CN102517523A - Iron-cobalt-based endogenous amorphous composite material - Google Patents
Iron-cobalt-based endogenous amorphous composite material Download PDFInfo
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- CN102517523A CN102517523A CN2011104214665A CN201110421466A CN102517523A CN 102517523 A CN102517523 A CN 102517523A CN 2011104214665 A CN2011104214665 A CN 2011104214665A CN 201110421466 A CN201110421466 A CN 201110421466A CN 102517523 A CN102517523 A CN 102517523A
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 90
- 239000000470 constituent Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000005275 alloying Methods 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 62
- 239000000956 alloy Substances 0.000 abstract description 62
- 238000002360 preparation method Methods 0.000 abstract description 40
- 239000000463 material Substances 0.000 abstract description 28
- 229910052752 metalloid Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 75
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 229910052802 copper Inorganic materials 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 17
- 238000001816 cooling Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 238000005303 weighing Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000005266 casting Methods 0.000 description 13
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 12
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000007712 rapid solidification Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 241000408529 Libra Species 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 239000005300 metallic glass Substances 0.000 description 4
- 229910002546 FeCo Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910015365 Au—Si Inorganic materials 0.000 description 1
- 244000187801 Carpobrotus edulis Species 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention relates to an iron-cobalt-based endogenous amorphous composite material. The iron-cobalt-based bulk amorphous composite material comprises, by volume, 15-85% of an amorphous phase and 85-15% of a crystal phase, and components of the composite material only contain 0-5% of metalloid elements. The formula of alloy components in the iron-cobalt-based amorphous composite material is (Fe1-xCox)aLabCecAldCueMfNgTh (by atom ratio), wherein M is one or more of rare earth elements except La and Ce, N is one or more of Ti, V, Cr, Mn, Ni, Zn, Zr, Nb, Mo, Ag, Hf, Ta and Ga, T is one or more B, C, Si and P, x is equal to or greater than 0.05 and equal to or less than 0.7, a is equal to or greater than 30 and equal to or less than 80, b is equal to or greater than 5 and equal to or less than 30, c is equal to or greater than 5 and equal to or less than 30, d is equal to or greater than 1 and equal to or less than 10, e is equal to or greater than 1 and equal to or less than 10, f is equal to or greater than 0 and equal to or less than 30, g is equal to or greater than 0 and equal to or less than 5, h is equal to or greater than 0 and equal to or less than 5, and the a+b+c+d+e+f+g+h value is 100. The alloy of the invention has the advantages of high glass formation capability, simple preparation process and low preparation cost, simultaneously possesses an amorphous matrix and an endogenous crystal structure in the material tissue structure, has the characteristics of high strength, high toughness, high heat stability, excellent soft magnetic performance and the like, and has a very wide application prospect.
Description
Technical field
The present invention relates to a kind of bulk amorphous composite materials; Specifically relating to a kind of is staple with the iron cobalt; Comprise a certain amount of amorphous phase and Nei Sheng crystal mutually, and only contain the iron cobalt-base body amorphous alloy that a spot of metalloid element does not even contain metalloid element in the composition.
Background technology
Generally speaking, the melt solidifying of the metal or alloy Shi Douhui that gets off forms crystal.The sixties in 20th century, the Duwez etc. of the U.S. adopted the method for rapid solidification to make the Au-Si non-crystaline amorphous metal first, thereby opened non-crystaline amorphous metal was formed theory, the research boom of physics, chemistry and mechanical characteristics.But the glass forming ability of the initial alloy system of finding is all lower, has only the precious metal alloys of minority can form block, has seriously limited the research and the practical applications of non-crystaline amorphous metal.Since the eighties in 20th century, the block amorphous alloy of a plurality of systems comes to light in succession, La-Al-Cu-Ni for example, Mg-Y-Cu, alloy systems such as Zr-Al-Ni-Cu.After this, block amorphous alloy has caused increasing concern as a kind of high performance material because of its HS, high firmness, superior corrosion resistance, excellent soft magnetic performance etc.
The iron-base block amorphous alloy tool is compared with the non-crystaline amorphous metal of other systems, has HS, high corrosion resistance, and the advantage of excellent soft magnetic performance and lower production cost receives the attention of investigation of materials worker and industry member.At present; With the Fe-Si-B alloy system is that the Fe-based amorphous-nanometer crystal alloy of representative has been widely applied in the X-former industry; Replace the traditional silicon steel disc can reduce the core loss in the X-former operational process effectively with it, reduce energy loss and greenhouse gas emission as the transformer fe core material.In addition, the iron cobalt base amorphous alloy of preparing with the ferro element of cobalt instead of part possesses better high-frequency soft magnetic performance.Traditional Fe-based amorphous alloy is because glass forming ability is low, and sample size is restricted.Nineteen ninety-five, Japanese Inoue etc. have found can to reach the Fe-of 2 mm by maximum diameter, and (Al Ga)-the metalloid block Fe-based amorphous alloy, has opened the prelude of research block Fe-based amorphous alloy.The critical diameter of the maximum sized Fe-based amorphous alloy Fe-Co-Cr-Mo-C-B-Y of report is 16 mm at present.
Although up to the present developed the multiple cobalt base amorphous or amorphous-crystal matrix material of block Fe-based/iron with superperformance and high glass forming ability; But that these iron-baseds or iron cobalt-base body amorphous alloy all contain is a large amount of (about 20%, atomic percent) metalloid element Si, B, C, P etc.These elements have high fusing point, volatile characteristic, exist impurity many during melting, and composition is difficult to shortcomings such as control, and too much the adding of metalloid element has caused the brittle rupture of iron-base block amorphous alloy to be inclined to.Develop the iron-based or the iron cobalt base amorphous alloy that do not contain metalloid element or contain a small amount of metalloid element and become the most important thing in the said material research.
Summary of the invention
Technical scheme of the present invention is: give birth to amorphous composite in a kind of iron cobalt-based, the crystal that the cobalt-base body amorphous matrix material of this iron comprises amorphous phase that volume percent is 15-85% and 85-15% mutually; The cobalt-base body amorphous matrix material alloying constituent of this iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eM
fN
gT
h(atomic ratio); Wherein, M is one or more in the REE except that La, Ce, and N is one or more among Ti, V, Cr, Mn, Ni, Zn, Zr, Nb, Mo, Ag, Hf, Ta, the Ga; T is one or more among B, C, Si, the P, and 0.05≤x≤0.7; 30≤a≤80,5≤b≤30,5≤c≤30,1≤d≤10,1≤e≤10,0≤f≤30,0≤g≤5,0≤h≤5, and a+b+c+d+e+f+g+h=100.
Preferably:
The cobalt-base body amorphous matrix material alloying constituent of described iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
e(atomic ratio), 0.05≤x≤0.7,30≤a≤80,5≤b≤30,5≤c≤30,1≤d≤10,1≤e≤10 wherein, and satisfy a+b+c+d+e=100.
The cobalt-base body amorphous matrix material alloying constituent of described iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eM
f(atomic ratio), wherein M is one or more in the REE except that La, Ce, 0.05≤x≤0.7,30≤a≤80,5≤b≤30,5≤c≤30,1≤d≤10,1≤e≤10,0≤f≤30 wherein, and satisfy a+b+c+d+e+f=100.
The cobalt-base body amorphous matrix material alloying constituent of described iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eN
g(atomic ratio) wherein N is among Ti, V, Cr, Mn, Ni, Zn, Zr, Nb, Mo, Ag, Hf, the Ta one or more, wherein 0.05≤x≤0.7,30≤a≤80; 5≤b≤30,5≤c≤30,1≤d≤10; 1≤e≤10,0≤g≤5, and satisfy a+b+c+d+e+g=100.
The cobalt-base body amorphous matrix material alloying constituent of described iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eT
h(atomic ratio) wherein T is among B, C, Si, the P one or more, 0.05≤x≤0.7,30≤a≤80,5≤b≤30,5≤c≤30,1≤d≤10,1≤e≤10,0≤h≤5 wherein, and satisfy a+b+c+d+e+h=100.
Above-mentioned FeCo is base block amorphous-and the preparation method of crystal matrix material specifically may further comprise the steps:
(1) preparation of mother alloy: in high-purity argon gas atmosphere, according to (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eM
fN
gT
H,, 0.05≤x≤0.7,30≤a≤80,5≤b≤30 wherein; 5≤c≤30,1≤d≤10,1≤e≤10; 0≤f≤30,0≤g≤5,0≤h≤5; Required atomic ratio is with the Fe in the said components, Co, La, Ce, Al, Cu and other component raw material meltings, and melt back at least 4 times is to guarantee the homogeneity of alloy.Obtain the alloy pig of mother alloy after the cooling.
(2), utilize the absorbing and casting device in the electric arc furnace that alloy is inhaled the bar-shaped or tabular sample of formation in casting to the copper mold of different casting molds with the mother alloy refuse in the step (1).
Described FeCo base alloy in the alloying constituent zone, utilizes copper mold casting method to prepare the above bulk amorphous composite materials bar of diameter 4 mm, obtains the amorphous composite bar of diameter 10 mm-15 mm in the part composition range.
The advantage of FeCo Ji Neisheng amorphous composite of the present invention is:
(1) contains the very small amount metalloid element in the alloying constituent; The part composition does not contain metalloid element; Obtained interior living amorphous-crystal matrix material; In the alloying constituent zone of regulation, can utilize copper mold casting method to prepare the above amorphous-crystal matrix material bar of diameter 4 mm, obtain the amorphous-crystal matrix material bar of diameter in the part composition range greater than 10 mm-15 mm.
(2) have the glass transformation temperature of 350 K-550 K, the temperature of fusion of 600 K-1170 K, and the supercooled liquid of 10 K-60 K is interval.
(3) owing to contain the amorphous phase of certain volume in the alloy; And amorphous phase can be regulated with not coexisting of composition is interior on a large scale with crystal ratio mutually; This alloy has high breaking tenacity 600 MPa-1500 MPa; Simultaneously since crystal in the breaking-down process of amorphous to the interception of shear zone, most of alloy has certain amount of plastic deformation 0-5%.
(4) this alloy system has good magnetic property, in conjunction with its higher intensity, has wide practical use at structured material and field of functional materials.
Description of drawings:
Fig. 1 is ESEM (SEM) photo of the diameter 6 mm amorphous-crystal composite sticks of embodiment 1 preparation;
Fig. 2 is that the heat of the diameter 6 mm amorphous-crystal composite sticks of embodiment 1 preparation is analyzed the DSC curve, and rate of heating is 20 K/min;
Fig. 3 is the Mechanics Performance Testing of the sample of embodiment 1,2,3, the stress-strain curve diagram in its compression process;
Fig. 4 is magnetism testing (vibrating sample magnetometer VSM) graphic representation of the sample of embodiment 1,2,3;
Fig. 5 is ESEM (SEM) photo of the diameter 6 mm amorphous-crystal composite sticks of embodiment 2 preparations;
Fig. 6 is that the heat of the diameter 6 mm amorphous-crystal composite sticks of embodiment 2 preparations is analyzed the DSC curve, and rate of heating is 20 K/min;
Fig. 7 is transmission electron microscope (TEM) photo and the SEAD of amorphous portion of the diameter 6 mm amorphous-crystal composite sticks of embodiment 2 preparation;
Fig. 8 is ESEM (SEM) photo of the diameter 10 mm amorphous-crystal composite sticks of embodiment 3 preparations;
Fig. 9 is that the heat of the diameter 10 mm amorphous-crystal composite sticks of embodiment 3 preparations is analyzed the DSC curve, and rate of heating is 20 K/min;
Figure 10 is transmission electron microscope (TEM) photo and the SEAD of amorphous portion of the diameter 6 mm amorphous-crystal composite sticks of embodiment 3 preparation;
Figure 11 is ESEM (SEM) photo of the diameter 6 mm amorphous-crystal composite sticks of embodiment 4 preparations;
Figure 12 is ESEM (SEM) photo of the diameter 6 mm amorphous-crystal composite sticks of embodiment 5 preparations.
Embodiment:
Below in conjunction with specific embodiment technical scheme of the present invention is further specified.
Preparation (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8Amorphous composite
With (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8Mother alloy.
Step 3, preparation (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-180 A.Melt and be drawn in the copper mold after 1-3 minute, obtain (Fe with the copper mold cooling
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8Amorphous composite bar or sheet material.
Shown in Fig. 1 ESEM (SEM) photo, above-mentioned 6 mm alloy bars comprise crystal and noncrystal substrate two mutually.The heat of Fig. 2 is analyzed the DSC curve display and is gone out that this alloy has tangible glass transition and crystallization process in heat-processed, contains a certain amount of amorphous phase in also provable this alloy, the glass transition temp (T of amorphous phase
g), crystallization begins temperature (T
x), width (the Δ T=T of supercooling liquid phase region
x-T
g) be respectively 401 K, 415 K, 14 K.Can calculate by similar many SEM photos statistics shown in Figure 1 that the shared volume(tric)fraction of amorphous phase is about 45% in this alloy system.With non-crystal bar intercepting φ 2 mm * 4 mm that produce, test its compression mechanical property, have higher breaking tenacity 713 MPa (see figure 3)s.The alloy of preparation is carried out magnetism testing, and its saturation magnetization is 22 emu/g (see figure 4)s.
Embodiment 2
Preparation (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2Amorphous composite
With (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2Mother alloy.
Step 3, preparation (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-180 A.Melt and be drawn in the copper mold after 1-3 minute, obtain (Fe with the copper mold cooling
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2Amorphous composite bar or sheet material.
Shown in Fig. 5 ESEM (SEM) photo, this alloy comprises crystal and noncrystal substrate two mutually.The heat of Fig. 6 is analyzed the DSC curve display and is gone out that this alloy has tangible glass transition and crystallization process in heat-processed, contains a certain amount of amorphous phase in also provable this alloy, and the crystallization of amorphous phase begins temperature (T
x) be 471 K.Fig. 7 is the transmission electron microscope photo and the SEAD of amorphous phase part, it is thus clear that present tangible amorphous characteristic.Can calculate by similar many SEM photos statistics shown in Figure 5 that the shared volume(tric)fraction of amorphous phase is about 47% in this alloy system.With non-crystal bar intercepting φ 2 mm * 4 mm that produce, test its compression mechanical property, have higher breaking tenacity 703 MPa (see figure 3)s.The alloy of preparation is carried out magnetism testing, and its saturation magnetization is 21 emu/g (see figure 4)s.
Embodiment 3
Preparation (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4Amorphous composite
With (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.44Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-200 A, and melt back guarantees the homogeneity of composition more than 4 times, and furnace cooling obtains (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4Mother alloy.
Step 3, (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-180 A.Melt and be drawn in the copper mold after 1-3 minute, obtain (Fe with the copper mold cooling
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4Amorphous composite bar or sheet material.
Shown in Fig. 8 ESEM (SEM) photo, this alloy is similar with embodiment 1,2, comprise crystal mutually with noncrystal substrate two mutually, different is that the contained noncrystal substrate phase ratio of this alloy reduces to some extent.The heat of Fig. 9 is analyzed the DSC curve display and is gone out that this alloy has tangible glass transition and crystallization process in heat-processed, contains a certain amount of amorphous phase in also provable this alloy, and the crystallization of amorphous phase begins temperature (T
x) be 443 K.Figure 10 is the transmission electron microscope photo and the SEAD of amorphous phase part, it is thus clear that present tangible amorphous characteristic.Can calculate by many SEM photos statistics shown in Figure 8 that the shared volume(tric)fraction of amorphous is about 30% in this alloy system.With non-crystal bar intercepting φ 2 mm * 4 mm that produce, test its compression mechanical property, have higher breaking tenacity 809 MPa (see figure 3)s.The alloy of preparation is carried out magnetism testing, and its saturation magnetization is 53 emu/g (see figure 4)s.
Embodiment 4
Preparation (Fe
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7Amorphous composite
With (Fe
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7Mother alloy.
Step 3, preparation (Fe
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5 normal atmosphere, regulates electric current to 50 A.Melt and be drawn in the copper mold after 1 minute, obtain (Fe with the copper mold cooling
0.71Co
0.29)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7Amorphous composite bar or sheet material.
Shown in Figure 11 ESEM (SEM) photo, similar with embodiment 1,2,3, this alloy comprises crystal and noncrystal substrate two mutually.Can calculate by similar many SEM photos statistics shown in Figure 11 that the shared volume(tric)fraction of amorphous phase is about 40% in this alloy system.
Embodiment 5
Preparation (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1Amorphous composite
With (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1Mother alloy.
Step 3, preparation (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5-0.8 normal atmosphere, regulates electric current to 50-180 A.Melt and be drawn in the copper mold after 1-3 minute, obtain (Fe with the copper mold cooling
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1Amorphous composite bar or sheet material.
Shown in Figure 12 ESEM (SEM) photo, similar with embodiment 1,2,3, this alloy comprises crystal and noncrystal substrate two mutually.Can calculate by similar many SEM photos statistics shown in Figure 12 that the shared volume(tric)fraction of amorphous phase is about 31% in this alloy system.
Embodiment 6
Preparation (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9Amorphous composite
With (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.8 normal atmosphere, regulates electric current to 200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9Mother alloy.
Step 3, preparation (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5 normal atmosphere, regulates electric current to 50 A.Melt and be drawn in the copper mold after 1.5 minutes, obtain (Fe with the copper mold cooling
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9Amorphous composite bar or sheet material.
Embodiment 7
Preparation (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5Amorphous composite
With (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.8 normal atmosphere, regulates electric current to 200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5Mother alloy.
Step 3, preparation (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5 normal atmosphere, regulates electric current to 50 A.Melt and be drawn in the copper mold after 1.5 minutes, obtain (Fe with the copper mold cooling
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5Amorphous composite bar or sheet material.
Embodiment 8
Preparation (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2Amorphous composite
With (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2The atomic percent of chemical ingredients be converted into mass ratio, with the accurate weighing of Libra.
Step 2, preparation (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2Mother alloy
With step 1 claim raw material put into vacuum melting furnace, suction to 5 * 10
-3Pa charges into argon shield gas, regulates air pressure to 0.8 normal atmosphere, regulates electric current to 200 A, and melt back is more than 4 times, and furnace cooling obtains (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2Mother alloy.
Step 3, preparation (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2Amorphous composite bar or sheet material
According to the bar that will prepare or an amount of mother alloy of big or small clip of sheet material, put into vacuum arc and inhale casting stove, suction to 5 * 10 with rapid solidification function
-3Pa charges into argon shield gas, regulates air pressure to 0.5 normal atmosphere, regulates electric current to 50 A.Melt and be drawn in the copper mold after 1.5 minutes, obtain (Fe with the copper mold cooling
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.2Amorphous composite bar or sheet material.
Claims (9)
1. give birth to amorphous composite in an iron cobalt-based, it is characterized in that the cobalt-base body amorphous matrix material of this iron is by the crystal phase composite of the amorphous phase that accounts for volume percent 15-85%, 85-15%; The cobalt-base body amorphous matrix material alloying constituent of this iron expression formula is: (Fe
1-xCo
x)
aLa
bCe
cAl
dCu
eM
fN
gT
h, wherein, M is one or more in the REE except that La, Ce, and N is one or more among Ti, V, Cr, Mn, Ni, Zn, Zr, Nb, Mo, Ag, Hf, Ta, the Ga, and T is one or more among B, C, Si, the P, and 0.05≤x≤0.7; 30≤a≤80,5≤b≤30,5≤c≤30,1≤d≤10,1≤e≤10,0≤f≤30,0≤g≤5,0≤h≤5, and a+b+c+d+e+f+g+h=100.
2. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.43; A=52.6, b=12, c=27, d=3.6, e=4.8, f=0, g=0, h=0, the expression formula of amorphous composite is (Fe
0.57Co
0.43)
52.6La
12Ce
27Al
3.6Cu
4.8
3. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.32; A=58.4, b=8.8, c=27.2, d=2.4, e=3.2, f=0, g=0, h=0, the expression formula of amorphous composite is (Fe
0.68Co
0.32)
58.4La
8.8Ce
27.2Al
2.4Cu
3.2
4. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.26; A=67.2, b=7.2, c=21.4, d=1.8, e=2.4, f=0, g=0, h=0, the expression formula of amorphous composite is (Fe
0.74Co
0.26)
67.2La
7.2Ce
21.4Al
1.8Cu
2.4
5. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.05; A=63.4, b=8.4, c=23.3, d=2.1, e=2.1, f=0, g=0.7, h=0, the expression formula of amorphous composite is (Fe
0.95Co
0.05)
63.4La
8.4Ce
23.3Al
2.1Cu
2.1Ag
0.7
6. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.29; A=62.8, b=8.3, c=23.0, d=2.1, e=2.8, f=0, g=0, h=1, the expression formula of amorphous composite is (Fe
0.71Co
0.29)
62..8La
8.3Ce
23.0Al
2.1Cu
2.8Si
1
7. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.4; A=50, b=13, c=23.7, d=4.8, e=6, f=0, g=1.6, h=0.9, the expression formula of amorphous composite is (Fe
0.6Co
0.4)
50.0La
13.0Ce
23.7Al
4.8Cu
6Mn
1.6C
0.9
8. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.7; A=30, b=21.3, c=24, d=8.0, e=7.7, f=6, g=2.5, h=0.5, the expression formula of amorphous composite is (Fe
0.3Co
0.7)
30.0La
21.3Ce
24.0Al
8.0Cu
7.7Pr
6V
2.5P
0.5
9. give birth to amorphous composite in a kind of iron cobalt-based according to claim 1, it is characterized in that X=0.39; A=46.5, b=15.3, c=16.7, d=5.2, e=5.3, f=8, g=2.5, h=0.5, the expression formula of amorphous composite is (Fe
0.61Co
0.39)
46.5La
15.3Ce
16.7Al
5.2Cu
5.3Yb
6Y
2Ni
1.5Cr
1.0B
0.3C
0.22.
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| CN103668007A (en) * | 2013-12-19 | 2014-03-26 | 南京信息工程大学 | Microcrystalline alloy thin belt with high saturation magnetic induction strength and preparation method thereof |
| CN103882348A (en) * | 2013-06-21 | 2014-06-25 | 洛阳威尔若普检测技术有限公司 | High-magnetic-conductivity amorphous soft magnetic alloy thin strip material for magneto-electric effect sensor and preparation method thereof |
| CN107344283A (en) * | 2017-05-16 | 2017-11-14 | 蚌埠市宏大制药机械有限公司 | A kind of preparation method of anticorrosive medicinal capsule mold |
| CN108493461A (en) * | 2018-05-08 | 2018-09-04 | 大连理工大学 | A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles |
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| CN108493461B (en) * | 2018-05-08 | 2021-01-19 | 大连理工大学 | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof |
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