CN110976848A - Aluminum alloy powder capable of blooming and preparation method and application thereof - Google Patents
Aluminum alloy powder capable of blooming and preparation method and application thereof Download PDFInfo
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- CN110976848A CN110976848A CN201911346317.XA CN201911346317A CN110976848A CN 110976848 A CN110976848 A CN 110976848A CN 201911346317 A CN201911346317 A CN 201911346317A CN 110976848 A CN110976848 A CN 110976848A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0832—Handling of atomising fluid, e.g. heating, cooling, cleaning, recirculating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/01—Use of vibrations
Abstract
The invention provides aluminum alloy powder capable of blooming and a preparation method and application thereof, and relates to the technical field of metal powder. The aluminum alloy powder capable of blooming is composed of a spherical aluminum matrix and nano particles dispersed in the spherical aluminum matrix; the nanoparticles comprise bismuth exclusive of tin, or comprise bismuth and tin; the aluminum alloy powder capable of blooming is spherical particles with smooth surfaces. The aluminum alloy powder capable of blooming is prepared by adopting an ultrasonic atomization quenching method. The aluminum alloy powder is used for reacting with gaseous water to generate hydrogen, has a flower-shaped appearance evolution process when reacting with the gaseous water, has high aluminum-hydrogen conversion efficiency, and can be widely applied to the fields of gaseous water hydrogen production, portable hydrogen supply and hydrogen medical treatment.
Description
Technical Field
The invention relates to the technical field of metal powder, in particular to aluminum alloy powder capable of blooming and a preparation method and application thereof.
Background
The exhaustion of traditional fossil energy sources forces people to pay more attention to green clean energy sources, such as wind energy, solar energy, hydrogen energy and water energy. Among them, hydrogen energy is considered as an ideal future energy source due to its excellent energy storage density and resource abundance. However, at present, the transportation and storage of hydrogen rely on high-pressure hydrogen cylinders, the hydrogen storage density is still low, and hydrogen is easy to leak in the collision process to cause safety accidents. Therefore, portable hydrogen production technology using a solid hydrogen storage material or an immediate hydrogen production material and having high hydrogen storage density and safety is receiving increasing attention.
For example, patent CN 101289163a describes an aluminum alloy for hydrogen production by hydrolysis, which comprises elemental metal aluminum (40-90 wt%), metal bismuth (8-50 wt%), low-melting metal (gallium, tin, zinc, cadmium, mercury, lead, indium, magnesium, germanium and/or calcium) (0-15 wt%), and water-soluble compound (1-40 wt%). The preparation method of the aluminum alloy is a mechanical ball milling method, wherein the mechanical ball milling method is characterized in that hard balls are used for strongly impacting, grinding and stirring raw materials by utilizing the rotation or vibration of a ball mill, powder particles are subjected to repeated processes of rolling, pressing, grinding and pressing (repeated processes of cold welding, crushing and cold welding), and finally the product is irregular flaky alloy powder. The aluminum alloy can react with water at normal temperature, and the hydrogen production can reach about 95% of a theoretical value.
For another example, patent CN 104190916 a discloses an antioxidant composite powder for hydrogen production by hydrolysis, which separates two liquid phases M and N simultaneously by liquid-liquid two-phase separation, and combines the liquid drops of the same liquid phase together, thereby forming a core/shell composite structure with half-wrapping or full-wrapping, so that the composite powder has a certain antioxidant property when stored in the air while rapidly producing hydrogen with water. The composite powder has stable property, strong oxidation resistance, simple preservation method and convenient carrying, the hydrogen production process is not limited by water and water, the problems of hydrogen storage and transportation are solved, the cost and the risk are reduced, and the composite powder has great application value and market prospect in civil fields such as mobile hydrogen sources, hydrogen-powered automobiles and the like and military fields such as submarines, ships, torpedoes and the like.
However, a problem with these water-based hydrogen production materials is that liquid water is required, which limits the application of portable hydrogen production technology.
Gaseous water is widely present in air, as compared to liquid water. Recent studies have found that Li, Mg, Zn, Bi, Sn and NaBH are doped4The aluminum-based material can react with high-temperature gaseous water, the initial temperature of the reaction with gaseous water can be reduced to 200 ℃, the conversion rate of aluminum-hydrogen reaches 87.83 percent, but the application is limited due to the high reaction temperature. However, no material has been found that can react continuously with gaseous water at temperatures below 200 ℃.
Disclosure of Invention
The invention aims to provide aluminum alloy powder capable of blooming and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
aluminum alloy powder capable of blooming is composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix; the nanoparticles comprise bismuth exclusive of tin, or comprise bismuth and tin; the aluminum alloy powder capable of blooming is spherical particles with smooth surfaces;
preferably, the content of bismuth is not less than 1% of the mass of the aluminum alloy powder, and when the nano particles comprise bismuth and tin, the total content of bismuth and tin in the aluminum alloy powder capable of blooming is not more than 10% of the mass of the aluminum alloy powder.
Preferably, the aluminum alloy powder capable of blooming further comprises other additional elements, and the other additional elements comprise one or more of iron, zinc and copper.
Preferably, the dosage of the other added elements is not more than 2% of the mass of the aluminum alloy powder capable of blooming, and when the nano particles comprise bismuth and do not comprise tin, the dosage of the other added elements is lower than the mass percentage of bismuth, and when the nano particles comprise bismuth and tin, the dosage of the other added elements is lower than the sum of the mass percentages of bismuth and tin.
Preferably, the content of particles with the particle size of 5-300 nm in the nano particles is more than 99%.
Preferably, the particle size of the aluminum alloy powder capable of blooming is 1-40 μm.
The invention provides a preparation method of aluminum alloy powder capable of blooming, which comprises the following steps:
(1) designing the components of the aluminum alloy powder to enable the components of the alloy to meet the component requirements of the technical scheme;
(2) introducing cooling water of 2-10 ℃ into a wall of an ultrasonic atomizing chamber of the ultrasonic atomizing furnace to cool the ultrasonic atomizing chamber to the temperature of 2-10 ℃, weighing each pure metal according to the designed components of the aluminum alloy powder, putting the pure metals into a crucible of a heating chamber of the ultrasonic atomizing furnace, vacuumizing to below 20Pa, filling protective gas to 0.01-0.1 MPa, heating the metals in the crucible by using heating equipment in the ultrasonic atomizing powder making furnace until all the metals are just melted, continuously heating to 100-250 ℃, introducing the molten liquid into the ultrasonic atomizing chamber, simultaneously using high-pressure inert gas of 8-15 MPa to generate ultrasonic oscillation airflow through an ultrasonic generating cavity of the ultrasonic atomizing furnace, impacting the molten liquid to atomize the molten liquid, and precipitating to obtain the flowering aluminum alloy powder.
Preferably, before the molten liquid is introduced into the ultrasonic atomization chamber, the temperature of the molten liquid is preferably kept for 8-15 min.
The invention provides application of the aluminum alloy powder capable of blooming or the aluminum alloy powder capable of blooming prepared by the preparation method in the scheme in preparation of hydrogen through reaction with gaseous water.
Preferably, the temperature of the gaseous water is between 10 ℃ and 300 ℃.
The principle of the invention is as follows:
the nano particles which are dispersed and distributed are introduced into the spherical aluminum matrix, so that when each aluminum powder is contacted with gaseous water or gaseous water in the air, water molecules can be adsorbed by the nano particles on the surface to rapidly permeate into the spherical aluminum matrix, and in the spherical aluminum matrix, the aluminum matrix around the nano activated particles which are dispersed and distributed reacts with the water molecules to generate hydrogen bubbles, so that the surface of the aluminum powder rapidly expands outwards, and the aluminum alloy powder has a blooming-like shape evolution process; the process makes the aluminum alloy powder open like a flower to continuously expose unreacted inner matrix of the powder to contact with air, thereby having high aluminum-hydrogen conversion efficiency.
The components of patent CN 104190916A pass through a liquid-liquid phase separation zone (L → L1+ L2) in the cooling process, the core of the separation is that two liquid phases M and N are separated out simultaneously through liquid-liquid two-phase separation, and liquid drops of the same liquid phase are combined together, so that a half-wrapped or full-wrapped core/shell type composite structure is formed. In order to obtain a higher cooling rate beyond the critical point for forming the core/shell composite structure, so that the separated liquid phase has nanometer scale and is instantly wrapped by the fast solidified matrix, ultrasonic atomization quenching powder preparation technology different from the traditional gas atomization powder preparation technology used in the patent is adopted, high-pressure inert gas generates ultrasonic oscillation airflow through an ultrasonic generation cavity of the ultrasonic atomization furnace and then impacts the molten liquid to generate high-frequency vibration, thereby crushing the molten liquid for atomization, rapidly solidifying the atomized alloy powder in a low-temperature atomization cavity at the temperature of 2-10 ℃, thereby leading the precipitated nano activated particles to be finer and preventing the nano activated particles from moving to the surface of the powder, thereby preventing the formation of a core-shell structure or a semi-wrapped core-shell structure and obtaining spherical aluminum alloy particles with nano particles dispersed in a spherical aluminum matrix.
Compared with the patent CN 104190916A, the antioxidant composite powder for hydrogen production by hydrolysis of the patent CN 104190916A is characterized in that the composite powder forms a half-wrapped or full-wrapped core/shell type composite structure, and microcracks and M-rich phase small particles exist in a shell layer. Due to the special structure, the modified starch has stable property and strong oxidation resistance, and can be stored in dry air for a long time without being oxidized. The invention improves the activity of the aluminum alloy powder reacting with gaseous water in the air by forming nano particles dispersed and distributed in the spherical aluminum matrix, thereby enabling the powder of the invention to be used for reacting with low-temperature gaseous water to generate hydrogen.
Compared with the aluminum alloy for hydrogen production by hydrolysis of CN 101289163A, the composite material for hydrogen production by hydrolysis of CN102992263A Al-Bi-NaCl-alkali metal or hydride and the preparation thereof, CN 101289163A and CN102992263A both adopt a ball milling technology to embed an active phase into a matrix in the ball milling process, so that the material has better hydrogen production performance. The invention adopts ultrasonic atomization quenching powder preparation technology, the activated particles have nanometer scale and are more uniformly distributed in the matrix by increasing the cooling speed, and in addition, the powder appearance of the invention has regular spherical shape, so that the sphere can react with low-temperature gaseous water to generate floriated shape change. Therefore, the invention can continuously react with low-temperature gaseous water to generate hydrogen.
Drawings
FIG. 1 is an internal TEM image of an aluminum alloy powder of example 1;
FIG. 2 is a diagram showing the appearance and flowering of the aluminum alloy powder according to example 1;
FIG. 3 is an SEM morphology of the aluminum alloy powder of example 1 after blooming;
FIG. 4 is a diagram showing the effect of the aluminum alloy powder of example 3 in hydrogen production.
Detailed Description
The invention provides aluminum alloy powder capable of blooming, which consists of a spherical aluminum matrix and nano particles dispersed in the spherical aluminum matrix; the nanoparticles comprise bismuth exclusive of tin, or comprise bismuth and tin; the aluminum alloy powder capable of blooming is spherical particles with smooth surfaces;
in the present invention, the content of bismuth in the aluminum alloy powder capable of blooming is preferably not less than 1% by mass of the aluminum alloy powder, and when the nanoparticles include bismuth and tin, the total content of bismuth and tin is preferably not more than 10% by mass of the aluminum alloy powder.
In the invention, the preferable proportion of particles with the particle size of 5-300 nm in the nano particles is more than 99%; the particle size of the aluminum alloy powder capable of blooming is preferably 1-40 μm, and more preferably 5-35 μm.
In the invention, the aluminum alloy powder capable of blooming preferably further comprises other added elements, and the other added elements preferably comprise one or more of iron, zinc and copper; the dosage of the other added elements is preferably not more than 2% of the mass of the aluminum alloy powder capable of flowering, and when the nano particles comprise bismuth and do not comprise tin, the dosage of the other added elements is lower than the mass percentage of bismuth, and when the nano particles comprise bismuth and tin, the dosage of the other added elements is lower than the sum of the mass percentages of bismuth and tin. When other additive elements are also contained, other additive elements are inevitably present in the nanoparticles and in the spherical aluminum matrix. The content distribution of the other additive elements in the nanoparticles and the spherical aluminum matrix is not particularly limited in the present invention.
The invention provides a preparation method of aluminum alloy powder capable of blooming, which comprises the following steps:
(1) designing the components of the aluminum alloy powder to enable the components of the alloy to meet the component requirements;
(2) introducing cooling water of 2-10 ℃ into a wall of an ultrasonic atomizing chamber of the ultrasonic atomizing furnace to cool the ultrasonic atomizing chamber to the temperature of 2-10 ℃, weighing each pure metal according to the designed components of the aluminum alloy powder, putting the pure metals into a crucible of a heating chamber of the ultrasonic atomizing furnace, vacuumizing to below 20Pa, filling protective gas to 0.01-0.1 MPa, heating the metals in the crucible by using heating equipment in the ultrasonic atomizing powder making furnace until all the metals are just melted, continuously heating to 100-250 ℃, introducing the molten liquid into the ultrasonic atomizing chamber, simultaneously using high-pressure inert gas of 8-15 MPa to generate ultrasonic oscillation airflow through an ultrasonic generating cavity of the ultrasonic atomizing furnace, impacting the molten liquid to atomize the molten liquid, and precipitating to obtain the flowering aluminum alloy powder.
The invention has no special requirement on the type of inert gas, and can be particularly but not exclusively argon, nitrogen and the like.
Before the molten liquid is introduced into the ultrasonic atomization chamber, the method preferably further comprises the step of preserving the temperature of the molten liquid for 8-15 min, and more preferably preserving the temperature for 10 min.
Due to the monotectic or sub-monotectic reaction of the aluminum-bismuth binary alloy or the aluminum-bismuth-tin ternary alloy, the material can generate the action of separating out the second liquid phase in the cooling process, the cooling speed is increased to exceed the critical point by adopting the ultrasonic atomization quenching powder preparation technology, the powder can be prevented from forming a core/shell structure or a semi-wrapped core-shell structure, the separated nano second liquid phase is rapidly solidified and wrapped by the matrix of the material, and the spherical aluminum alloy particles with nano particles dispersed and distributed in the spherical aluminum matrix are obtained.
The invention provides application of the aluminum alloy powder capable of blooming or the aluminum alloy powder capable of blooming prepared by the preparation method in the scheme in preparation of hydrogen through reaction with gaseous water. In the present invention, the temperature of the gaseous water is preferably 10 to 300 ℃, and more preferably normal temperature. The invention has no special requirement on the source of the gaseous water, and can be used in any environment containing the gaseous water, such as air with certain humidity. The aluminum alloy powder capable of being bloomed is preferably placed in an environment containing gaseous water to react to prepare hydrogen.
The existing aluminum alloy powder reacts with liquid water to prepare hydrogen, and the aluminum alloy powder capable of blooming is introduced with the nano activated particles which are dispersed and distributed in an aluminum matrix, so that when each aluminum powder is contacted with gaseous water or gaseous water in the air, water molecules can be adsorbed by the active nano particles on the surface to rapidly permeate into the aluminum alloy powder, and in the aluminum alloy powder, the aluminum matrix around the nano activated particles which are dispersed and distributed reacts with the water molecules to spontaneously generate hydrogen bubbles so that the surface of the aluminum powder rapidly expands outwards, so that the aluminum alloy powder has a blooming-like shape evolution process; the process ensures that the aluminum alloy powder is like flowers and continuously exposes the unreacted internal matrix of the powder, so that the aluminum alloy powder not only has high aluminum-hydrogen conversion efficiency, but also has the advantages of continuously increasing the surface area to volume ratio and stronger adsorption effect in the reaction process, and can be widely used for preparing hydrogen in gaseous water environment.
The aluminum alloy powder capable of blooming and the preparation method and application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 96.6% aluminum-3.4% bismuth by mass as a basic component, adding iron into the basic component to enable the final component to be 95.6% aluminum-3.4% bismuth-1% iron by mass, then proportioning metal raw materials according to the proportion, putting the alloy raw materials into a crucible of an ultrasonic atomization powder making furnace, vacuumizing an atomization furnace chamber to 10Pa, filling argon to 0.05MPa, meanwhile, introducing 10 ℃ cooling water into the wall of an ultrasonic atomization chamber of the ultrasonic atomization furnace to cool the ultrasonic atomization chamber to 10 ℃, then heating the raw materials in the crucible to 657 ℃ by using a medium-frequency induction coil in the ultrasonic atomization powder making furnace to completely melt the metal, continuously heating to 100 ℃ on the basis, and preserving the temperature for 10min to enable the raw materials to be uniformly melted. And then filling argon into the furnace chamber of the ultrasonic atomization furnace to 0.1MPa, immediately enabling the molten liquid to flow into the ultrasonic atomization chamber, simultaneously enabling the argon with the pressure of 10MPa to pass through an ultrasonic generation chamber of the ultrasonic atomization furnace to generate ultrasonic oscillation airflow, impacting the molten liquid to atomize, cooling and depositing atomized powder into a collection tank, taking down the collection tank, quickly putting the collection tank into a glove box under the argon protective atmosphere, and then taking out the powder in the collection tank to obtain the aluminum alloy powder capable of blooming.
The appearance and internal structure of the obtained powder were observed, and as a result, fig. 1 and 2 show, and fig. 1 is a TEM image of the inside of the aluminum alloy powder of example 1. FIG. 1 shows that, when the aluminum alloy powder prepared in example 1 is cut open and observed by a transmission electron microscope, the internal structure has a nano-dispersion structure (FIGS. (a) and (b)) and the nanoparticles are detected by an element spectrometer as a bismuth-rich phase (FIGS. (c) and (d)) in FIG. 1. Fig. 2 shows that the aluminum alloy powder prepared in example 1 is spherical aluminum alloy particles with smooth surfaces, which are composed of both spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix, and exhibits an open-type morphology evolution process in an environment containing gaseous water.
Example 2
Taking the mass fraction of 98 percent of aluminum and 2 percent of bismuth as a basic component, adding zinc and copper into the basic component to ensure that the final component is 97 percent of aluminum, 2 percent of bismuth, 0.5 percent of zinc and 0.5 percent of copper, then proportioning metal raw materials according to the proportion, putting the alloy raw materials into a crucible of an ultrasonic atomization powder making furnace, vacuumizing the furnace chamber of the atomization furnace to 10Pa, filling argon to 0.05MPa, meanwhile, introducing 2 ℃ cooling water into the furnace wall of an ultrasonic atomization chamber of the ultrasonic atomization furnace to ensure that the ultrasonic atomization chamber is cooled to the temperature of 2 ℃, then heating the raw materials in the crucible to the temperature of 658 ℃ by using a medium-frequency induction coil in the ultrasonic atomization powder making furnace to completely melt the metal, continuously heating to 125 ℃ on the basis, and preserving heat for 10min to ensure that the metal is uniformly melted. And then filling argon into the furnace chamber of the ultrasonic atomization furnace to 0.1MPa, immediately enabling the molten liquid to flow into the ultrasonic atomization chamber, simultaneously enabling the argon with the pressure of 8MPa to pass through an ultrasonic generation chamber of the ultrasonic atomization furnace to generate ultrasonic oscillation airflow, impacting the molten liquid to atomize, cooling and depositing atomized powder into a collection tank, taking down the collection tank, quickly putting the collection tank into a glove box under the argon protective atmosphere, and then taking out the powder in the collection tank to obtain the aluminum alloy powder capable of blooming.
The appearance and the internal structure of the obtained powder are observed, and the result is similar to that of example 1, and the aluminum alloy powder prepared in example 2 is spherical aluminum alloy particles with smooth surfaces, which are composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix, and shows an open-type morphology evolution process in an environment containing gaseous water.
Example 3
Taking 90.45% of aluminum, 3.1% of bismuth and 6.45% of tin by mass fraction as basic components, adding no other additive elements, proportioning metal raw materials according to the proportion, proportioning the metal raw materials according to the proportion, putting the alloy raw materials into a crucible of an ultrasonic atomization powder making furnace, vacuumizing an atomization furnace chamber to 1Pa, filling argon to 0.05MPa, introducing 5 ℃ cooling water into a furnace wall of an ultrasonic atomization chamber of the ultrasonic atomization furnace to cool the ultrasonic atomization chamber to 5 ℃, heating the raw materials in the crucible to 647 ℃ by using a medium-frequency induction coil in the ultrasonic atomization powder making furnace to completely melt the metal, continuously heating to 150 ℃ on the basis, and keeping the temperature for 10min to uniformly melt the metal. And then filling argon into the furnace chamber of the ultrasonic atomization furnace to 0.1MPa, immediately enabling the molten liquid to flow into the ultrasonic atomization chamber, simultaneously enabling the argon with the pressure of 12MPa to pass through an ultrasonic generation chamber of the ultrasonic atomization furnace to generate ultrasonic oscillation airflow, impacting the molten liquid to atomize, cooling and depositing atomized powder into a collection tank, taking down the collection tank, quickly putting the collection tank into a glove box under the argon protective atmosphere, and then taking out the powder in the collection tank to obtain the aluminum alloy powder capable of blooming.
The appearance and the internal structure of the obtained powder were observed, and the results are similar to those of example 1, which shows that the aluminum alloy powder prepared in example 3 is spherical aluminum alloy particles with smooth surfaces, which are composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix, and shows an open-type morphology evolution process in an environment containing gaseous water.
Flowering Effect test of examples
The aluminum alloy powder obtained in example 1 was placed in a water vapor environment with a humidity of 70 RH% and a temperature of 20 ℃, and the morphology change of the powder was observed at different times, with the result shown in fig. 2. Fig. 2 shows that the original aluminum alloy powder is spherical, and as the aluminum alloy powder is placed in a water vapor environment for a longer time, the aluminum alloy powder rapidly expands, bursts and grows into petals. This is because: when the alloy powder is placed in an environment containing gaseous water, water molecules contact and are adsorbed on the surface of the material, and perform rapid replacement reaction with aluminum in the area of nanoparticles on the surface and evolve hydrogen at nearby defects, so that the concentration of hydroxyl in a local area is increased due to rapid evolution of hydrogen, and then the hydrogen permeates into the inner layer of the material. Because the interior of the material is also provided with dispersed nano-activated particles, the nano-activated particles can promote the penetrated water molecules to be mixed with aluminum matrix in Al: Al (OH) like the nano-activated particles on the surface of the material3The reaction interface continuously generates replacement reaction and separates out hydrogen, and the inside of the powder particles generates higher hydrogen separation pressure to push the surfaces of the particles to bulge outwards quickly, so that the powder particles are burst. After the powder bursts, the aluminum inside the powder will continue to react with water molecules in the environment, releasing hydrogen gas, as it is exposed to the air, whereby petals grow outwardly from the surface of the powder. The appearance of the powder particles is changed from the original spherical shape to the flower shape shown in figure 3.
The aluminum alloy powders obtained in the embodiments 2 and 3 are respectively placed in a water vapor environment with the humidity of 70 RH% and the temperature of 20 ℃, the appearance change of the powders is observed at different time, the result is similar to that in the figure 2, obvious flowering processes are all generated, and the appearance of the flowering products is shown in the figure 3.
Performance testing of the examples
The aluminum alloy powder obtained in example 3 was reacted with gaseous water to produce hydrogen, and 0.05g of the powder was weighed and placed in a reaction environment of approximately 100 RH% relative humidity, and the hydrogen production efficiency and the hydrogen production amount at 30 ℃, 40 ℃ and 50 ℃ were shown in FIG. 4.
As can be seen from FIG. 4, at 50 deg.C, the aluminum alloy powder can reach 92% conversion efficiency within 50 minutes, and the hydrogen yield is 1045 mL/g. At 40 ℃ 84% conversion efficiency was achieved in 75 minutes with a hydrogen yield of 948 mL/g. At 30 ℃ a conversion efficiency of 71% was achieved in 100 minutes, with a hydrogen yield of 809 mL/g. The aluminum alloy powder can react with gaseous water at a lower temperature even at normal temperature to generate hydrogen, and has a higher reaction rate and higher aluminum-hydrogen conversion efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The aluminum alloy powder capable of blooming is characterized by consisting of a spherical aluminum matrix and nano particles dispersed in the spherical aluminum matrix; the nanoparticles comprise bismuth exclusive of tin, or comprise bismuth and tin; the aluminum alloy powder capable of blooming is spherical particles with smooth surfaces.
2. The aluminum alloy powder capable of blooming according to claim 1, wherein the content of bismuth is not less than 1% by mass of the aluminum alloy powder, and when the nanoparticles comprise bismuth and tin, the total content of bismuth and tin in the aluminum alloy powder capable of blooming is not more than 10% by mass of the aluminum alloy powder.
3. The aluminum alloy powder capable of flowering according to claim 1 further comprising other additive elements including one or more of iron, zinc and copper.
4. The aluminum alloy powder capable of blooming according to claim 3, wherein the amount of the other additive elements is not more than 2% by mass of the aluminum alloy powder capable of blooming, and when the nanoparticles include bismuth but not tin, the amount of the other additive elements is less than the mass percentage of bismuth, and when the nanoparticles include bismuth and tin, the amount of the other additive elements is less than the sum of the mass percentages of bismuth and tin.
5. The aluminum alloy powder capable of blooming according to any one of claims 1 to 4, wherein the nanoparticles are composed of particles having a particle diameter of 5 to 300nm in an amount of 99% or more.
6. The aluminum alloy powder capable of blooming according to any one of claims 1 to 4, wherein the particle size of the aluminum alloy powder capable of blooming is 1 to 40 μm.
7. The method for preparing aluminum alloy powder capable of blooming according to any one of claims 1 to 6, comprising the following steps:
(1) designing the components of the aluminum alloy powder to enable the components of the alloy to meet the component requirements of any one of claims 1-6;
(2) introducing cooling water of 2-10 ℃ into a wall of an ultrasonic atomizing chamber of the ultrasonic atomizing furnace to cool the ultrasonic atomizing chamber to the temperature of 2-10 ℃, weighing each pure metal according to the designed components of the aluminum alloy powder, putting the pure metals into a crucible of a heating chamber of the ultrasonic atomizing furnace, vacuumizing to below 20Pa, filling protective gas to 0.01-0.1 MPa, heating the metals in the crucible by using heating equipment in the ultrasonic atomizing powder making furnace until all the metals are just melted, continuously heating to 100-250 ℃, introducing the molten liquid into the ultrasonic atomizing chamber, simultaneously using high-pressure inert gas of 8-15 MPa to generate ultrasonic oscillation airflow through an ultrasonic generating cavity of the ultrasonic atomizing furnace, impacting the molten liquid to atomize the molten liquid, and precipitating to obtain the flowering aluminum alloy powder.
8. The method of claim 7, wherein the step of maintaining the temperature of the molten liquid for 8-20 min before introducing the molten liquid into the ultrasonic atomization chamber is preferably further included.
9. Use of the aluminum alloy powder capable of blooming according to any one of claims 1 to 6 or the aluminum alloy powder capable of blooming prepared by the preparation method according to any one of claims 7 to 8 in preparation of hydrogen by reaction with gaseous water.
10. Use according to claim 9, wherein the gaseous water has a temperature of 10 ℃ to 300 ℃.
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| PCT/CN2020/138834 WO2021129704A1 (en) | 2019-12-24 | 2020-12-24 | Aluminum alloy powder that is capable of blooming, preparation method therefor, and use thereof |
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Cited By (2)
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|---|---|---|---|---|
| WO2021129704A1 (en) * | 2019-12-24 | 2021-07-01 | 哈尔滨工业大学（深圳） | Aluminum alloy powder that is capable of blooming, preparation method therefor, and use thereof |
| CN115121800A (en) * | 2022-06-15 | 2022-09-30 | 北京理工大学 | Preparation method of AlTiZr-based multi-principal-element alloy powder with combustion micro-explosion characteristic |
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