CN112981278A - High-energy-content amorphous alloy material, and preparation method and application thereof - Google Patents
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 124
- 239000000956 alloy Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000000463 material Substances 0.000 claims abstract description 103
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 239000002360 explosive Substances 0.000 claims abstract description 9
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- 238000000034 method Methods 0.000 claims description 35
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- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 230000006698 induction Effects 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
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- 239000007787 solid Substances 0.000 claims description 10
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- 239000001257 hydrogen Substances 0.000 description 31
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- 239000001301 oxygen Substances 0.000 description 29
- 229910052749 magnesium Inorganic materials 0.000 description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000003860 storage Methods 0.000 description 16
- 238000003723 Smelting Methods 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052755 nonmetal Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000010891 electric arc Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
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- 239000004570 mortar (masonry) Substances 0.000 description 4
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 3
- 238000005280 amorphization Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 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
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
Abstract
The invention provides a high-energy-content amorphous alloy material, which contains one or more of the following elements: mg, Al, La, Ce, Zr; and the heat value of the high-energy-content amorphous alloy material is 0.7-30 kJ/g, preferably 10-25 kJ/g. The amorphous alloy high-energy-content material provided by the invention has a lower ignition point, retains a higher combustion heat value, and is safer, lower in cost and higher in yield compared with crystalline alloy nano powder. The amorphous alloy high-energy-content material can be applied to the fields of explosives, leads, fireworks, solid propellants and the like.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a high-energy-content amorphous alloy material, and a preparation method and application thereof.
Background
An energetic material is a metastable material with high energy, which releases a large amount of heat when subjected to a certain external stimulus. Specifically, energetic materials are compounds or mixtures having explosive groups or containing oxidants and combustibles, capable of independently carrying out chemical reactions and outputting energy, and are important components of military explosives, propellants and rocket propellant formulations. At present, the non-metal energetic material is widely used for explosives or fuels due to low burning point, but the combustion heat value is only within 3000-6000J/g. The crystalline metal energetic material can have a high combustion heat value of 7000-30000J/g, and is developed or applied to rocket solid propellants, submarine underwater propellants and firework display in a small amount. However, the high ignition temperature of crystalline metals prevents subsequent applications of such energetic materials. Taking aluminum as an example, although the calorific value of aluminum can reach 30000J/g, the actual ignition temperature thereof is higher than 2000 ℃, thus making the crystalline pure aluminum energetic material difficult to ignite and apply.
In order to maintain a high combustion heat value of the metal and significantly reduce the ignition temperature, the existing strategy is to pulverize and sufficiently reduce the size of the powder, and specific approaches are chemical synthesis, mechanical alloying, thermal hydrogen treatment, catalysts and the like. The research shows that after the metal aluminum and the metal magnesium are processed into nano particles through powdering, the ignition temperature of the metal aluminum and the metal magnesium can be obviously reduced, and the combustion efficiency can be improved. Many metal powders exhibit liquid-like characteristics when the diameter of the nanoparticles is below ten nanometers. However, the powdering method has high cost, low yield, poor stability, low safety, high risk in the production, storage and transportation of metal powder, and is not suitable for practical use, and therefore, it is necessary to develop other means for utilizing metal as energetic material.
Amorphization of the alloy may provide another route to the preparation of metallic high energy materials. The amorphous alloy material can freeze the liquid structure of the alloy in the solid, store a large amount of liquid energy in the solid, and store gas with small molecular size such as hydrogen or oxygen in the solid, thereby improving energy, increasing chemical activity, reducing the ignition point of the material, ensuring more sufficient combustion reaction and improving the combustion heat value of the material. Meanwhile, as a typical metastable material, the amorphous alloy can stably maintain high energy for hundreds of years at room temperature, and the explosion danger of alloy particles caused by instability is avoided. The existing research shows that the amorphous alloy strip prepared by a quenching and strip-casting method is easier to be oxidized. By testing the oxidizability of a series of alloy samples, amorphous alloys > quasicrystalline alloys > crystalline alloys. This indicates that the amorphous state is the most suitable material for combustion in the alloy. In addition, the amorphous alloy strip, the filament and the powder have mature preparation process, low cost, large yield and good mechanical property, so the amorphous alloy strip, the filament and the powder are suitable for being used as novel high-energy materials.
Disclosure of Invention
Therefore, the invention aims to overcome the defects in the prior art and provide a high-energy-content amorphous alloy material, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a high energy content amorphous alloy material, which contains one or more of the following elements: mg, Al, La, Ce, Zr; and the heat value of the high-energy-content amorphous alloy material is 0.7-30 kJ/g, preferably 10-25 kJ/g.
The amorphous alloy material according to the first aspect of the present invention, wherein the volume fraction of the amorphous phase in the material is not less than 80%.
The amorphous alloy material according to the first aspect of the present invention, wherein when Mg and/or Al is contained in the material, the amorphous alloy material is represented by general formula I:
MguAlvCuwGdxYyHzOq (I)，
wherein u, v, w, x, y, z, q are atomic percentages, and 0< u <70, 0< v <90, 0< w <30, 5< x <15, 0< y <30,0< z <0.05,0< q < 0.05.
The amorphous alloy material according to the first aspect of the present invention, wherein when La and/or Ce is contained in the material, the amorphous alloy material is represented by general formula II:
LajCekColNimCunAloHpOq (II)，
wherein J, k, l, m, n, o, p and q are atomic percentages, J is more than or equal to 50 and less than or equal to 70, k is more than or equal to 0 and less than or equal to 40, l is more than or equal to 0 and less than or equal to 40, m is more than or equal to 0 and less than or equal to 40, n is more than or equal to 0 and less than or equal to 30, o is more than or equal to 0 and less than or equal to 30, p is more than or equal to 0 and.
The amorphous alloy material according to the first aspect of the present invention, wherein, when Zr is contained in the material, the amorphous alloy material is represented by general formula III:
ZraTibCucNidAleHfOg (III)，
wherein a, b, c, d, e, f and g are atomic percent, a is more than or equal to 0 and less than or equal to 60, b is more than 0 and less than 10, c is more than 0 and less than 30, d is more than 0 and less than 20, e is more than 0 and less than 20, f is more than 0 and less than 0.05, and g is more than 0 and less than 0.05.
The second aspect of the present invention provides a method for preparing the amorphous alloy material of the first aspect, the method comprising the following steps:
(1) proportioning raw materials according to the raw material proportion and carrying out vacuum tube sealing;
(2) performing multiple arc melting or induction melting on the raw materials in the step (1) to uniformly mix the components, and cooling to obtain a master alloy ingot;
(3) and (3) crushing the mother alloy cast ingot in the step (2), and carrying out high-temperature quenching to obtain the amorphous alloy material.
The production method according to the second aspect of the invention, wherein, in the step (3), the high-temperature quenching is performed in a high-vacuum argon atmosphere; and/or
The high-temperature heating temperature is 1000-2000 ℃, and preferably 1200-1500 ℃.
The third aspect of the invention provides a high-energy-content amorphous alloy strip, which is made of the amorphous alloy material of the first aspect;
preferably, the thickness of the amorphous alloy strip is 20-50 μm.
The fourth aspect of the present invention provides a method for preparing the high energy content amorphous alloy ribbon described in the third aspect, the method comprising the following steps:
(a) proportioning raw materials according to the raw material proportion and carrying out vacuum tube sealing;
(b) performing multiple arc melting or induction melting on the raw materials in the step (1) to uniformly mix the components, and cooling to obtain a master alloy ingot;
(c) b, strip throwing, namely crushing the mother alloy cast ingot in the step (b), heating at high temperature until the mother alloy cast ingot starts to flow, and spraying argon onto the surface of a water-cooled copper wheel with the linear speed of 30-50m/s to obtain the strip;
preferably, the linear speed of the water-cooling copper wheel is 30-50 m/s.
The fifth aspect of the invention provides application of the high-energy-content amorphous alloy material in the first aspect in preparation of explosive leads, electric ignition powder, solid rocket propellant, underwater propellant, aviation fuel and/or fireworks.
The invention relates to a method for preparing a high-energy-content material with high combustion heat value and an ignition point between non-metal and crystalline metal, namely a method for improving the combustion heat value and reducing the ignition point by amorphizing an alloy material.
The invention discloses a method for preparing a high-energy-content material by using alloy non-crystallization, in particular to a method for preparing a magnesium-based, rare earth-based or zirconium-based amorphous alloy high-energy-content material. The components of the material are mainly magnesium aluminum, rare earth or zirconium, and are matched with a certain amount of copper, nickel, cobalt or aluminum. The preparation of the material comprises the steps of firstly mixing various components according to a proper proportion, then smelting in an induction smelting furnace for 3-5 minutes to obtain an alloy ingot with uniform components, then smashing the ingot into a plurality of small blocks of 3-5g, respectively placing the small blocks in different conical quartz tubes, carrying out induction heating until the small blocks are melted in a liquid state, blowing the small blocks onto the surface of a copper wheel rotating at a high speed through high-pressure argon gas to carry out rotary quenching and throwing out, and thus obtaining the strip or filament of the amorphous alloy high-energy-content material. Powder samples were obtained by high energy ball milling of filament samples. In addition, the filament can be obtained by rapidly drawing the high-temperature molten liquid in the quartz tube, and the powder sample can be prepared in an air atomization mode. Since many amorphous alloy materials have the characteristic of easy absorption of hydrogen or oxygen, the combustion heat value or combustion efficiency of the amorphous alloy high-energy material can be improved by storing hydrogen or oxygen. The method comprises arc melting the master alloy in a hydrogen atmosphere; doping the amorphous alloy with hydrogen at high temperature and high pressure; adding a small amount of metal oxide with the same metal component into the master alloy raw material; annealing the amorphous alloy in oxygen at a constant temperature below the glass transition temperature, and the like. The calorific value of the magnesium-aluminum-based, lanthanum-cerium-based or zirconium-based high-energy-content amorphous alloy material prepared by the invention can reach 10-25kJ/g, and is higher than that of the existing non-metal explosive; the ignition temperature can be reduced by 50 ℃, and is far lower than that of the existing crystalline alloy energetic material; the combustion efficiency can be improved by 10-15% compared with the same crystalline alloy; the strips, filaments and powder material can all be ignited in air by a 2.5v tesla coil tip or with a lighter.
The invention aims to provide a novel method for preparing a metal high-energy material by using alloy amorphization. The amorphous alloy high-energy material has lower ignition point, retains higher combustion heat value, and is safer, lower in cost and higher in yield compared with crystalline alloy nano powder. The amorphous alloy high-energy-content material can be applied to the fields of explosives, leads, fireworks, solid propellants and the like.
It is another object of the present invention to provide several possible formulations of amorphous alloy materials for energetic materials, which have adjustable heat of combustion and fire point ranges, and which are comparable to existing solid energetic materials.
The purpose of the invention is realized by the following technical scheme:
the invention provides an amorphous alloy high-energy-content material, which is prepared into amorphous alloy high-energy-content materials in the shapes of strips, filaments and powder by material preparation, vacuum tube sealing, electric arc melting or induction melting, ingot casting crushing, high-temperature quenching, melt spinning, wire drawing, ball milling and high pressure or annealing.
The method provided by the invention is used for preparing the amorphous alloy high-energy-content material, the energy state of the alloy is improved by utilizing the amorphization of the alloy, and the alloy usually contains magnesium aluminum element, lanthanum cerium element or zirconium element.
The thickness of the amorphous alloy high-energy-content strip is 20-50 mu m. The relaxation enthalpy below the glass transition temperature obtained by DSC test is about 50J/g; the volume fraction of the amorphous phase is not less than 80%.
The preparation of the amorphous alloy strip comprises the following steps:
1) preparing materials: mixing the single components of the alloy required by the formula according to molar ratio;
2) ingot casting: mixing the single components, placing the mixture in an argon vacuum arc furnace for titanium adsorption, and repeatedly and uniformly smelting until all the components are uniformly mixed to obtain a master alloy ingot;
3) smashing the alloy ingot by using a melt-spun method, taking 3-5g of small blocks, putting the small blocks into a melt-spun glass tube, carrying out induction heating to 1200-1500 ℃ in a high-vacuum argon atmosphere, spraying argon onto the surface of a copper wheel at the moment when liquid begins to flow, and carrying out rapid cooling to obtain the high-energy amorphous alloy strip.
4) Annealing crystallization the flaked amorphous strip is put into a quartz tube, the tube is sealed by vacuumizing, then the tube is put into an annealing furnace, and the annealing is carried out for 2 hours above the glass transition temperature, so as to obtain a crystallized amorphous strip for comparison.
According to the preparation method, the purity of the used raw materials such as La, Ni, Al, Mg, Cu, Gd, Ce, Co, Zr and the like is not lower than 99.5 wt%.
The amorphous alloy high-energy-content material has the following characteristics:
1) the state of matter is amorphous;
2) the ignition point is low, and the lighter is easy to ignite;
3) the burning speed is faster than that of the same kind of crystalline metal;
4) the combustion efficiency is higher than that of crystalline metal;
5) the combustion heat is larger than that of the crystalline non-metallic energetic material.
The amorphous alloy strip has a high energy state, can be ignited by a lighter in the air at room temperature, and can maintain a spontaneous combustion process. Is suitable for being used as an explosive lead.
The amorphous alloy strip and the amorphous alloy powder have low ignition point and high combustion speed, can be ignited by a Tesla coil with 2.5v voltage, are suitable for electric ignition powder of an electronic detonator, and can shorten the ignition time and improve the safety.
The heat value of the amorphous alloy strip and the amorphous alloy powder is higher than that of crystalline nonmetal energetic materials, and the amorphous alloy strip and the amorphous alloy powder can be used for solid rocket propellants, underwater propellants, aviation fuels and the like in the future.
The amorphous alloy strips and powder of the invention are fiercely combusted, accompanied by sparks, and can obtain wide color selection due to the wide material component database of the amorphous alloy, and can be used for demonstration of fireworks.
The formula of the magnesium-aluminum based amorphous alloy energetic material is as follows:
MguAlvCuwGdxYyHzOq； (I)
wherein the content of the first and second substances,
mg, Al, Cu, Gd, Y, H and O respectively represent magnesium, aluminum, copper, gadolinium, ytterbium, hydrogen and oxygen, u, v, w, x, Y, z and q are atomic percent, namely coordination numbers of the components, and the variation range is 0< u <70, 0< v <90, 0< w <30, 5< x <15, 0< Y <30,0< z <0.05 and 0< q < 0.05.
The formula of the lanthanum-cerium based amorphous alloy energetic material is as follows:
LajCekColNimCunAloHpOq； (II)
wherein the content of the first and second substances,
la, Ce, Co, Ni, Cu, Al, H, O respectively represent lanthanum, cerium, cobalt, nickel, copper, aluminum, hydrogen and oxygen, J, k, l, m, n, O, p, q are atomic percent, the variation range is that J is more than or equal to 50 and less than or equal to 70, k is more than or equal to 0 and less than or equal to 40, l is more than or equal to 0 and less than or equal to 40, m is more than or equal to 0 and less than or equal to 40, n is more than or equal to 0 and less than or equal to 30, O is more than or equal to 0 and less than or equal to 30, p is more than or equal.
The formula of the zirconium-based amorphous alloy energetic material is as follows:
ZraTibCucNidAleHfOg； (III)
wherein the content of the first and second substances,
a, b, c, d, e, f and g are atomic percent, the variation range is that a is more than or equal to 0 and less than or equal to 60, b is more than 0 and less than 10, c is more than 0 and less than 30, d is more than 0 and less than 20, e is more than 0 and less than 20, f is more than 0 and less than 0.05, and g is more than 0 and less than 0.05.
The preparation of the amorphous alloy energetic material strip, the filament and the powder comprises the following steps (taking magnesium-based amorphous alloy as an example):
1) preparing materials: mixing the magnesium block, the copper block and the gadolinium block according to the atomic percentage of 50-70%, 25-30% and 5-15%.
2) Ingot casting: the materials are smelted in an induction smelting furnace at the temperature of 1200 ℃ and 1500 ℃ for 3-5 minutes, and an alloy ingot is obtained after cooling. And crushing the cast ingot into small blocks of 3-5g, and respectively placing the small blocks in a vacuum quartz tube for later use.
3) Belt throwing: at a vacuum degree of 10-3-10-4In a Pa vacuum melt-spun furnace, the rotating speed of a copper roller is adjusted to be 30-40m/s, the material in a quartz tube is inductively smelted to be liquid, and the liquid is sprayed on the surface of the copper roller after the smelting is uniform, so that the amorphous strip with the thickness of 20-100 mu m can be obtained.
4) Throwing: at a vacuum degree of 10-3-10-4In a Pa vacuum filament throwing furnace, adjusting the rotating speed of a copper roller with a convex groove to be 30-40m/s, carrying out induction melting on the material in a quartz tube to be in a liquid state, and spraying the liquid to the convex groove of the copper roller after uniform melting to obtain the amorphous filament with the diameter of 10-30 microns.
5) Drawing: at a vacuum degree of 10-4In a vacuum drawing furnace of Pa, an amorphous rod having an exposed 1.5mm diameter portion with a 2mm diameter inside is accommodated in a glass tube, the exposed portion is wrapped with a nickel wire, and a weight of about 50g to 100g is suspended. The material in the quartz glass tube is induction melted to a red hot state for two or three seconds, then the heating is stopped, and then amorphous wires of about 10 cm can be pulled out under the traction of a weight.
5) Mechanical grinding to prepare powder: placing the amorphous strip in a mortar, and grinding for a few minutes until the amorphous strip becomes fragments; the amorphous powder with the grain diameter below 500nm can be obtained by mechanically grinding the amorphous powder by a planetary ball mill and selecting a proper ball milling process and time.
6) Gas atomization powder preparation: namely, high-pressure inert gas is used for impacting the amorphous alloy broken ingot to achieve the purpose of breaking the amorphous alloy broken ingot into small particles, and the particle size range of the amorphous alloy broken ingot is 10-200 mu m.
7) Smelting and storing hydrogen: charging a proper amount of hydrogen into a high vacuum electric arc furnace, preparing an amorphous alloy ingot by adopting a common electric arc melting method, crushing the ingot, and then carrying out melt spinning, wire drawing or ball milling to obtain the amorphous alloy high-energy-content material in the shapes of strips, filaments and powder.
8) High-pressure hydrogen storage: amorphous alloy powder is filled into a container in a certain mode, and hydrogen is adsorbed to the surface of the alloy at high temperature and high pressure and is diffused into the alloy to form hydride.
9) Annealing and oxygen storage: in a tube furnace with oxygen atmosphere, the amorphous alloy strips are annealed for a certain time to obtain amorphous alloys with different oxygen contents.
10) Synthesizing and storing oxygen: when the master alloy is smelted, various pure elements and titanium oxide are used as raw materials, and the amorphous alloy material for storing oxygen can be obtained through arc smelting or induction smelting and high-temperature quenching.
Compared with the existing crystalline metal energetic material, the amorphous alloy energetic material provided by the invention has the following beneficial effects:
1. the ignition point is about 50 degrees lower. Is easier to ignite than crystalline metal and can maintain self-propagating combustion reaction. For example, with a tip discharge of a Tesla coil, a 25 μm thick lanthanum-based amorphous strip can be ignited, but a lanthanum crystalline strip of similar thickness cannot.
2. The efficiency of the combustion reaction is significantly improved, which can approach 80% of the theoretical complete combustion. For example, the mass of the lanthanum-based amorphous ribbon can increase by 20% after combustion, comparable to the theoretical maximum oxidation mass increase of 25%.
3. Compared with alloy powder, the alloy powder has good stability and no risk of dust explosion; for example, lanthanum-based amorphous alloy strips prepared ten years ago can still maintain high energy value after ten years, and cannot explode due to external mechanical stimulation.
4. The amorphous strip or filament with the length of more than one meter can be prepared in one step, does not need subsequent processing, and can be used for application of leads and the like.
5. The amorphous alloying method of the present invention is applicable to almost all metal elements other than alkali metals. Nearly 1000 materials known to date can be prepared by this method.
6. The zirconium-based and titanium-based amorphous alloys can be kept amorphous while dissolving a large amount of oxygen in the solid in advance. The method has the advantages of low melting point, full reaction and high efficiency.
7. The combustion heat value of the amorphous alloy can keep 50-90% of the energetic material of the same metal. The amorphous alloy after storing hydrogen, such as magnesium-based amorphous alloy, can further improve the heat value by 50 percent.
Compared with the existing non-metal energetic material, the amorphous alloy high energetic material of the invention has the following beneficial effects:
1. the combustion heat value of unit mass is improved by 10-50%.
2. The mechanical strength and the elastic modulus are in the magnitude of 10-100Gpa, while the non-metal energetic material is only in the magnitude of 100 MPa.
3. Part of the amorphous alloy high-energy material can emit fierce strong light when burning, and is suitable for fireworks display and other purposes.
4. The production process of the amorphous alloy high-energy material is completely physical change (such as high temperature and rapid cooling) and does not generate chemical change, so that the amorphous alloy high-energy material is safer than a non-metal energetic material.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 shows the thermal analysis curves of the magnesium-based, lanthanum-based, zirconium-based, cerium-based amorphous alloy ribbons in examples 1, 5, 8, 10. The temperature rise speed is 20K/min, and the temperature range is 50-350 ℃.
Fig. 2 shows X-ray diffraction patterns of magnesium-based and lanthanum-based amorphous ribbons of examples 1 and 8 after annealing at different temperatures.
Fig. 3 shows photographs of the magnesium-based amorphous ribbon and the magnesium-based crystalline ribbon of example 1 during the burning process, respectively, in which fig. 3a is the magnesium-based amorphous ribbon and fig. 3b is the magnesium-based crystalline ribbon.
Fig. 4 shows the thermogravimetric curve of the lanthanum based amorphous alloy ribbon of example 8, from which the ignition point and mass change can be deduced.
Figure 5 shows the heat of combustion versus the ignition point for various amorphous alloy ribbons versus prior energetic materials.
FIG. 6 shows X-ray diffraction patterns before and after doping oxygen in the titanium-based oxygen-containing amorphous material in Experimental example 2.
FIG. 7 shows the magnesium-based amorphous powder (ingredient Mg) of example 1275Ce15Ni10) SEM photographs (average particle diameter 80 to 100 μm) before and after hydrogen storage. Wherein FIG. 7(a) is an SEM photograph before hydrogen storage and FIG. 7(b) is an SEM photograph after hydrogen storage. The powder size did not change after hydrogen storage.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
The reagents and instrumentation used in the following examples are as follows:
reagent:
Mg，Cu，Gd，La，Ni，Al，Zr、Ti、TiO2ce, Al, Cu, Co, from Beijing Jiaming platinum non-ferrous metals, Inc.
The instrument comprises the following steps:
the high-vacuum tape throwing machine is purchased from the department of physical and electrical technology Limited company, model WK-IIB;
an electric arc furnace, purchased from a device for preparing multifunctional new materials of type WK, manufactured by Biotech, Inc;
high pressure hydrogen storage Gas Reactor, available from AMC, USA, model AMC 7700.
Example 1
This example illustrates the preparation of Mg61Cu28Gd11Magnesium-based amorphous ribbon high energy content material.
Mg, Cu and Gd with the raw material purity of 99.5 wt.% (weight percentage) are mixed according to the proportion of 61: 28: 11 (atomic percent) for proportioning; putting the quartz tube into the quartz tube for tube sealing treatment; repeatedly carrying out induction melting for multiple times in a high-vacuum melt-spun machine; after the components are uniformly mixed, cooling to obtain a master alloy ingot; crushing the cast ingot and putting 5g of crushed materials into a conical quartz tube of a melt-spun machine; heating to 800 ℃ in an atmosphere of vacuumizing and then filling argon; the spray button was quickly pressed at the moment the liquid was about to flow, so that the liquid was blown down onto the surface of a water-cooled and high-speed rotating (30m/s) copper wheel with high-speed argon gas for spinning. Thus, an amorphous alloy ribbon having a thickness of 50 μm and a length of about 1 m was obtained.
As shown in fig. 3a, the mg-based amorphous alloy ribbon has good combustion performance and has a firework exhibiting effect accompanied with sparks. The magnesium-based crystal ribbon as shown in fig. 3b burns with a darker flame, is less efficient in burning, and does not produce the flaming effect of sparks.
Example 2
This example illustrates the preparation of La55Co20Al25The lanthanum-based amorphous alloy filament high-energy-content material.
Preparing La, Co and Al with the raw material purity of more than 99.5 wt% (weight percentage) according to the atomic percentage of 55:20: 25; mixing and smelting the components in an argon arc furnace for titanium adsorption for more than 5 times until the components are uniformly mixed; cooling to obtain a mother alloy ingot, crushing, and putting 4g of crushed materials into a special glass tube of a melt-spun machine; heating to a temperature higher than the temperature of the glass substrate under the atmosphere of vacuumizing and filling argon; when the liquid is about to flow, the liquid is sprayed onto the surface of a copper roller with convex grooves, which is water-cooled and rotates at high speed (the linear speed is 30-50 m/s). Thereby throwing out the lanthanum-based amorphous alloy wire with the diameter of 10-30 mu m. The rotating speed is high, and the strip is thin.
Carrying out suction casting on the master alloy ingot in an electric arc furnace into a copper mold with a round hole with the upper diameter of 2mm and the lower diameter of 1.5mm to obtain a solid amorphous rod; firstly, the lower end of a bar material is tied with a weight of 10-100g, then the bar material is heated in an induction coil to be near the glass transition temperature point, and then the amorphous alloy wire with uniform diameter can be obtained by drawing and drawing the wire by utilizing the gravity of a heavy object.
The prepared strip was ground vigorously in a mortar for about 20 minutes to obtain a finely divided alloy in powder form, the material still remaining amorphous.
Example 3
This example illustrates the preparation (Mg)61Cu28Gd11)0.97H0.03The magnesium-based amorphous alloy powder is a high-energy-content material.
The magnesium-based amorphous ribbon prepared in example 1 was ground vigorously in a mortar for 20 minutes, or after being spun and then ball milled using a high-speed ball mill (180rpm, 3 hours), and then sieved through a 200-mesh sieve, to obtain a powder sample of about 10 μm in size, the material of which still remained amorphous. As shown in fig. 6, the ball-milled amorphous powder had uniformly distributed particle sizes.
The amorphous alloy scraps were impacted using high-pressure argon gas, and the scraps gradually changed into a powder shape having a particle size ranging from 10 to 200 μm for about 2 hours.
2g of magnesium-based amorphous alloy powder is filled in a high-pressure hydrogen storage device, a hydrogen atmosphere of 20mL/min is introduced, the temperature is raised to 300 ℃, and the temperature is maintained for 30min, so that the high-energy-content magnesium-based hydrogen-containing amorphous alloy powder material is obtained. Compared with pure amorphous alloy powder, the combustion heat value of the amorphous alloy powder with 3 wt% of hydrogen storage is improved to 150%.
Example 4
This example illustrates the preparation of Zr55Cu30Ni5Al10The zirconium-based amorphous alloy strip is a high-energy material.
1) The method comprises the following steps: and (4) arc melting. Mixing Zr, Cu, Ni and Al with the purity of more than 99.5 wt% (weight percentage) according to the atomic percentage of 55:30:5: 10; mixing and smelting the components in an argon arc furnace for titanium adsorption for more than 5 times until the components are uniformly mixed; cooling to obtain a mother alloy ingot, crushing, and placing 5g of the ingot in a conical quartz tube; heating to 1000 ℃ in an atmosphere of vacuumizing and then filling argon; immediately before the liquid was flowed, it was rapidly sprayed onto the surface of a copper roll which was water-cooled and rotated at a high speed (linear velocity of 30 m/s). Thereby obtaining the high-energy-content material of the zirconium-based oxygen-containing amorphous alloy strip.
2) The second method comprises the following steps: and (5) annealing and oxidizing. Preparing Zr, Cu, Ni and Al with the raw material purity of more than 99.5 wt% (weight percentage) according to the atomic percentage of 55:30:5:10 and carrying out melt spinning to obtain an amorphous strip; and placing the amorphous strip in a tubular annealing furnace, sealing, vacuumizing, introducing oxygen atmosphere, and annealing at 350 ℃ for 1.5h and 3h respectively to obtain the zirconium-based oxygen-containing amorphous alloy strip high-energy-content material with oxygen concentration of 3000ppm and 6000ppm respectively.
Example 5
This example illustrates the preparation of Ce by the wire throwing method68Al10Cu20Co2Amorphous alloy wire and is used as high energy containing material.
The components of Ce, Al, Cu and Co with the raw material purity of 99.5 percent (mass percentage) are mixed according to the mol ratio of 68: 10: 20:2, burdening; mixing and smelting the components in an argon arc furnace for titanium adsorption for at least 5 times until the components are uniformly mixed. And cooling to obtain a mother alloy ingot, crushing, putting 5g of crushed ingot into a quartz glass tube for melt spinning, heating to 700 ℃ in a vacuum argon atmosphere, and quickly spraying the crushed ingot onto the surface of a water-cooled copper wheel with the linear velocity of 30-50m/s when liquid is about to flow. At 104And throwing the lanthanum-based amorphous alloy strip with the thickness of 25-40 mu m (the higher the rotating speed, the smaller the thickness) at the cooling speed of K/s.
The prepared strip is forcibly ground in a mortar for about 20 minutes to obtain a finely-divided powdered alloy, and the material still keeps an amorphous state;
the method comprises the steps of carrying out suction casting on a master alloy ingot in an electric arc furnace by adopting a copper die with an upper part being 2mm and a lower part being 1.5mm in hole to obtain 6 solid amorphous bars, tying a proper weight on the lower end of each bar, heating the bar in an induction coil until the temperature is close to the glass and the transition temperature point, naturally pulling the tail of each bar into a filamentous shape under the pulling of the weight, and adjusting the heating time and the weight material amount to obtain the amorphous wires with different diameters. The correspondence between the mass of the particles and the diameter of the amorphous wire is shown in Table 1.
TABLE 1 correspondence of mass by weight and diameter of amorphous wire
| Weight of substance/g | 22 | 37 | 40 | 50 |
| Diameter/nm of |
1200 | 1000 | 800 | 500 |
And (3) taking part of the original strip, putting the original strip into a quartz tube, sealing the tube in vacuum, and then annealing at a constant temperature of 105 ℃ to obtain a crystalline alloy strip for comparison.
Examples 6 to 11
This example illustrates the properties of amorphous alloy ribbons prepared by the method of the present invention.
Amorphous alloy strips were prepared by the methods of examples 1-5, respectively, wherein examples 6-11 were prepared by the method of example 1, respectivelyThe difference is only in the replacement of raw materials and the adjustment of the raw material proportion, and the thermodynamic properties are shown in the following table 2. Wherein Q isGHeat of combustion, Q, of amorphous alloysXFor the heat of combustion, Δ Q, of the corresponding crystalGDifference in combustion heat, Δ Q, between amorphous and crystallineG/QXIs the ratio of the difference between the combustion heat of the amorphous and crystalline particles to the calorific value of the crystalline particles, Δ HGIs an amorphous alloy with respect to the enthalpy of crystal, Delta QG/ΔHGThe ratio of the combustion heat difference value and the relative enthalpy value of the amorphous and the crystalline is adopted.
TABLE 2 Properties of amorphous alloy ribbons prepared by the method of the invention
FIG. 1 shows the DSC curve of an amorphous high energy content material that absorbs and releases heat, absorbs heat upward, and releases heat downward at a temperature rise of 20 degrees per minute. Which are the amorphous alloys prepared in examples 1, 5, 8, and 10, respectively.
Figure 2 shows the XRD pattern of the amorphous high energy content material. Which are the amorphous alloys prepared in examples 1 and 8, respectively.
FIG. 4 shows lanthanum-based amorphous high energy content materials (La) with different energy states55Co20Al25) The material was weighted upward and weighted downward in an open vessel at a mass change of 10 degrees per minute during the heating process.
FIG. 5 shows a preferred plot of reciprocal ignition points and heat of combustion values for various amorphous alloy ribbons with existing energetic materials. The top right corner is optimal and the bottom left corner is worst.
Example 12
This example illustrates the preparation of Mg75Ce15Ni10The magnesium-based amorphous alloy strip high-energy-content material.
1) And (4) induction melting. Mixing Mg, Ce and Ni components with the purity of more than 99.5 wt% (weight percentage) according to the ratio of 75:15:10 (atomic percentage); firstly, mixing and smelting Ce and Ni elements in an argon arc furnace for titanium adsorption for more than 5 times until the components are mixed uniformlyHomogenizing; cooling to obtain an intermediate master alloy ingot; then sealing the intermediate alloy ingot and Mg metal in a quartz tube in vacuum; placing the quartz tube in an induction smelting furnace, and heating an induction coil by using 20A current until the liquid is melted for 10 seconds; cooling and smashing the quartz tube to obtain Mg75Ce15Ni10And (3) alloy ingots.
2) And (4) throwing the belt. Carrying out induction heating to 1000 ℃ in an atmosphere of vacuumizing firstly and then filling argon; immediately before the liquid was flowed, it was rapidly sprayed onto the surface of a copper roll which was water-cooled and rotated at a high speed (linear velocity of 30 m/s). Therefore, the magnesium-based amorphous alloy strip high-energy-content material can be obtained.
3) After the melt spinning, the sample was ball milled using a high speed ball mill (180rpm, 3 hours) and then sieved through a 200 mesh sieve to obtain a powder sample of about 10 μm size (as shown in FIG. 7), the material still remaining amorphous.
4) Storing hydrogen. 2g of magnesium-based amorphous alloy powder is filled in a high-pressure hydrogen storage device, a hydrogen atmosphere of 20mL/min is introduced, the temperature is raised to 300 ℃, and the temperature is maintained for 30min, so that the high-energy-content magnesium-based hydrogen-containing amorphous alloy powder material is obtained. Compared with pure amorphous alloy powder, the combustion heat value of the amorphous alloy powder with 3 wt% of hydrogen storage is improved to 150%.
FIG. 7 shows the magnesium-based amorphous powder (ingredient Mg) of example 1275Ce15Ni10) SEM photographs (average particle diameter 80 to 100 μm) before and after hydrogen storage. Wherein FIG. 7(a) is an SEM photograph before hydrogen storage and FIG. 7(b) is an SEM photograph after hydrogen storage. The powder size did not change after hydrogen storage.
Test example 1
This example is used to illustrate the use of the product of the present invention as an electric primer for an electronic detonator.
Amorphous powder is added into a basic formula (potassium chlorate/charcoal powder/polyvinyl alcohol: 80/20/proper amount) of a common electric ignition powder head, and the influence of the content and proportion of the amorphous powder on the ignition time of the electric ignition powder head is researched. The change in the decomposition temperature of the ignition charge was measured by DSC, and it was found that as the amount of Mg-based amorphous added was gradually increased, the decomposition temperature of the material was gradually decreased before 5000ppm, and after exceeding 5000ppm, the decomposition temperature of the material began to rise again. The lowest temperature drop is 50 degrees celsius. The reasons for improving the performance are two: the amorphous alloy has higher thermal conductivity than nonmetal, large thermal mobility and better heat transfer; the amorphous is higher in energy than the metal crystal and can be released in combustion.
Test example 2
Preparation of Ti45Zr5Cu45Ni5And titanium-based oxygen-containing amorphous alloys and used for combustion.
The raw materials of Ti, Zr, Cu, Ni and TiO with the purity of more than 99.5 percent2The raw materials are respectively 45 atom percent: 5: 45: 5: 0 and 45: 5: 45: 5: 0.5, mixing, and smelting for more than 5 times until the mixture is uniform. The flammability was then tested in air at room temperature with a lighter and it was found that both oxygen-containing and non-oxygen containing amorphous alloy ribbons ignited easily. After TGA testing, the oxygen-containing amorphous alloy ribbon was found to have an ignition point of 960 ℃ and 980 ℃ respectively, i.e., the oxygen-containing amorphous ribbon was high in ignition point but burned more sufficiently. The inventors also prepared Ti according to the same method45Zr5Cu45Ni5O0.2And Ti45Zr5Cu45Ni5O0.05FIG. 6 shows the X-ray diffraction pattern of the titanium-based oxygen-containing amorphous material before and after oxygen doping.
The reasons for the improved performance are: the oxygen absorbing and dissolving capacity of the zirconium element can reach 30%, oxygen is doped into gaps of alloy atoms as a raw material, a solid solution with a certain concentration can be formed, so that the oxygen is in close contact with surrounding metal atoms, conversely, the metal atoms are more thoroughly exposed in an oxygen environment, so that the zirconium element can be oxidized in advance, and the combustion reaction is more complete.
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (10)
1. The high-energy-content amorphous alloy material is characterized by comprising one or more of the following elements: mg, Al, La, Ce, Zr; and the heat value of the high-energy-content amorphous alloy material is 0.7-30 kJ/g, preferably 10-25 kJ/g.
2. The amorphous alloy material of claim 1, wherein the volume fraction of the amorphous phase in the material is not less than 80%.
3. The amorphous alloy material according to claim 1 or 2, which is represented by general formula I when Mg and/or Al is contained in the material:
MguAlvCuwGdxYyHzOq (I)，
wherein u, v, w, x, y, z, q are atomic percentages, and 0< u <70, 0< v <90, 0< w <30, 5< x <15, 0< y <30,0< z <0.05,0< q < 0.05.
4. The amorphous alloy material according to claim 1 or 2, which is represented by general formula II when La and/or Ce is contained in the material:
LajCekColNimCunAloHpOq (II)，
wherein J, k, l, m, n, o, p and q are atomic percentages, J is more than or equal to 50 and less than or equal to 70, k is more than or equal to 0 and less than or equal to 40, l is more than or equal to 0 and less than or equal to 40, m is more than or equal to 0 and less than or equal to 40, n is more than or equal to 0 and less than or equal to 30, o is more than or equal to 0 and less than or equal to 30, p is more than or equal to 0 and.
5. The amorphous alloy material according to claim 1 or 2, which is represented by general formula III when Zr is contained in the material:
ZraTibCucNidAleHfOg (III)，
wherein a, b, c, d, e, f and g are atomic percent, a is more than or equal to 0 and less than or equal to 60, b is more than 0 and less than 10, c is more than 0 and less than 30, d is more than 0 and less than 20, e is more than 0 and less than 20, f is more than 0 and less than 0.05, and g is more than 0 and less than 0.05.
6. The method for preparing the amorphous alloy material according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) proportioning raw materials according to the raw material proportion and carrying out vacuum tube sealing;
(2) performing multiple arc melting or induction melting on the raw materials in the step (1) to uniformly mix the components, and cooling to obtain a master alloy ingot;
(3) and (3) crushing the mother alloy cast ingot in the step (2), and carrying out high-temperature quenching to obtain the amorphous alloy material.
7. The method according to claim 6, wherein in the step (3), the high-temperature quenching is performed in a high-vacuum argon atmosphere; and/or
The high-temperature heating temperature is 1000-2000 ℃, and preferably 1200-1500 ℃.
8. A high energy content amorphous alloy ribbon, wherein the amorphous alloy ribbon is made of the amorphous alloy material of any one of claims 1 to 5;
preferably, the thickness of the amorphous alloy strip is 20-50 microns.
9. Method for the preparation of amorphous alloy ribbon according to claim 8, characterized in that it comprises the following steps:
(a) proportioning raw materials according to the raw material proportion and carrying out vacuum tube sealing;
(b) performing multiple arc melting or induction melting on the raw materials in the step (1) to uniformly mix the components, and cooling to obtain a master alloy ingot;
(c) b, strip throwing, namely crushing the mother alloy cast ingot in the step (b), heating at high temperature until the mother alloy cast ingot starts to flow, and spraying argon onto the surface of a water-cooled copper wheel with the linear speed of 30-50m/s to obtain the strip;
preferably, the linear speed of the water-cooling copper wheel is 30-50 m/s.
10. Use of the high energy content amorphous alloy material of any one of claims 1 to 5 for the preparation of explosive leads, electric fuse charges, solid rocket propellants, underwater propellants, aviation fuels and/or fireworks.
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| CN114346237B (en) * | 2021-12-11 | 2023-07-11 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
| CN114480994A (en) * | 2022-01-27 | 2022-05-13 | 沈阳工业大学 | Device and process for improving deep cooling circulation induced rejuvenation capability of Zr-based amorphous alloy |
| CN114480994B (en) * | 2022-01-27 | 2022-11-08 | 沈阳工业大学 | Device and process for improving deep cooling circulation induced rejuvenation capability of Zr-based amorphous alloy |
| CN116334664A (en) * | 2023-05-30 | 2023-06-27 | 中石油深圳新能源研究院有限公司 | Amorphous nano powder for water electrolysis and preparation method and preparation device thereof |
| CN116334664B (en) * | 2023-05-30 | 2023-09-22 | 中石油深圳新能源研究院有限公司 | Amorphous nano powder for water electrolysis and preparation method and preparation device thereof |
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