CN110438360B - Preparation method of foamed aluminum or aluminum alloy material - Google Patents
Preparation method of foamed aluminum or aluminum alloy material Download PDFInfo
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- CN110438360B CN110438360B CN201910768617.0A CN201910768617A CN110438360B CN 110438360 B CN110438360 B CN 110438360B CN 201910768617 A CN201910768617 A CN 201910768617A CN 110438360 B CN110438360 B CN 110438360B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- 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
- C22C1/08—Alloys with open or closed pores
- C22C1/083—Foaming process in molten metal other than by powder metallurgy
- C22C1/086—Gas foaming process
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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Abstract
The invention relates to a preparation method of a foamed aluminum alloy material, which comprises the following steps: heating metal aluminum or aluminum alloy to a temperature above the liquidus line to completely melt the metal aluminum or aluminum alloy to form a liquid phase aluminum or aluminum alloy melt; introducing gas into liquid-phase aluminum or aluminum alloy melt in batches, wherein the gas is required to be subjected to high-speed shearing, emulsifying and dispersing on gas flow every time, so that moving bubbles with fixed diameters and fixed initial motion acceleration are generated in the melt, and the melt is converted into suspension liquid in which the bubbles are uniformly dispersed; and carrying out subsequent cooling processing treatment on the suspension to prepare the foamed aluminum alloy material. The preparation method of the foamed aluminum alloy material successfully solves the problems that bubbles are easy to agglomerate and grow and are dispersed unevenly in the traditional method, and meanwhile, the method has the advantages of easily available raw materials, simple equipment, short process flow, high efficiency and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of preparation of foam metal materials, in particular to a preparation method of a foam aluminum or aluminum alloy material.
Background
The foamed aluminum is a porous material with high porosity, has small specific gravity, heat resistance, sound absorption and shock resistance, has special physical and chemical properties, and can be used as a functional material and a structural material; the composite material has wide application prospect in the fields of machinery, electronics, buildings, transportation, light chemical industry, military industry and the like, such as light decorative building materials, light chemical industry fillers and catalysts, heat exchangers, flame-retardant materials, sound insulation and noise elimination, shock absorption and impact resistance, electromagnetic shielding and the like.
The traditional preparation method of the foamed aluminum mainly comprises the following steps:
1. powder metallurgy: mixing a foaming agent and metal powder to prepare a prefabricated block, and melting the metal powder and decomposing the foaming agent through molding and sintering to obtain a porous structure; the method has higher cost, is suitable for casting and processing some small parts, and is not suitable for large-scale industrial production.
2. An electrolytic deposition method: taking organic foaming materials such as polyurethane and the like as a framework, carrying out aluminum electrolytic deposition, and then heating to remove the organic foaming materials to prepare foamed aluminum; the method has the disadvantages of high price of foaming material, complex technology and limited application.
3. And (3) seepage casting: piling solid particles with certain size such as soluble salt, glass, ceramic and the like together, then injecting molten metal into gaps of the solid particles under the action of pressure, cooling, and removing the solid particles through sintering or dissolving to obtain a metal foam material; the foam metal material produced by the method has good aperture uniformity, but has complex process and higher cost.
4. Melt foaming method: adding a tackifier into the molten aluminum, stirring uniformly, adding foaming agents such as TiH2, ZrH2 and CaCO3 into the molten metal, stirring to uniformly mix the foaming agents, putting the mixture into a mold at a certain temperature, heating the foaming agents to decompose gas, and cooling to form a foamed metal material; the method has simple process and low cost, and is suitable for industrial production.
In the traditional preparation process for producing foamed aluminum by a melt foaming method, the control of the uniformity of the size of bubbles is always a key process problem. Most of the existing melt foaming methods adopt mechanical stirring, and the tackifier and the foaming agent in the melt are dispersed by a stirring paddle. In the foaming process, as pure mechanical stirring is adopted, the stirring force of the foaming agent is gradually reduced from the center to the edge of the melt, so that the edge of the melt cannot be fully stirred, and the foaming agent cannot be uniformly mixed, thus the uniformity of the pore structure of the prepared foamed aluminum is reduced; the melting temperature of the aluminum alloy is 580-650 ℃, the foaming agent begins to decompose and release gas at 550-580 ℃, and the foaming temperature of the foaming agent is lower than the melting temperature of the aluminum alloy, so that the powdery foaming agent begins to decompose violently before the powdery foaming agent is fully dispersed, the gas is released, further dispersion of powder particles is influenced, the foaming agent is concentrated, and generated bubbles are overlarge. When the bubbles are too large, the stress of the aluminum alloy material is too concentrated, so that the mechanical property of the material is reduced. Meanwhile, in the heat preservation foaming link, because of the influence of gravity, bubbles in the foamed aluminum naturally float upwards after being formed, the melt sinks, a density gradient distributed along the vertical direction is easily formed, the melt at the bottom has high density, the bubble at the top has low density, the density and the porosity of the foamed aluminum are uneven, the yield is reduced, and the production cost is improved. How to obtain fine, compact and uniform bubbles without reducing the porosity is a problem which is difficult to solve.
The published Chinese patent application 201610051526.1 proposes a method for preparing foamed aluminum alloy by using a melt level shearing process, which comprises the steps of dispersing melt through surface shearing to prepare gas-liquid mixed foam to obtain a foamed aluminum alloy structural material. From the practical point of view, the gas-liquid mixed foam produced by surface shearing is only positioned on the upper surface of the mixed melt, the gas-liquid mixed foam is difficult to be introduced into the lower part of the melt, and the practical industrial application has the practical problem; in addition, the method needs to add a tackifier into the melt as in the traditional melt foaming method, the viscosity of the melt is strictly controlled, gas escapes and increases when the viscosity is too low, meanwhile, bubbles are partially gathered to form holes with different sizes, and the foaming agent is difficult to uniformly disperse in the melt when the viscosity is too high, so that the process complexity is improved, and impurities are introduced. In addition, the method also needs to lead out the foam in the gas-liquid mixed foam body by means of traction or mechanical transmission, so that the uniformity of the dispersed bubbles is influenced.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of foamed aluminum or aluminum alloy material.
According to the invention, the preparation method of the foamed aluminum or aluminum alloy material comprises the following steps: heating the metal aluminum or the aluminum alloy to a temperature above a liquidus line to completely melt the metal aluminum or the aluminum alloy to form a liquid-phase aluminum or aluminum alloy melt; introducing gas into liquid-phase aluminum or aluminum alloy melt in batches, wherein the melt is required to be subjected to high-speed shearing, emulsification and dispersion in each gas introduction, so that the melt is generated with the diameter D and the initial motion acceleration GoptThe melt is converted into suspension with the bubbles uniformly dispersed; and carrying out conventional subsequent cooling processing treatment on the suspension to prepare the foamed aluminum or aluminum alloy material.
Wherein D is 1-999nm, Gopt30-100G, G is the acceleration of gravity.
Wherein, the volume ratio of the gas introduced into each batch to the melt is 60-90%, and the processing time of each batch is 1-30 min.
In the step of introducing gas and shearing at high speed, a shearing emulsifying device which performs relative high-speed rotation on a rotor and a stator is used for emulsifying and dispersing, wherein the flow of the gas introduced into each batch is 100-1000 cm3And/s, wherein the linear speed of the rotor during emulsification shearing of each batch is 30-60 m/s.
Wherein the introduced gas is air, water vapor, oxygen, carbon dioxide or inert gas.
Wherein, in the conventional subsequent processing step, the processing time is 1-60 min.
Wherein, in the step of forming the melt, the temperature to which the metal aluminum or the aluminum alloy is heated is 630-700 ℃.
In the process of preparing the foamed aluminum alloy by introducing bubbles from an external source, the density of the bubbles is generally greatly different from that of a matrix metal, and the bubbles and the matrix metal are not wetted with each other, so that the bubbles are easy to float upwards and agglomerate in an alloy melt to form larger bubbles. The Stokes particle sink velocity v is expressed as:
υ＝2gr2(ρmetal melt-ρNanoparticles)/9η
Wherein η is the viscosity (Pa · s) of the molten metal; r is the nanoparticle radius; g is the acceleration of gravity; ρ is the density.
According to the above formula, the sinking and floating rate of the bubbles in the metal melt is proportional to the density difference between the bubbles and the metal melt and the square of the radius of the bubbles, and inversely proportional to the viscosity of the metal melt. The viscosity of the metal melt is improved, the radius of the bubbles is reduced, so that the floating rate of the bubbles is reduced, the dispersed phases of the bubbles are not easy to aggregate and agglomerate to form larger bubbles, the organization of the foam alloy is uniform, and the performance of the foam alloy is improved. Under the premise of selecting specific melt and adding gas, the melt viscosity, the melt density and the gas density are constant values, the floating and sinking rate of bubbles in the melt is in direct proportion to the square of the bubble size, and therefore the size of the bubbles has the greatest influence on floating and agglomeration growth of the bubbles caused by the floating and sinking rate.
The invention utilizes the relative action of a high-speed rotor and a stator through a high-speed shearing emulsification process, and on one hand, according to an acceleration formula a ═ v2And/r, the acceleration of the bubbles just beginning to separate from the shearing emulsifying device can reach 30-100 times of the gravity acceleration through the specific shearing linear velocity, so that the bubbles are always kept in a highly moving state in the melt, and the probability of static agglomeration is very small until the bubbles are dispersed at each corner of the melt. On the other hand, through ensuring the shearing force and the shearing line speed matched with the gas flow, the added bubbles are repeatedly broken and dispersed, the bubbles are separated into small bubbles with single nanometer-scale sizes, the radius of the bubbles is minimized, the particle sinking and floating speed is further reduced to the maximum extent, and finally the formed suspended bubbles can be always kept in a stable state in the subsequent processing time beyond the conventional processing time. In the whole preparation process, only the subsequent cooling processing technology is needed to be carried out according to a conventional mode, and the invention can keep the bubbles in the finally formed foam aluminum alloy in a uniformly dispersed state all the time.
According to the preparation method of the foamed aluminum or aluminum alloy material, the gas is introduced into the aluminum metal or aluminum alloy melt, and the specific emulsification stirring is carried out, so that the particle size of the formed bubbles is very small and reaches the nanometer level, and the formed nano bubbles are moved in the melt at a high enough initial acceleration, and further are fully and uniformly dispersed in the melt, and the problems that the bubbles are easy to agglomerate and grow and the bubbles are not uniformly dispersed in the traditional method are successfully solved.
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Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 shows a flow chart of a method of preparing an aluminum foam or aluminum alloy material according to an embodiment of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below according to examples. While exemplary embodiments of the present disclosure have been shown in the specification, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
As shown in fig. 1, the invention provides a preparation method of a foamed aluminum or aluminum alloy material, which comprises the following steps: heating the metal aluminum or the aluminum alloy to a temperature above a liquidus line to completely melt the metal aluminum or the aluminum alloy to form a liquid-phase aluminum or aluminum alloy melt; introducing gas into liquid-phase aluminum or aluminum alloy melt in batches, wherein the gas is required to be subjected to high-speed shearing, emulsification and dispersion in each gas introduction, and the diameter D and the initial motion acceleration G are formed in the meltoptForming a suspension in which the bubbles are uniformly mixed; and carrying out subsequent cooling processing treatment on the suspension to prepare the foamed aluminum or aluminum alloy material.
In the above step, the diameter D of the bubble is 1-999nm, and in some specific embodiments, the diameter D of the bubble may be 10nm, 50nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 700nm, 800nm, 850nm, 900 nm.
In the above step, the high-speed shearing is that the initial acceleration of the bubble separation emulsification equipment is 300-100GoptSpecifically, 30G, 40G, 50G, 60G, 70G, 80G, 90G, and 100G may be used. G is the acceleration of gravity, with a value of about 9.8 m/s.
In the above step, emulsification and dispersion may be performed by using a shear emulsifying device in which a rotor and a stator rotate at a relatively high speed. During emulsification shearing, the rotating linear speed of the rotor is 30-60m/s, specifically 30m/s, 40m/s, 50m/s and 60 m/s. In particular, 60% to 90% of the volume of the melt of the gas introduced per batch may be 60%, 70%, 80%, 90%. The gas flow introduced in each batch is 100-1000 cm3The specific length of the second electrode is 100cm3/s、200cm3/s、300cm3/s、400cm3/s、500cm3/s、600cm3/s、700cm3/s、800cm3/s、900cm3/s、1000cm3/s。
The processing time of each batch is 1-30min, specifically 15min, 20min, 25min, and 30 min. The control of the emulsification time and the feeding and acceleration in batches can accelerate all bubbles in the melt as much as possible, thereby ensuring that the distribution of the nano particles in the suspension and the finally obtained metal or alloy product is more uniform.
In the above steps, the time of the subsequent cooling processing is 1-60min, specifically, 10min, 20min, 30min, 40min, 50min, 60 min. The subsequent cooling process includes cooling the suspension to form alloy block, casting the suspension to form alloy rod, plate, foamed aluminum or aluminum alloy material and other alloy products, and other processes to obtain different alloy products.
In the above steps, the heating temperature for forming the aluminum melt or the alloy aluminum melt is 630-.
In the above step, the introduced gas is air, water vapor, oxygen, carbon dioxide or inert gas.
The production of the foamed aluminum alloy of the present invention will be described in further detail below by way of specific examples.
Example 1
3kg of pure metal aluminum ingot is placed in a graphite smelting furnace and heated to 660 ℃ under the protection of nitrogen atmosphere to form a volume of 1112cm3The pure aluminum melt of (2). Introducing 100cm into pure aluminum melt3Carbon dioxide gas, keeping the flow rate of the gas at 100cm3And/s, extending an emulsifying head of the graphite high-shear emulsifying dispersion machine into the melt, starting and gradually raising the speed to 60m/s to carry out high-speed shear emulsifying dispersion on the melt. At this time, the bubbles generated by aeration were broken up to about 100nm, and the initial acceleration of the formed bubbles when they were removed from the apparatus could reach 30G. Shearing at high speed for emulsifying for 30min, and adding 100cm3The carbon dioxide gas was again subjected to high-speed emulsification shearing while maintaining the same gas flow rate, emulsification shearing rate and emulsification time. Repeating the aeration and emulsification shearing process for ten times until the cumulative total of 1000cm3Carbon dioxide gas is introduced into the melt. And pouring the carbon dioxide bubble-aluminum melt suspension into a mould, and naturally cooling for 30min to obtain the foamed aluminum alloy special-shaped casting.
And (3) detection: the performance test of the prepared foamed aluminum alloy special-shaped piece shows that the porosity is 92.5 percent, the average pore diameter is 1.07mm, the average pore diameter spacing is 184 mu m, and the density is 0.28g/cm3The yield strength is 5.31 MPa.
Example 2
2kg of aluminum-magnesium alloy is placed in a graphite smelting furnace, and is heated to 650 ℃ under the protection of argon to form a volume of 825cm3The aluminum magnesium alloy melt of (1). After the alloy ingot is completely melted, 500cm of alloy ingot is introduced into the melt at one time3Argon gas, flow rate of gas 300cm3And secondly, extending an emulsifying head of the graphite high-speed shearing emulsifying dispersion machine into the aluminum-magnesium solution, starting and gradually increasing the speed to 40m/s, so that bubbles formed by introducing gas are broken to about 200nm, and the bubbles are separated from emulsifying equipmentThe initial acceleration reaches 40G, bubbles are uniformly dispersed at all corners of the melt after high-speed shearing, emulsification and dispersion for 20min, at the moment, argon bubble-aluminum-magnesium alloy melt turbid liquid is poured into a mould, circulating water is adopted for rapid cooling for 20min, and then the cooled casting block is subjected to cutting, cleaning and drying treatment to obtain the foam aluminum-magnesium alloy plate.
And (3) detection: the performance test of the prepared foamed aluminum-magnesium alloy plate shows that the porosity is 91 percent, the average pore diameter is 1.01mm, the average pore diameter spacing is 167 mu m, and the density is 0.23g/cm3The yield strength is 5.87 MPa.
Example 3
1.5kg of aluminum-copper alloy ingot is placed in a graphite smelting furnace and heated to 700 ℃ under the protection of nitrogen atmosphere to form the aluminum-copper alloy ingot with the volume of 683cm3The aluminum-copper alloy melt of (1). Firstly introducing 200cm into the aluminum-copper melt3Oxygen gas, keeping the flow rate of the introduced gas at 1000cm3And then extending an emulsifying head of the graphite high-shear emulsifying and dispersing machine into the melt, starting and gradually increasing to the linear speed of 30 m/s. At this time, the formed bubbles are broken to about 50nm, and the initial acceleration of the formed bubbles when they exit the apparatus can reach 45G. Shearing at high speed for emulsifying for 10min, and adding 200cm3Oxygen gas, keeping the same gas flow, emulsifying and shearing speed and emulsifying time, and then carrying out high-speed emulsifying and shearing again. The aeration and emulsification shearing process was repeated three times in this way until 600cm was cumulatively added3And introducing oxygen gas into the alloy melt. Pouring the oxygen bubble-aluminum copper melt suspension into a mould, and naturally cooling for 15min to obtain the foamed aluminum copper alloy special-shaped casting.
And (3) detection: the performance test of the prepared special-shaped foamed aluminum copper alloy piece shows that the porosity is 87.3 percent, the average pore diameter is 1.42mm, the average pore diameter spacing is 203 mu m, and the density is 0.64g/cm3The yield strength is 5.54 MPa.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A preparation method of foamed aluminum or aluminum alloy material is characterized by comprising the following steps:
heating the metal aluminum or the aluminum alloy to a temperature above a liquidus line to completely melt the metal aluminum or the aluminum alloy to form a liquid-phase aluminum or aluminum alloy melt;
introducing gas into liquid-phase aluminum or aluminum alloy melt in batches, wherein the gas is required to be subjected to high-speed shearing, emulsification and dispersion in each gas introduction, so that the melt is generated with the diameter D and the initial motion acceleration GoptThe melt is converted into suspension with uniformly dispersed bubbles by moving the bubbles; wherein D is 1-999nm, Gopt30-100g, g is the acceleration of gravity; the volume ratio of the gas introduced into each batch to the melt is 60-90%, and the processing time of each batch is 1-30 min; in the step of introducing gas and shearing at a high speed, a shearing emulsifying device which performs relative high-speed rotation by using a rotor and a stator is used for emulsifying and dispersing, wherein the flow of the gas introduced into each batch is 100-1000 cm3The linear speed of the rotor during each batch of emulsification shearing is 30-60 m/s; the introduced gas is oxygen, carbon dioxide or inert gas;
and carrying out conventional subsequent cooling processing treatment on the bubble-suspension liquid to prepare the foamed aluminum alloy material.
2. The method according to claim 1, wherein the reaction mixture,
in the conventional subsequent cooling processing step, the processing time is 1-60 min.
3. The method according to claim 1, wherein the reaction mixture,
in the step of forming the melt, the metal aluminum or the aluminum alloy is heated to the temperature of 660-700 ℃.
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| CA2087791A1 (en) * | 1993-01-21 | 1994-07-22 | Martin Thomas | Production of particle-stabilized metal foams |
| US7195662B2 (en) * | 2001-06-15 | 2007-03-27 | Huette Klein-Reichenbach Gesellschaft Mbh | Device and process for producing metal foam |
| AT410103B (en) * | 2001-06-15 | 2003-02-25 | Huette Klein Reichenbach Gmbh | METHOD FOR PRODUCING A LIGHTWEIGHT MOLDED BODY AND MOLDED BODY FROM METAL FOAM |
| JP3895292B2 (en) * | 2003-03-24 | 2007-03-22 | 独立行政法人科学技術振興機構 | Method for producing metal foam |
| CN100487146C (en) * | 2007-09-11 | 2009-05-13 | 同济大学 | Foam metal and preparation method thereof |
| CN101259463B (en) * | 2008-04-30 | 2010-09-08 | 东北大学 | Preparation of foam aluminum alloy base wave-absorbing material |
| KR101551003B1 (en) * | 2013-12-13 | 2015-09-07 | 현대자동차주식회사 | Method for producing porous aluminium |
| CN106995888B (en) * | 2016-01-26 | 2018-12-18 | 同济大学 | A method of foam aluminium alloy is prepared using melt liquid level shearing process |
| CN108842078B (en) * | 2018-08-21 | 2020-07-24 | 安徽省一鸣新材料科技有限公司 | Vacuum-pumping foamed aluminum batch forming method based on probe control |
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Inventor after: An Ning Inventor after: He Huijun Inventor after: Lin Zhuoxian Inventor after: Wang Zhigang Inventor after: Liu Xixue Inventor after: Liu Jian Inventor after: Zhao Chaohui Inventor after: Zhu Jie Inventor after: Zhang Huankun Inventor after: Zhu Xuexin Inventor before: He Huijun Inventor before: An Ning Inventor before: Lin Zhuoxian Inventor before: Wang Zhigang Inventor before: Liu Xixue Inventor before: Liu Jian Inventor before: Zhao Chaohui Inventor before: Zhu Jie Inventor before: Zhang Huankun Inventor before: Zhu Xuexin |