CN102517523B - Iron-cobalt-based endogenous amorphous composite material - Google Patents
Iron-cobalt-based endogenous amorphous composite material Download PDFInfo
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- CN102517523B CN102517523B CN 201110421466 CN201110421466A CN102517523B CN 102517523 B CN102517523 B CN 102517523B CN 201110421466 CN201110421466 CN 201110421466 CN 201110421466 A CN201110421466 A CN 201110421466A CN 102517523 B CN102517523 B CN 102517523B
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 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 13
- 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
- 239000011521 glass Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 75
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 239000012071 phase Substances 0.000 description 24
- 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
- 230000001105 regulatory effect Effects 0.000 description 16
- 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
- 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
- 230000005540 biological transmission Effects 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
- 238000004098 selected area electron diffraction Methods 0.000 description 4
- 229910002546 FeCo Inorganic materials 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 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
- 238000011835 investigation 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
- 238000007906 compression Methods 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
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 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 relate to a kind of take the iron cobalt as main component, comprise a certain amount of amorphous phase and Nei Sheng crystal mutually, and only contain the iron cobalt-base body amorphous alloy that a small amount 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, only has the precious metal alloys of minority can form block, has seriously limited research and the engineering of non-crystaline amorphous metal and has used.Since the eighties in 20th century, the block amorphous alloy of a plurality of systems is found in succession, La-Al-Cu-Ni for example, Mg-Y-Cu, the 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 high strength, high rigidity, good erosion 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 high strength, high corrosion resistance, and the advantage of excellent soft magnetic performance and lower production cost is subject to the attention of investigation of materials worker and industry member.At present, with the Fe-Si-B alloy be representative Fe-based amorphous-nanometer crystal alloy has been widely applied in the transformer industry, replace traditional silicon steel disc can effectively reduce core loss in the transformer operational process as the transformer fe core material with it, reduce energy loss and greenhouse gas emission.In addition, the iron cobalt base amorphous alloy that replaces the ferro element of part to prepare with cobalt 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 that maximum diameter can reach the Fe-(Al, Ga) of 2 mm-metalloid block Fe-based amorphous alloy, have 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 multiple have superperformance and high glass forming ability block Fe-based/the cobalt base amorphous or amorphous-crystal matrix material of iron, 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 the 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 that do not contain metalloid element or contain a small amount of metalloid element or iron cobalt base amorphous alloy and become the most important thing in such investigation of materials.
Summary of the invention
Technical scheme of the present invention is: the crystal that a kind of iron cobalt-based endogenous amorphous composite material, the cobalt-base body amorphous matrix material of this iron comprise 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 rare earth element except 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 rare earth element except 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 composite 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 wherein, 5≤b≤30,5≤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, melt back at least 4 times is to guarantee the homogeneity of alloy.Obtain the alloy pig of mother alloy after the cooling.
(2) with the mother alloy refuse in the step (1), utilize the absorbing and casting device in the electric arc furnace that alloy suction casting is formed bar-shaped or tabular sample to the copper mold of different casting molds.
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 in the alloying constituent and seldom measure metalloid element, 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 diameter in the part composition range greater than the amorphous-crystal matrix material bar of 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 with interior adjusting the on a large scale that do not coexist of composition with the ratio of crystal phase, 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 scanning electron microscope (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 embodiment 1,2,3 sample, the stress-strain curve diagram in its compression process;
Fig. 4 is magnetism testing (vibrating sample magnetometer VSM) graphic representation of embodiment 1,2,3 sample;
Fig. 5 is scanning electron microscope (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 selected area electron diffraction of amorphous portion of the diameter 6 mm amorphous-crystal composite sticks of embodiment 2 preparation;
Fig. 8 is scanning electron microscope (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 selected area electron diffraction of amorphous portion of the diameter 6 mm amorphous-crystal composite sticks of embodiment 3 preparation;
Figure 11 is scanning electron microscope (SEM) photo of the diameter 6 mm amorphous-crystal composite sticks of embodiment 4 preparations;
Figure 12 is scanning electron microscope (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 described further.
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 is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-200 A to 0.5-0.8 normal atmosphere, 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-180 A to 0.5-0.8 normal atmosphere.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 scanning electron microscope (SEM) photo, above-mentioned 6 mm alloy bars comprise crystal and noncrystal substrate two-phase.The heat of Fig. 2 is analyzed the DSC curve display and is gone out that this alloy has obvious glass transition and crystallization process in heat-processed, also contains a certain amount of amorphous phase in 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 be calculated by similar many SEM photos statistics shown in Figure 1 that the shared volume fraction of amorphous phase is about 45% in this alloy system.The non-crystal bar of producing is intercepted φ 2 mm * 4 mm, test its Compressive Mechanical Properties, have higher breaking tenacity 713 MPa(and see Fig. 3).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 is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-200 A to 0.5-0.8 normal atmosphere, 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-180 A to 0.5-0.8 normal atmosphere.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 scanning electron microscope (SEM) photo, this alloy comprises crystal and noncrystal substrate two-phase.The heat of Fig. 6 is analyzed the DSC curve display and is gone out that this alloy has obvious glass transition and crystallization process in heat-processed, also contains a certain amount of amorphous phase in provable this alloy, and the crystallization of amorphous phase begins temperature (T
x) be 471 K.Fig. 7 is transmission electron microscope photo and the selected area electron diffraction of amorphous phase part, as seen presents obvious amorphous characteristic.Can be calculated by similar many SEM photos statistics shown in Figure 5 that the shared volume fraction of amorphous phase is about 47% in this alloy system.The non-crystal bar of producing is intercepted φ 2 mm * 4 mm, test its Compressive Mechanical Properties, 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 is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-200 A to 0.5-0.8 normal atmosphere, 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-180 A to 0.5-0.8 normal atmosphere.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 scanning electron microscope (SEM) photo, this alloy and embodiment 1,2 similar comprise crystal phase and noncrystal substrate two-phase, and 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 obvious glass transition and crystallization process in heat-processed, also contains a certain amount of amorphous phase in provable this alloy, and the crystallization of amorphous phase begins temperature (T
x) be 443 K.Figure 10 is transmission electron microscope photo and the selected area electron diffraction of amorphous phase part, as seen presents obvious amorphous characteristic.Can be calculated by many SEM photos statistics shown in Figure 8 that the shared volume fraction of amorphous is about 30% in this alloy system.The non-crystal bar of producing is intercepted φ 2 mm * 4 mm, test its Compressive Mechanical Properties, 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 is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-200 A to 0.5-0.8 normal atmosphere, 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure to 0.5 normal atmosphere is regulated 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 scanning electron microscope (SEM) photo, with embodiment 1,2,3 similar, this alloy comprises crystal and noncrystal substrate two-phase.Can be calculated by similar many SEM photos statistics shown in Figure 11 that the shared volume 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 is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-200 A to 0.5-0.8 normal atmosphere, 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure is regulated electric current to 50-180 A to 0.5-0.8 normal atmosphere.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 scanning electron microscope (SEM) photo, with embodiment 1,2,3 similar, this alloy comprises crystal and noncrystal substrate two-phase.Can be calculated by similar many SEM photos statistics shown in Figure 12 that the shared volume 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 is filled with argon shield gas, and adjustable pressure to 0.8 normal atmosphere is regulated 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure to 0.5 normal atmosphere is regulated 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 is filled with argon shield gas, and adjustable pressure to 0.8 normal atmosphere is regulated 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure to 0.5 normal atmosphere is regulated 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 is filled with argon shield gas, and adjustable pressure to 0.8 normal atmosphere is regulated 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
The mother alloy an amount of according to the big or small clip of bar to be prepared or sheet material put into the vacuum arc with rapid solidification function and inhaled casting stove, suction to 5 * 10
-3Pa is filled with argon shield gas, and adjustable pressure to 0.5 normal atmosphere is regulated 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. an iron cobalt-based endogenous amorphous composite material 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 rare earth element except 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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. a kind of iron cobalt-based endogenous amorphous composite material according to claim 1 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
0.2
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| US4668310A (en) * | 1979-09-21 | 1987-05-26 | Hitachi Metals, Ltd. | Amorphous alloys |
| CN102011049A (en) * | 2010-11-22 | 2011-04-13 | 北京航空航天大学 | Ta-doped FeCo-based soft magnetic alloy and preparation method thereof |
| CN102254665A (en) * | 2010-05-17 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | Iron-cobalt-based nano-crystalline soft magnetic alloy and preparation method thereof |
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| US4668310A (en) * | 1979-09-21 | 1987-05-26 | Hitachi Metals, Ltd. | Amorphous alloys |
| CN102254665A (en) * | 2010-05-17 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | Iron-cobalt-based nano-crystalline soft magnetic alloy and preparation method thereof |
| CN102011049A (en) * | 2010-11-22 | 2011-04-13 | 北京航空航天大学 | Ta-doped FeCo-based soft magnetic alloy and preparation method thereof |
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