n are atomic percentage conc;
x=29.31%、y=21.83%、z=3.53%、s=7.08%、t=3.25%、m=25%、n=10%。
Described Ce is cerium, La is lanthanum, Pr is praseodymium, Sm is samarium, Gdt is gadolinium, Co is cobalt, Al is aluminium.
Above-mentioned corrosion block rare earth based metallic glass, can adopt suction casting method to be prepared from, its glass transition temperature
Degree (Tg) and initial crystallization temperature (Tx) are respectively 175 DEG C and 211 DEG C; Its microhardness (Hv) is 224;
Corrosion potential E in 3.5%NaCl solution
corrfor-1.14V and corrosion electric current density log (I
corr) be
-.0024mA/mm
2。Described suction casting method is: by lanthanum block, cerium block, praseodymium block, samarium block, gadolinium block, cobalt block and aluminium
In proportion, under atmosphere protection condition, melting is even for block, obtains the female ingot of alloy; Then female for alloy ingot is passed through to inhale
Casting is prepared into block amorphous alloy.The purity of metal used is more than 99.5%.
2, the method for annealing of above-mentioned corrosion block rare earth based metallic glass;
Block rare earth based metallic glass is annealed under atmosphere protection condition, then uses water cooling, obtain corrosion resistant
Erosion block rare earth based metallic glass;
Annealing temperature is 100-175 DEG C; Annealing time is 1-4 hour;
Described atmosphere protection condition, refers to rare gas element, nitrogen, SF
6protective condition.
Above-mentioned preparation method, preferably, anneals 1 hour or anneals 4 hours at 175 DEG C at 100 DEG C.
Above-mentioned preparation method, preferably, rare gas element is preferably argon gas.
Above-mentioned preparation method, preferably, the temperature of described water is-20-35 DEG C; Preferably 0-20 DEG C.
The corrosion block rare earth based metallic glass of scheme 1, after above-mentioned anneal, its microhardness (Hv) is 297-331; Corrosion potential E in 3.5%NaCl solution
corrfor-0.064 ~-0.53V and corrosion electric current density log (I
corr) be-0.020 ~-0.023mA/mm
2.
Beneficial effect
1. corrosion block rare earth based metallic glass of the present invention is single amorphous phase, and amorphous formation ability is strong;
2. the corrosion block rare earth based metallic glass after annealed process is still non-crystalline state; Its erosion resistance significantly increases, and amplification reaches 49.5%; Its hardness is significantly improved;
3. annealing treating process is simple, easy to control.
Accompanying drawing explanation
Fig. 1 is the XRD curve of the corrosion-proof rare earth bast block metal glass of embodiment 1;
Fig. 2 is the DSC curve of the corrosion-proof rare earth bast block metal glass of embodiment 1;
Fig. 3 is the XRD curve of the corrosion-proof rare earth bast block metal glass of embodiment 6;
Fig. 4 is the changes in hardness figure of corrosion block rare earth based metallic glass of the present invention before and after annealing;
Fig. 5 is the dynamic potential polarization curve of corrosion block rare earth based metallic glass of the present invention in 3.5%NaCl solution;
Fig. 6 is the size photo of rare-earth-base amorphous alloy sample of the present invention;
Wherein Fig. 4 and Fig. 5 draws according to the statistic data of embodiment 2-7 to form.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, it is to be understood that following explanation is only to explain the present invention, do not limit its content.
embodiment1
According to atomic percent 29.31% cerium, 21.83 lanthanums, 3.53 praseodymiums, 7.08% samarium, 3.25% gadolinium, 25% cobalt and 10% aluminium (purity >=99.5%, mass ratio), nominal gets 50g.Being placed on by raw metal is connected with in the copper mold of circulating water, passes into the argon gas of 0.6MPa under vacuum, and under 380v voltage, the distance regulating tungsten electrode and raw metal is 1cm; Opening power, starting the arc material; Melting 3 times, guarantees that alloying constituent mixes repeatedly.Powered-down, opens simultaneously and inhales casting valve, and control pressure difference starts to inhale casting at 0.4MPa, obtains erosion resistance rare earth based block metal glass sample.
Embodiment 2
Lower-temperature atmosphere tube furnace (argon shield condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 100 DEG C, be incubated 1 hour, takes out rapidly the beaker that the water being equipped with 0 DEG C put into by sample.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 3
Lower-temperature atmosphere tube furnace (argon shield condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 100 DEG C, be incubated 4 hours, takes out rapidly the beaker that the water being equipped with 0 DEG C put into by sample.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 4
Cryogenic vacuum tube furnace (argon shield condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 175 DEG C, be incubated 4 hours, takes out rapidly sample and puts into the beaker that 0 DEG C of water is housed.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 5
Cryogenic vacuum tube furnace (argon shield condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 175 DEG C, be incubated 1 hour, takes out rapidly sample and puts into the beaker that 0 DEG C of water is housed.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 6
Cryogenic vacuum tube furnace (radon gas protective condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 150 DEG C, be incubated 3 hours, takes out rapidly the beaker that the water that normal temperature is housed put into by sample.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 7
Cryogenic vacuum tube furnace (argon shield condition) put into by erosion resistance rare earth based metallic glass sample embodiment 1 prepared, at 120 DEG C, be incubated 2 hours, takes out rapidly the beaker that the water that normal temperature is housed put into by sample.Erosion resistance rare earth based block metal glass is taken out to obtain after the cooling of non-crystaline amorphous metal sample.After testing, the alloy after anneal is still non-crystalline state completely.
Embodiment 2 ~ 7 erosion resistance rare earth based metallic glass, the corrosion potential (E in 3.5%NaCl solution
corr) and corrosion electric current density (log (I
corr)), and intensive parameter is as table 1;
Table 1
| Intensive parameter (Hv) | E corr(v) | Log I corr(mA/mm 2) | |
| Embodiment 1 | 224 | -1.05 | -.0024 |
| Embodiment 2 | 297 | -0.64 | -0.021 |
| Embodiment 3 | 302 | -0.65 | -0.020 |
| Embodiment 4 | 299 | -0.61 | -0.021 |
| Embodiment 5 | 311 | -0.58 | -0.020 |
| Embodiment 6 | 331 | -0.60 | -0.021 |
| Embodiment 7 | 316 | -0.53 | -0.023 |
Corrosion block rare earth based metallic glass after annealed process, its hardness significantly increases, and amplification reaches 48%.Its corrosion electric current density does not change substantially, but corrosion potential sharply increases, and adds 0.52v, and amplification reaches 49.5%.That is alloy is enough at structural relaxation to a certain degree, and the erosion resistance of alloy is significantly improved.
Claims (1)
1. a corrosion block rare earth based metallic glass, is characterized in that, it consists of Ce
xla
ypr
zsm
sgd
tco
mal
n, wherein, x, y, z, s, t, m, n are atomic percentage conc;
x=29.31%、y=21.83%、z=3.53%、s=7.08%、t=3.25%、m=25%、n=10%；
Its preparation method is:
Block rare earth based metallic glass is annealed under atmosphere protection condition, then uses water cooling, obtain corrosion resistant
Erosion block rare earth based metallic glass;
Annealing temperature is 100-175 DEG C; Annealing time is 1-4 hour;
Described atmosphere protection condition, refers to rare gas element, nitrogen, SF
6protective condition;
Its microhardness (Hv) is 297-331; Corrosion potential E in 3.5%NaCl solution
corrfor-0.064 ~-0.53V and corrosion electric current density log (I
corr) be-0.020 ~-0.023mA/mm
2.
2.a method for annealing for corrosion block rare earth based metallic glass according to claim 1, is characterized in that,
Block rare earth based metallic glass is annealed under atmosphere protection condition, then uses water cooling, obtain corrosion resistant
Erosion block rare earth based metallic glass;
Annealing temperature is 100-175 DEG C; Annealing time is 1-4 hour;
Described atmosphere protection condition, refers to rare gas element, nitrogen, SF
6protective condition.
3.method for annealing according to claim 2, is characterized in that, anneals 1 hour or anneal 4 hours at 175 DEG C at 100 DEG C.
4.the method for annealing of corrosion block rare earth based metallic glass according to claim 2, is characterized in that, rare gas element is argon gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0406770B1 (en) * | 1989-07-04 | 1994-11-30 | Ykk Corporation | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| CN1936058A (en) * | 2006-09-30 | 2007-03-28 | 北京航空航天大学 | La-Ce base amorphous alloy |
| CN101280398A (en) * | 2007-04-02 | 2008-10-08 | 比亚迪股份有限公司 | Rare earth-based amorphous alloy and preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212561A (en) * | 1997-01-28 | 1998-08-11 | Akihisa Inoue | Amorphous alloy excellent in workability |
-
2013
- 2013-05-30 CN CN201310208651.5A patent/CN103290341B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0406770B1 (en) * | 1989-07-04 | 1994-11-30 | Ykk Corporation | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| CN1936058A (en) * | 2006-09-30 | 2007-03-28 | 北京航空航天大学 | La-Ce base amorphous alloy |
| CN101280398A (en) * | 2007-04-02 | 2008-10-08 | 比亚迪股份有限公司 | Rare earth-based amorphous alloy and preparation thereof |
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