WO2021129704A1 - 一种能开花的铝合金粉体及其制备方法和应用 - Google Patents
一种能开花的铝合金粉体及其制备方法和应用 Download PDFInfo
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- WO2021129704A1 WO2021129704A1 PCT/CN2020/138834 CN2020138834W WO2021129704A1 WO 2021129704 A1 WO2021129704 A1 WO 2021129704A1 CN 2020138834 W CN2020138834 W CN 2020138834W WO 2021129704 A1 WO2021129704 A1 WO 2021129704A1
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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
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- the invention relates to the technical field of metal powders, in particular to a bloomable aluminum alloy powder and a preparation method and application thereof.
- the patent CN 101289163A introduces an aluminum alloy for hydrogen production by hydrolysis. Its composition is simple metal aluminum (40-90wt%), metallic bismuth (8-50wt%), low melting point metals (metal gallium, tin, zinc, cadmium, Mercury, lead, indium, magnesium, germanium and/or calcium) (0-15wt%), water-soluble compounds (1-40wt%).
- the preparation method of the aluminum alloy is mechanical ball milling.
- the mechanical ball milling method uses the rotation or vibration of the ball mill to make the hard balls strongly impact, grind and agitate the raw materials.
- the powder particles are calendered, compacted, crushed, and recompressed. Repeated process (repeated cold welding-crushing-cold welding), the final product is irregular flake alloy powder.
- the aluminum alloy can react with water at room temperature, and the hydrogen production can reach about 95% of the theoretical value.
- patent CN 104190916 A discloses an anti-oxidant hydrolysis hydrogen production composite powder, which simultaneously separates two liquid phases M and N through liquid-liquid two-phase separation, and the droplets of the same liquid phase merge together to form
- the half-wrapped or fully-wrapped core/shell composite structure enables the composite powder to quickly produce hydrogen with water, and has a certain degree of oxidation resistance when stored in the air.
- the composite powder has stable properties, strong anti-oxidation ability, simple storage method, easy to carry, and the hydrogen production process is not limited by water temperature and water quality, solves the storage and transportation problems of hydrogen, reduces costs and risks, and is used in mobile hydrogen sources and hydrogen-powered vehicles. It has great application value and market prospects in civilian fields such as submarines, ships, torpedoes and other military fields.
- the purpose of the present invention is to provide a bloomable aluminum alloy powder and a preparation method and application thereof.
- the aluminum alloy powder of the present invention can continuously react with gaseous water at normal temperature to generate hydrogen and has a high aluminum-hydrogen conversion rate.
- a flowerable aluminum alloy powder is composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix; the nanoparticle includes bismuth but not tin; the flowerable aluminum alloy powder has Spherical particles with a smooth surface.
- the nanoparticles include bismuth and tin.
- the content of the bismuth is not less than 1% of the mass of the aluminum alloy powder
- the total content of bismuth and tin in the bloomable aluminum alloy powder does not exceed 10% of the mass of the aluminum alloy powder.
- the composition of the aluminum alloy powder is 90.45% aluminum-3.1% bismuth-6.45% tin.
- the flowerable aluminum alloy powder further includes other additional elements, and the other additional elements include one or more of iron, zinc and copper.
- the amount of the other additional elements does not exceed 2% of the mass of the flowerable aluminum alloy powder, and when the nanoparticles include bismuth but not tin, the amount of the other additional elements is lower than that of bismuth.
- the mass percentage content When the nanoparticles include bismuth and tin, the amount of the other added elements is lower than the sum of the mass percentages of bismuth and tin.
- the composition of the aluminum alloy powder is 95.6% aluminum-3.4% bismuth-1% iron, or 97% aluminum-2% bismuth-0.5% zinc-0.5% copper.
- particles with a particle size of 5 to 300 nm in the nanoparticles account for more than 99%.
- the particle size of the bloomable aluminum alloy powder is 1-40 ⁇ m.
- the present invention provides a method for preparing the bloomable aluminum alloy powder described in the above solution, which includes the following steps:
- the molten liquid is introduced into the ultrasonic atomization chamber, and at the same time, 8-15MPa high-pressure inert gas is used to generate it through the ultrasonic generation chamber of the ultrasonic atomization furnace.
- the supersonic oscillating airflow impacts the molten liquid to make it atomized, and the aluminum alloy powder that can bloom is obtained after precipitation.
- the molten liquid before the molten liquid is introduced into the ultrasonic atomization chamber, it preferably further includes keeping the molten liquid for 8-20 minutes.
- the present invention provides the application of the aluminum alloy powder capable of blooming according to the above-mentioned scheme or the aluminum alloy powder capable of blooming prepared by the preparation method according to the above-mentioned scheme in reacting with gaseous water to produce hydrogen.
- the temperature of the gaseous water is 10°C to 300°C.
- the invention introduces dispersed nanoparticles into the spherical aluminum matrix, so that when each aluminum powder is in contact with gaseous water or gaseous water in the air, water molecules can be adsorbed by the surface nanoparticles to quickly penetrate into the spherical aluminum matrix.
- the aluminum matrix around the dispersed nano-activated particles reacts with water molecules to spontaneously generate hydrogen bubbles, which makes the surface of the aluminum powder expand outward rapidly, so that the aluminum alloy powder has a flowering-like morphological evolution process;
- the process causes the aluminum alloy powder to continuously expose the unreacted internal matrix of the powder like a flower, making it contact with the air, thereby having a high aluminum-hydrogen conversion efficiency.
- patent CN 104190916 A pass through the liquid-liquid separation zone (L ⁇ L1+L2) during the cooling process.
- the core is to separate two liquid phases M and N simultaneously through liquid-liquid two-phase separation, and droplets of the same liquid phase. Merge together to form a half-wrapped or full-wrapped core/shell composite structure.
- the present invention makes the precipitated liquid phase have nanometer scale and is instantly wrapped by a rapidly solidified matrix. It uses a different method from the above-mentioned patents.
- Ultrasonic atomization quenching powder making technology of traditional gas atomization technology uses high-pressure inert gas to pass through the ultrasonic generation cavity of the ultrasonic atomization furnace to generate a supersonic oscillating airflow and then impact the molten liquid, causing the molten liquid to produce high-frequency vibration. Thereby, the molten liquid is broken and atomized.
- the atomized alloy powder solidifies rapidly in the low-temperature atomization chamber at 2 ⁇ 10°C, so that the precipitated nano-activated particles are smaller, and the nano-activated particles are prevented from moving to the surface of the powder, thereby preventing the formation
- a core-shell structure or a semi-encapsulated core-shell structure obtains spherical aluminum alloy particles with nanoparticles dispersed in a spherical aluminum matrix.
- the anti-oxidant hydrolysis hydrogen production composite powder of the patent CN 104190916 A is characterized in that the composite powder forms a semi-encapsulated or fully-encapsulated core/shell composite structure, and the shell layer There are microcracks and small particles of M-rich phase. Due to its special structure, it has stable properties and strong anti-oxidation ability. It can be stored in dry air for a long time without being oxidized.
- the present invention improves the activity of the aluminum alloy powder to react with gaseous water in the air by forming nanoparticles dispersedly distributed in the spherical aluminum matrix, so that the powder of the patent can be used to react with low-temperature gaseous water to generate hydrogen.
- both CN101289163A and CN102992263A adopt ball milling technology.
- the activated phase is embedded in the matrix during the ball milling process, so that the material has better hydrogen production performance.
- the present invention adopts supersonic atomization quenching powder milling technology, by increasing the cooling rate, the activated particles have nanometer scale and are more evenly distributed in the matrix.
- the powder of the present invention has a regular spherical appearance, so that the sphere can be combined with The low-temperature gaseous water reacts with a flower-like morphological change. Therefore, the present invention can continuously react with low-temperature gaseous water to generate hydrogen.
- Figure 1 is an internal TEM image of the aluminum alloy powder of Example 1;
- Example 2 is a diagram of the appearance and flowering process of the aluminum alloy powder of Example 1;
- Figure 3 is a SEM morphology of the aluminum alloy powder of Example 1 after blooming
- Example 4 is an effect diagram of the aluminum alloy powder of Example 3 used for hydrogen production.
- the present invention provides a bloomable aluminum alloy powder, which is composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix; the nanoparticles include bismuth but not tin, or include bismuth and tin;
- the bloomable aluminum alloy powder is spherical particles with a smooth surface;
- the content of bismuth in the bloomable aluminum alloy powder is preferably not less than 1% of the mass of the aluminum alloy powder, and when the nanoparticles include bismuth and tin, the total content of bismuth and tin is preferably It does not exceed 10% of the mass of aluminum alloy powder.
- particles with a particle size of 5 to 300 nm in the nanoparticles preferably account for more than 99%; the particle size of the flowerable aluminum alloy powder is preferably 1 to 40 ⁇ m, more preferably 5 to 35 ⁇ m.
- the bloomable aluminum alloy powder preferably further includes other additional elements, and the other additional elements preferably include one or more of iron, zinc and copper; the amount of the other additional elements is preferably not More than 2% of the mass of the aluminum alloy powder capable of blooming, and when the nanoparticles include bismuth but not tin, the amount of the other added elements is lower than the mass percentage of bismuth, when the nanoparticles include In the case of bismuth and tin, the amount of the other added elements is lower than the sum of the mass percentages of bismuth and tin.
- other additional elements are also contained, other additional elements are inevitably present in the nanoparticles and the spherical aluminum matrix.
- the present invention does not specifically limit the content distribution of the other additive elements in the nano particles and the spherical aluminum matrix.
- the present invention provides a method for preparing the bloomable aluminum alloy powder described in the above solution, which includes the following steps:
- the molten liquid is introduced into the ultrasonic atomization chamber, and at the same time, 8-15MPa high-pressure inert gas is used to generate it through the ultrasonic generation chamber of the ultrasonic atomization furnace.
- the supersonic oscillating airflow impacts the molten liquid to make it atomized, and the aluminum alloy powder that can bloom is obtained after precipitation.
- the present invention has no special requirements on the type of inert gas, which can be specifically but not limited to argon, nitrogen and the like.
- the present invention preferably further includes keeping the molten liquid for 8-15 minutes, more preferably for 10 minutes.
- the present invention provides the application of the aluminum alloy powder capable of blooming according to the above-mentioned scheme or the aluminum alloy powder capable of blooming prepared by the preparation method according to the above-mentioned scheme in reacting with gaseous water to produce hydrogen.
- the temperature of the gaseous water is preferably 10°C to 300°C, more preferably normal temperature.
- the present invention has no special requirements on the source of the gaseous water, and any environment containing gaseous water is acceptable, such as air with a certain humidity.
- it is preferable that the bloomable aluminum alloy powder is placed in an environment containing gaseous water for reaction to produce hydrogen.
- the existing aluminum alloy powder reacts with liquid water to produce hydrogen.
- the bloomable aluminum alloy powder of the present invention introduces dispersedly distributed nano-activated particles into the aluminum matrix, so that each aluminum powder interacts with gaseous water or air. When in contact with gaseous water, water molecules can be absorbed by the active nanoparticles on the surface and quickly penetrate into the aluminum alloy powder.
- the aluminum matrix around the dispersed nano-activated particles reacts with water molecules spontaneously
- the hydrogen bubbles cause the surface of the aluminum powder to expand rapidly, giving the aluminum alloy powder a flowering-like morphological evolution process; this process makes the aluminum alloy powder open like a flower and continuously expose the unreacted internal matrix of the powder, making it not only It has high aluminum-hydrogen conversion efficiency, and its surface area to volume ratio continues to increase during the reaction process, and the adsorption effect becomes stronger and stronger.
- the aluminum alloy powder can be widely used for hydrogen production in a gaseous water environment.
- the ultrasonic atomization chamber furnace of the ultrasonic atomization furnace Pass 10°C cooling water into the wall to cool the ultrasonic atomization chamber to a temperature of 10°C, and then use the intermediate frequency induction coil in the ultrasonic atomization powder making furnace to heat the raw materials in the crucible to a temperature of 657°C and the metal is completely melted. And on this basis, continue to increase the temperature by 100°C and keep it for 10 minutes to make it evenly smelt.
- the ultrasonic atomization furnace fills the cavity of the ultrasonic atomization furnace with argon gas to 0.1MPa, and then even the molten liquid flows into the ultrasonic atomization chamber, and at the same time, the argon gas with a pressure of 10MPa is generated through the ultrasonic generation chamber of the ultrasonic atomization furnace After the supersonic oscillating airflow impacts the molten liquid to atomize, the atomized powder cools and settles in the collection tank, remove the collection tank, quickly put it into a glove box with an argon atmosphere, and then take out the powder in the collection tank To obtain aluminum alloy powder capable of blooming.
- FIG. 1 is an internal TEM image of the aluminum alloy powder of Example 1.
- Figure 1 shows that after the aluminum alloy powder prepared in Example 1 is cut open and observed with a transmission electron microscope, its internal structure has a nano-dispersed structure (Figure 1 (a) and (b)), and an elemental spectrometer is used The detection shows that the nanoparticles are in the bismuth-rich phase ( Figure 1 (c) and (d)).
- Figure 2 shows that the aluminum alloy powder prepared in Example 1 is a spherical aluminum alloy particle with a smooth surface composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix, and is in an environment containing gaseous water Presents a flowering process of morphological evolution.
- the alloy raw materials are put into the crucible of the ultrasonic atomization powder making furnace, the cavity of the atomization furnace is evacuated to 10Pa and then filled with argon gas to 0.05MPa.
- the ultrasonic atomization furnace Pass 2°C cooling water into the furnace wall of the ultrasonic atomization chamber to cool the ultrasonic atomization chamber to a temperature of 2°C, and then use the intermediate frequency induction coil in the ultrasonic atomization powder making furnace to heat the raw materials in the crucible to temperature
- the metal at 658°C is completely melted, and on this basis, the temperature is increased to 125°C, and the temperature is kept for 10 minutes to make it evenly melted.
- the atomized powder cools and settles in the collection tank, remove the collection tank, quickly put it into the glove box of argon protective atmosphere, and then take out the powder in the collection tank To obtain aluminum alloy powder capable of blooming.
- the appearance and internal structure of the obtained powder were observed, and the results were similar to those in Example 1.
- the aluminum alloy powder prepared in Example 2 was composed of a spherical aluminum matrix and nanoparticles dispersed in the spherical aluminum matrix. Spherical aluminum alloy particles with a smooth surface, and in an environment containing gaseous water, present a flowering-like morphological evolution process.
- the temperature is increased to 150°C, and the temperature is kept for 10 minutes to make the melting uniform.
- the atomized powder cools and settles in the collection tank, remove the collection tank, quickly put it into the glove box of argon protective atmosphere, and then take out the powder in the collection tank To obtain aluminum alloy powder capable of blooming.
- Example 2 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° C., and the changes in the morphology of the powder at different times were observed. The results are shown in FIG. 2.
- Figure 2 shows that the original aluminum alloy powder has a spherical shape. With the prolonged storage time in a water vapor environment, the aluminum alloy powder expands rapidly, bursts and grows petals. This is because: when the alloy powder is placed in an environment containing gaseous water, water molecules contact and adsorb on the surface of the material, and rapidly replace with aluminum in the area of the nanoparticles on the surface, and precipitate hydrogen at nearby defects.
- Example 2 The aluminum alloy powders obtained in Example 2 and Example 3 were respectively placed in a water vapor environment with a humidity of 70RH% and a temperature of 20°C. The changes in the morphology of the powders at different times were observed. The results were similar to those in Fig. 2 with obvious During the flowering process, the morphology of the product after flowering is shown in Figure 3.
- Example 3 The aluminum alloy powder prepared in Example 3 was reacted with gaseous water to produce hydrogen, and 0.05 g of the powder was weighed and placed in a reaction environment close to 100RH% relative humidity. The hydrogen production efficiency and hydrogen production volume are shown in Figure 4.
- the aluminum alloy powder can reach a conversion efficiency of 92% within 50 minutes, and the hydrogen output is 1045 mL/g.
- the conversion efficiency reached 84% in 75 minutes, and the hydrogen output was 948mL/g.
- the conversion efficiency reached 71% within 100 minutes, and the hydrogen output was 809 mL/g. It shows that the aluminum alloy powder of the present invention can react with gaseous water to generate hydrogen at a lower temperature or even at a normal temperature, and has a faster reaction rate and a high aluminum-hydrogen conversion efficiency.
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Abstract
一种能开花的铝合金粉体及其制备方法和应用,该能开花的铝合金粉体由球形铝基体和弥散分布于所述球形铝基体中的纳米颗粒组成;所述纳米颗粒包括铋不包括锡,或者包括铋和锡;所述能开花的铝合金粉体为具有光滑表面的球形颗粒;所述能开花的铝合金粉体通过采用超音雾化急冷法制备;该铝合金粉体用于与气态水反应产生氢气,在与气态水反应时具有开花状的外观形貌演变过程,具有很高的铝‑氢气转换效率,可广泛应用于气态水制氢,便携式供氢及氢医疗领域。
Description
本申请要求于2019年12月24日提交中国专利局、申请号为201911346317.X、发明名称为“一种能开花的铝合金粉体及其制备方法和应用”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本发明涉及金属粉体技术领域,尤其涉及一种能开花的铝合金粉体及其制备方法和应用。
传统矿物能源的枯竭迫使人们更加关注绿色清洁能源,如风能、太阳能、氢能和水能。其中,氢能由于具有良好的储能密度和资源丰富性,被认为是一种理想的未来能源。然而,目前氢气的运输和储存都依赖于高压氢气瓶,其储氢密度仍然较低,在碰撞过程中容易泄露氢气造成安全事故。因此,使用固体储氢材料或即时制氢材料并具有高储氢密度和安全性的便携式制氢技术日益受到人们的关注。
如专利CN 101289163A介绍了一种水解制氢的铝合金,其成分为单质金属铝(40~90wt%)、金属铋(8~50wt%)、低熔点金属(金属镓、锡、锌、镉、汞、铅、铟、镁、锗和/或钙)(0~15wt%)、水溶性化合物(1~40wt%)。该铝合金的制备方法为机械球磨法,机械球磨法是利用球磨机的转动或振动使硬球对原料进行强烈的冲击、研磨和搅拌,粉末颗粒经过压延、压和、又碾碎、再压和的反复过程(冷焊—粉碎—冷焊的反复进行),最后产品为不规则片状合金粉末。该铝合金可以在常温与水反应,并且产氢量可以达到理论值的95%左右。
又如专利CN 104190916 A公开了一种抗氧化的水解制氢复合粉体,其通过液液两相分离同时析出两种液相M和N,同种液相的液滴合并在一起,从而形成半包裹或全包裹的核/壳型复合结构使复合粉体,能够与水进行快速制氢,在空气中储存时具有一定的抗氧化性。该复合粉性质稳定,抗氧化能力强,保存方法简单,携带方便,产氢过程不受水温水质限制,解决了氢气的存储和运输问题,降低了成本和风险,在移动氢源、氢动力汽车等民用领域以及在潜艇、船舰、鱼雷等军用领域都具有极大的应 用价值和市场前景。
然而,这些水基制氢材料制氢时存在的问题是需要液态水,这限制了便携式制氢技术的应用。
与液态水相比,气态水在空气中广泛存在。最近的研究发现,掺Li、Mg、Zn、Bi、Sn和NaBH
4的铝基材料能与高温气态水反应,与气态水反应的起始温度可降低到200℃,铝-氢气转化率达87.83%,但由于反应温度高,限制了其应用。但到目前为止,还未能找到一种能在200℃以下与气态水发生连续反应的材料。
发明内容
本发明的目的在于提供一种能开花的铝合金粉体及其制备方法和应用,本发明的铝合金粉体能在常温下与气态水连续反应生成氢气并具有高铝-氢气转换率。
为了实现上述发明目的,本发明提供以下技术方案:
一种能开花的铝合金粉体,由球形铝基体和弥散分布于所述球形铝基体中的纳米颗粒组成;所述纳米颗粒包括铋不包括锡;所述能开花的铝合金粉体为具有光滑表面的球形颗粒。
优选的,所述纳米颗粒包括铋和锡。
优选的,所述铋的含量不少于铝合金粉体质量的1%;
当所述纳米颗粒包括铋和锡时,所述能开花的铝合金粉体中铋和锡的总含量不超过铝合金粉体质量的10%。
优选的,以质量分数计,所述铝合金粉体的成分为90.45%铝-3.1%铋-6.45%锡。
优选的,所述能开花的铝合金粉体还包括其他添加元素,所述其他添加元素包括铁、锌和铜中的一种或多种。
优选的,所述其他添加元素的用量不超过所述能开花的铝合金粉体质量的2%,且当所述纳米颗粒包括铋不包括锡时,所述其他添加元素的用量低于铋的质量百分含量,当所述纳米颗粒包括铋和锡时,所述其他添加元素的用量低于铋与锡元素的质量百分比之和。
优选的,以质量分数计,所述铝合金粉体的成分为95.6%铝-3.4%铋-1%铁,或为97%铝-2%铋-0.5%锌-0.5%铜。
优选的,所述纳米颗粒中粒径为5~300nm的颗粒占99%以上。
优选的,所述能开花的铝合金粉体的粒径为1~40μm。
本发明提供了上述方案所述能开花的铝合金粉体的制备方法,包括以下步骤:
(1)设计铝合金粉体的成分,使合金的成分满足上述能开花的铝合金粉体的成分要求;
(2)在超音雾化炉的超音雾化室炉壁内通入2~10℃冷却水,使超音雾化室冷却至2~10℃的温度,按设计的铝合金粉体的成分称量各纯金属,放入超音雾化炉加热室坩埚中,抽真空达到20Pa以下后,充保护气体至0.01~0.1MPa,利用超音雾化制粉炉内的加热设备将坩埚内的金属加热至全部金属刚好熔化,继续升温100~250℃以后,将熔融液体导入超音雾化室,与此同时用8~15MPa的高压惰性气体通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,沉淀后即得能开花的铝合金粉体。
优选的,将熔融液体导入超音雾化室前,优选还包括对熔融液体保温8~20min。
本发明提供了上述方案所述能开花的铝合金粉体或上述方案所述制备方法制备得到的能开花的铝合金粉体在与气态水反应制取氢气中的应用。
优选的,所述气态水的温度在10℃~300℃。
本发明的原理:
本发明在球形铝基体中引入弥散分布的纳米颗粒,使每颗铝粉与气态水或空气中的气态水接触时,水分子能被表面的纳米颗粒吸附从而迅速的渗透到球形铝基体内部,在球形铝基体内部,弥散分布的纳米活化颗粒周围的铝基体与水分子反应自发产生氢气泡而使得铝粉的表面迅速向外膨胀,使铝合金粉体具有开花般的形貌演变过程;该过程使得铝合金粉体像花朵开放般不断露出粉末未反应的内部基体,使其与空气接触,从而具有很高的铝-氢气转换效率。
专利CN 104190916 A的成分在冷却过程中通过液液相分离区(L→L1+L2),其核心是通过液液两相分离同时析出两种液相M和N, 同种液相的液滴合并在一起,从而形成半包裹或全包裹的核/壳型复合结构。而本发明为了获得更高的冷却速度使之超过形成核/壳型复合结构的临界点,从而使析出的液相具有纳米尺度并瞬间被快速凝固的基体所包裹,采用不同于上述专利使用的传统气雾化制粉技术的超音雾化急冷制粉技术,用高压惰性气体通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体,使熔融液体产生高频振动,从而破碎熔融液体雾化,雾化后的合金粉体在2~10℃的低温雾化腔中快速凝固,从而使析出纳米活化颗粒更加细小,阻碍纳米活化颗粒向粉体表面移动,从而预防形成核壳结构或半包裹的核壳结构,获得纳米颗粒弥散分布于球形铝基体中的球形铝合金颗粒。
本发明与专利CN 104190916 A相比,专利CN 104190916 A的一种抗氧化的水解制氢复合粉体的特征在于该复合粉体形成半包裹或全包裹的核/壳型复合结构,并且壳层中存在微裂纹以及富M相的小颗粒。由于特殊的结构导致其性质稳定,抗氧化能力强,可以在干燥空气中长期存放而不被氧化。而本发明通过形成纳米颗粒弥散分布于球形铝基体中,提升了铝合金粉体在空气中与气态水反应的活性,从而使得本专利的粉体可用于与低温气态水反应生成氢气。
本发明与专利CN 101289163A一种水解制氢的铝合金、与CN102992263A一种Al-Bi-NaCl-碱金属或氢化物水解制氢用复合材料及其制备相比,CN 101289163A和CN102992263A都采用球磨技术将活化相在球磨过程中嵌入基体,从而使材料具有较好的制氢性能。而本发明采用了超音雾化急冷制粉技术,通过提高冷速使得活化颗粒具有纳米尺度并更加均匀地分布于基体中,另外本发明的粉体外观具有规则的球形,故使得球体可以与低温气态水反应发生开花状的形貌变化。因而本发明可以与低温气态水连续反应生成氢气。
图1为实施例1铝合金粉体的内部TEM图;
图2为实施例1铝合金粉体的外观与开花过程图;
图3为实施例1铝合金粉体开花后的SEM形貌图;
图4为实施例3的铝合金粉体用于氢气制取的效果图。
本发明提供了一种能开花的铝合金粉体,由球形铝基体和弥散分布于所述球形铝基体中的纳米颗粒组成;所述纳米颗粒包括铋不包括锡,或者包括铋和锡;所述能开花的铝合金粉体为具有光滑表面的球形颗粒;
在本发明中,所述能开花的铝合金粉体中铋的含量优选不少于铝合金粉体质量的1%,且当所述纳米颗粒包括铋和锡时,铋和锡的总含量优选不超过铝合金粉体质量的10%。
在本发明中,所述纳米颗粒中粒径为5~300nm的颗粒优选占99%以上;所述能开花的铝合金粉体的粒径优选为1~40μm,更优选为5~35μm。
在本发明中,所述能开花的铝合金粉体优选还包括其他添加元素,所述其他添加元素优选包括铁、锌和铜中的一种或多种;所述其他添加元素的用量优选不超过所述能开花的铝合金粉体质量的2%,且当所述纳米颗粒包括铋不包括锡时,所述其他添加元素的用量低于铋的质量百分含量,当所述纳米颗粒包括铋和锡时,所述其他添加元素的用量低于铋与锡元素的质量百分比之和。当还含有其他添加元素时,所述纳米颗粒中以及球形铝基体中都不可避免的存在其他添加元素。本发明对所述其他添加元素在纳米颗粒和球形铝基体中的含量分配没有特殊限定。
本发明提供了上述方案所述能开花的铝合金粉体的制备方法,包括以下步骤:
(1)设计铝合金粉体的成分,使合金的成分满足上述成分要求;
(2)在超音雾化炉的超音雾化室炉壁内通入2~10℃冷却水,使超音雾化室冷却至2~10℃的温度,按设计的铝合金粉体的成分称量各纯金属,放入超音雾化炉加热室坩埚中,抽真空达到20Pa以下后,充保护气体至0.01~0.1MPa,利用超音雾化制粉炉内的加热设备将坩埚内的金属加热至全部金属刚好熔化,继续升温100~250℃以后,将熔融液体导入超音雾化室,与此同时用8~15MPa的高压惰性气体通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,沉淀后即得能开花的铝合金粉体。
本发明对惰性气体的种类没有特殊要求,具体可以但无局限于氩气、氮气等。
将熔融液体导入超音雾化室前,本发明优选还包括对熔融液体保温8~15min,更优选保温10min。
由于铝-铋二元合金或铝-铋-锡三元合金的偏晶或亚偏晶反应,材料在冷却过程中会发生析出第二液相的行为,通过采用超音雾化急冷制粉技术提高冷却速度至超过临界点,可以阻止粉末形成核/壳结构或半包裹的核壳结构,并使得材料的基体快速凝固包裹析出的纳米第二液相,获得纳米颗粒弥散分布于球形铝基体中的球形铝合金颗粒。
本发明提供了上述方案所述能开花的铝合金粉体或上述方案所述制备方法制备得到的能开花的铝合金粉体在与气态水反应制取氢气中的应用。在本发明中,所述气态水的温度优选在10℃~300℃,更优选为常温。本发明对所述气态水的来源没有特殊要求,任意含有气态水的环境均可,如具备一定湿度的空气。本发明优选将所述能开花的铝合金粉体置于含有气态水的环境中进行反应制取氢气。
现有的铝合金粉体均与液态水反应制取氢气,本发明的能开花的铝合金粉体因在铝基体中引入弥散分布的纳米活化颗粒,使每颗铝粉与气态水或空气中的气态水接触时,水分子能被表面的活性纳米颗粒吸附从而迅速的渗透到铝合金粉体内部,在铝合金粉体内部,弥散分布的纳米活化颗粒周围的铝基体与水分子反应自发产生氢气泡而使得铝粉的表面迅速向外膨胀,使铝合金粉体具有开花般的形貌演变过程;该过程使得铝合金粉体像花朵般开放不断露出粉末未反应的内部基体,使其不但具有很高的铝-氢气转换效率,且在反应过程中其表面积与体积比不断增大,吸附效应越来越强,该铝合金粉体可广泛用于气态水环境下的氢气制取。
下面结合实施例对本发明提供的能开花的铝合金粉体及其制备方法和应用进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
取96.6%铝-3.4%铋质量分数作为基础成分,在该基础成分加入铁,使最终成分为95.6%铝-3.4%铋-1%铁质量分数,然后按该比例配比金属原料,将合金原料放入超音雾化制粉炉的坩埚内,将雾化炉炉腔抽真空至10Pa后充入氩气至0.05MPa,与此同时,在超音雾化炉的超音雾化室炉 壁内通入10℃冷却水,使超音雾化室冷却至10℃的温度,然后利用超音雾化制粉炉内的中频感应线圈将坩埚内的原料加热到温度657℃金属完全融化,并在此基础上继续升温100℃,保温10min使其熔炼均匀。然后向超音雾化炉炉腔充入氩气至0.1MPa,随即使熔融液体流入超音雾化室,与此同时使气压为10MPa的氩气通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,待雾化粉末冷却并沉淀到收集罐中,将收集罐取下,快速放入氩气保护气氛的手套箱内,然后取出收集罐中的粉体,得到能开花的铝合金粉体。
对得到的粉体的外观和内部组织进行观察,结果如图1和图2所示,图1为实施例1铝合金粉体的内部TEM图。图1显示,将实施例1制备得到的铝合金粉体剖开后,用透射电镜观察,其内部组织具有纳米弥散结构(图1中(a)和(b)),且用元素能谱仪探测可知纳米颗粒为富铋相(图1中(c)和(d))。图2显示实施例1制备得到的铝合金粉体为由球形铝基体和弥散分布于球形铝基体内的纳米颗粒两者组成的具有光滑表面的球形铝合金颗粒,并在含有气态水的环境中呈现开花式的形貌演变过程。
实施例2
取98%铝-2%铋质量分数作为基础成分,在该基础成分加入锌、铜,使最终成分为97%铝-2%铋-0.5%锌-0.5%铜质量分数,然后按该比例配比金属原料,将合金原料放入超音雾化制粉炉的坩埚内,将雾化炉炉腔抽真空至10Pa后充入氩气至0.05MPa,与此同时,在超音雾化炉的超音雾化室炉壁内通入2℃冷却水,使超音雾化室冷却至2℃的温度,然后利用超音雾化制粉炉内的中频感应线圈将坩埚内的原料加热到温度658℃金属完全融化,并在此基础上继续升温125℃,保温10min使其熔炼均匀。然后向超音雾化炉炉腔充入氩气至0.1MPa,随即使熔融液体流入超音雾化室,与此同时使气压为8MPa的氩气通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,待雾化粉末冷却并沉淀到收集罐中,将收集罐取下,快速放入氩气保护气氛的手套箱内,然后取出收集罐中的粉体,得到能开花的铝合金粉体。
对得到的粉体的外观和内部组织进行观察,结果与实施例1相似,实施例2制备得到的铝合金粉体为由球形铝基体和弥散分布于球形铝基体 内的纳米颗粒两者组成的具有光滑表面的球形铝合金颗粒,并在含有气态水的环境中呈现开花式的形貌演变过程。
实施例3
取90.45%铝-3.1%铋-6.45%锡质量分数作为基础成分,不添加其他添加元素,然后按该比例配比金属原料,然后按该比例配比金属原料,将合金原料放入超音雾化制粉炉的坩埚内,将雾化炉炉腔抽真空至1Pa后充入氩气至0.05MPa,与此同时,在超音雾化炉的超音雾化室炉壁内通入5℃冷却水,使超音雾化室冷却至5℃的温度,然后利用超音雾化制粉炉内的中频感应线圈将坩埚内的原料加热到温度647℃金属完全融化,并在此基础上继续升温150℃,保温10min使其熔炼均匀。然后向超音雾化炉炉腔充入氩气至0.1MPa,随即使熔融液体流入超音雾化室,与此同时使气压为12MPa的氩气通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,待雾化粉末冷却并沉淀到收集罐中,将收集罐取下,快速放入氩气保护气氛的手套箱内,然后取出收集罐中的粉体,得到能开花的铝合金粉体。
对得到的粉体的外观和内部组织进行观察,结果与实施例1相似,显示实施例3制备得到的铝合金粉体为由球形铝基体和弥散分布于球形铝基体内的纳米颗粒两者组成的具有光滑表面的球形铝合金颗粒,并在含有气态水的环境中呈现开花式的形貌演变过程。
实施例的开花效果测试
将实施例1得到的铝合金粉体置于湿度为70RH%温度为20℃的水汽环境中,观察不同时间粉体的形貌变化,结果如图2所示。图2显示,原始的铝合金粉体为圆球状,随着在水汽环境中放置时间的延长,铝合金粉体快速膨胀,爆开并长出花瓣。这是因为:当合金粉末放置在含有气态水的环境中时,水分子接触并吸附在材料的表面,并在表面的纳米颗粒的区域与铝进行快速的置换反应并在附近的缺陷处析出氢气,由于氢气的快速析出,将会导致氢氧根在局部区域的浓度上升,进而渗透到材料内层。由于材料的内部同样存在弥散分布的纳米活化颗粒,同它们在材料表面的行为一样,这些颗粒将会促进渗透的水分子同铝基体在Al:Al(OH)
3反应界面继续发生置换反应并析出氢气,由于粉粒的内部产生了较高的氢气析 出压力,推动着粒子的表面向外迅速凸起,从而使粉粒爆开。在粉粒爆开之后,由于粉粒内部的铝暴露在空气中,它将继续与环境中的水分子反应,释放氢气,从而粉粒的表面向外长出花瓣。其粉粒的形貌由原先的球形变成了如附图3所示的花型。
将实施例2、实施例3得到的铝合金粉体分别置于湿度为70RH%温度为20℃的水汽环境中,观察不同时间粉体的形貌变化,结果与图2相似,均出现明显的开花过程,开花后的产物形貌如图3所示。
实施例的性能测试
将实施例3制得的铝合金粉体同气态水反应制取氢气,称取0.05g粉体放置在接近100RH%相对湿度的反应环境中,其在30℃、40℃、50℃温度下的制氢效率及制氢量如图4所示。
由图4可知,在50℃时,50分钟之内铝合金粉体可达到92%的转换效率,氢气产量为1045mL/g。在40℃时,75分钟内达到84%的转换效率,氢气产量为948mL/g。在30℃时,100分钟内达到71%的转换效率,氢气产量809mL/g。说明本发明的铝合金粉体能够在较低的温度甚至常温下与气态水反应产生氢气,且具有较快的反应速率及很高的铝-氢气转换效率。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (12)
- 一种能开花的铝合金粉体,其特征在于,由球形铝基体和弥散分布于所述球形铝基体中的纳米颗粒组成;所述纳米颗粒包括铋不包括锡;所述能开花的铝合金粉体为具有光滑表面的球形颗粒。
- 根据权利要求1所述的能开花的铝合金粉体,其特征在于,所述纳米颗粒包括铋和锡。
- 根据权利要求1或2所述的能开花的铝合金粉体,其特征在于,所述铋的含量不少于铝合金粉体质量的1%;当所述纳米颗粒包括铋和锡时,所述能开花的铝合金粉体中铋和锡的总含量不超过铝合金粉体质量的10%。
- 根据权利要求3所述的能开花的铝合金粉体,其特征在于,以质量分数计,所述铝合金粉体的成分为90.45%铝-3.1%铋-6.45%锡。
- 根据权利要求1或2所述的能开花的铝合金粉体,其特征在于,所述能开花的铝合金粉体还包含其他添加元素,所述其他添加元素包括铁、锌和铜中的一种或多种。
- 根据权利要求5所述的能开花的铝合金粉体,其特征在于,所述其他添加元素的用量不超过所述能开花的铝合金粉体质量的2%,且当所述纳米颗粒包括铋不包括锡时,所述其他添加元素的用量低于铋的质量百分含量,当所述纳米颗粒包括铋和锡时,所述其他添加元素的用量低于铋与锡元素的质量百分比之和。
- 根据权利要求6所述的能开花的铝合金粉体,其特征在于,以质量分数计,所述铝合金粉体的成分为95.6%铝-3.4%铋-1%铁,或为97%铝-2%铋-0.5%锌-0.5%铜。
- 根据权利要求1或2任一项所述的能开花的铝合金粉体,其特征在于,所述纳米颗粒中粒径为5~300nm的颗粒占99%以上。
- 根据权利要求1或2任一项所述的能开花的铝合金粉体,其特征在于,所述能开花的铝合金粉体的粒径为1~40μm。
- 权利要求1~9任一项所述能开花的铝合金粉体的制备方法,其特征在于,包括以下步骤:(1)设计铝合金粉体的成分,使合金的成分满足权利要求1~9任一项所述的能开花的铝合金粉体的成分要求;(2)在超音雾化炉的超音雾化室炉壁内通入2~10℃冷却水,使超音雾化室冷却至2~10℃的温度,按设计的铝合金粉体的成分称量各纯金属,放入超音雾化炉加热室坩埚中,抽真空达到20Pa以下后,充保护气体至0.01~0.1MPa,利用超音雾化制粉炉内的加热设备将坩埚内的金属加热至全部金属刚好熔化,继续升温100~250℃以后,将熔融液体导入超音雾化室,与此同时用8~15MPa的高压惰性气体通过超音雾化炉的超音波发生腔产生超音振荡气流后冲击熔融液体使其雾化,沉淀后得能开花的铝合金粉体。
- 根据权利要求10所述的制备方法,其特征在于,将熔融液体导入超音雾化室前,还包括对熔融液体保温8~20min。
- 权利要求1~9任一项所述能开花的铝合金粉体或权利要求10~11任一项所述制备方法制备得到的能开花的铝合金粉体在与气态水反应制取氢气的应用,所述气态水的温度在10℃~300℃。
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