WO2019192070A1 - Foam metal preparation method - Google Patents

Foam metal preparation method Download PDF

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Publication number
WO2019192070A1
WO2019192070A1 PCT/CN2018/089575 CN2018089575W WO2019192070A1 WO 2019192070 A1 WO2019192070 A1 WO 2019192070A1 CN 2018089575 W CN2018089575 W CN 2018089575W WO 2019192070 A1 WO2019192070 A1 WO 2019192070A1
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Prior art keywords
metal
foam
heat treatment
preparing
diffusion
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PCT/CN2018/089575
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French (fr)
Chinese (zh)
Inventor
吴江明
钟一锋
孙兆荣
Original Assignee
吴江明
钟一锋
孙兆荣
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Priority claimed from CN201810281497.7A external-priority patent/CN108456904B/en
Priority claimed from CN201810281496.2A external-priority patent/CN108456795B/en
Application filed by 吴江明, 钟一锋, 孙兆荣 filed Critical 吴江明
Publication of WO2019192070A1 publication Critical patent/WO2019192070A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the invention relates to the technical field of foam metal preparation, and in particular to a method for preparing a metal foam.
  • Foam metal is an excellent functional environmentally friendly material. It combines the functions of mechanics, thermals, electricity, and acoustics, and has an irreplaceable important position in the field of materials. High porosity and high specific surface area are the structural characteristics and important characteristics of foam metal. They are also the key properties that determine the application advantages of foam metal in the fields of sound absorption, damping, electromagnetic shielding, filtration separation and so on.
  • the three-dimensional network of open-cell foam metal is mainly prepared by electrodeposition and vapor deposition, and the surface of the prepared foam metal fiber is smooth or nearly smooth, as shown in Fig. 1-2. This results in a difficulty in further increasing the high specific surface area of the metal foam, which limits its wider application.
  • the present invention aims to provide a method for preparing a metal foam based on the difference in diffusion rate of a dissimilar metal in a high temperature interdiffusion process, and rapidly lowering the temperature during the most vigorous diffusion to allow the diffusion reaction to stop rapidly, thereby Defects such as vacancies and holes remaining due to incomplete diffusion remain, forming an ultra-high specific surface area foam metal.
  • the present invention adopts one of the following technical solutions:
  • a method for preparing a metal foam comprising the steps of:
  • step S2 the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
  • step S3 depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy
  • step S4 performing a diffusion heat treatment on the metal foam obtained in step S3 under a reducing atmosphere of hydrogen gas, the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the diffusion heat treatment is finished, rapidly cooling to room temperature, the cooling rate is greater than 10 ° C / min Finally, a foam metal alloy with an ultra-high specific surface area is obtained.
  • the metal in step S1 is nickel, copper or iron.
  • step S1 the specification of the foam metal substrate is 5PPI-200PPI.
  • step S2 the heat treatment time is from 10 min to 300 min.
  • step S3 the deposition is performed by electrodeposition or vapor deposition.
  • the metal material is nickel, copper or iron.
  • step S4 the diffusion heat treatment time is 1 h-20 h.
  • a method for preparing a metal foam comprising the steps of:
  • step S2 the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
  • step S3 depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy
  • the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the end of the diffusion heat treatment, rapid cooling to room temperature, the cooling rate is greater than 10 ° C / min, and finally obtain a foam metal alloy with ultra-high specific surface area.
  • the metal in step S1 is nickel, copper or iron.
  • step S1 the specification of the foam metal substrate is 5PPI-200PPI.
  • step S2 the heat treatment time is from 10 min to 300 min.
  • step S3 the deposition is performed by electrodeposition or vapor deposition.
  • the metal material is nickel, copper or iron.
  • step S4 the diffusion heat treatment time is 1 h-20 h.
  • the invention is based on the difference of diffusion rate of dissimilar metals in the process of high temperature interdiffusion, and the rapid cooling down when the diffusion is most intense causes the diffusion reaction to stop rapidly, thereby retaining defects such as vacancies and holes left by incomplete diffusion, and forming a defect.
  • Ultra high specific surface area foam metal Ultra high specific surface area foam metal.
  • FIG. 1 is a schematic view showing the surface morphology of a foam metal prepared by the prior art
  • Figure 2 is an enlarged schematic view of Figure 1;
  • FIG. 3 is a schematic view showing the surface morphology of a metal foam prepared by one of the methods of the present invention
  • Figure 4 is an enlarged schematic view of Figure 3;
  • Figure 5 is a schematic view showing the surface morphology of a metal foam prepared by another method of the present invention.
  • Figure 6 is an enlarged schematic view of Figure 5.
  • Conductive treatment was carried out on a 45 PPI polyurethane foam to realize electrodeposition of a nickel metal element, and a foamed nickel having a bulk density of 0.3 Pg/cm 3 of 45 PPI was obtained, and the specific surface area was 2000 cm 2 /cm 3 .
  • the foamed nickel was heat-treated at 900 ° C for 1 hour in a hydrogen atmosphere to remove the polyurethane.
  • metal copper was electrodeposited on the heat-treated foamed nickel to obtain a foamed nickel-copper alloy having a bulk density of 0.6 P/cm 3 of 45 PPI, and subjected to diffusion heat treatment for 8 hours under a hydrogen reducing atmosphere at 800 ° C, and then at 10 ° C.
  • the cooling rate of /min was rapidly cooled to room temperature to obtain an ultrahigh specific surface area foamed nickel-copper alloy having a 45 PPI specific surface area of 6300 cm 2 /cm 3 , which increased the specific surface area by more than three times compared with the original metal foam.
  • the surface topography of the foamed nickel-copper alloy obtained in this embodiment is shown in Figs. 3-4, and the surface thereof has a microporous structure as seen from Fig. 3-4.
  • Conductive treatment was carried out on a 100 PPI polyurethane foam, and a nickel metal element was electrodeposited to obtain a foamed nickel having a 100 PPI bulk density of 0.15 g/cm 3 and a specific surface area of 6500 cm 2 /cm 3 .
  • the foamed nickel was subjected to heat treatment at 800 ° C for 1.5 hours in a hydrogen atmosphere to remove the polyurethane.
  • metal iron was vapor-deposited on the heat-treated foamed nickel to obtain a foamed nickel-iron alloy having a 100 PPI bulk density of 0.22 g/cm 3 .
  • the foamed nickel-iron alloy was subjected to diffusion heat treatment in a hydrogen atmosphere at a temperature of 950 ° C for 10 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain an ultrahigh specific surface area having a specific surface area of 15000 cm 2 /cm 3 .
  • Foamed nickel-iron alloy which has more than doubled the specific surface area compared to the original metal foam.
  • the surface topography of the foamed nickel-iron alloy obtained in this example was similar to that of Example 1.
  • Conductive treatment was carried out on a 120 PPI polyurethane foam, and a copper metal element was electrodeposited to obtain a foamed copper having a bulk density of 0.18 g/cm 3 of 120 PPI and a specific surface area of 6000 cm 2 /cm 3 .
  • the heat treatment was carried out for 3 hours at a temperature of 700 ° C in a hydrogen atmosphere to remove the polyurethane.
  • metal iron was electrodeposited on the heat-treated copper foam to obtain a foamed copper-iron alloy having a 120 PPI bulk density of 0.24 g/cm 3 .
  • the foamed copper-iron alloy was subjected to a diffusion heat treatment in a hydrogen atmosphere at a temperature of 980 ° C for 14 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain an ultra-high ratio of a specific surface area of 18,500 cm 2 /cm 3 .
  • the surface area of the foamed copper-iron alloy increases the specific surface area by more than three times compared to the original metal foam.
  • the surface topography of the foamed copper-iron alloy obtained in this example was similar to that of Example 1.
  • Conductive treatment was carried out on a 45 PPI polyurethane foam to realize electrodeposition of a nickel metal element, and a foamed nickel having a bulk density of 0.3 Pg/cm 3 of 45 PPI was obtained, and the specific surface area was 2000 cm 2 /cm 3 .
  • the foamed nickel was heat-treated at 900 ° C for 1 hour in a hydrogen atmosphere to remove the polyurethane.
  • metal copper is electrodeposited on the heat-treated foamed nickel to obtain a foamed nickel-copper alloy having a bulk density of 0.6 P/cm 3 of 45 PPI, and is subjected to a protective atmosphere of nitrogen, argon or helium at 800 ° C for 8 hours.
  • the surface topography of the foamed nickel-copper alloy obtained in this embodiment is shown in Fig. 5-6. It can be seen from Fig. 5-6 that the surface has a microporous structure.
  • Conductive treatment was carried out on a 100 PPI polyurethane foam, and a nickel metal element was electrodeposited to obtain a foamed nickel having a 100 PPI bulk density of 0.15 g/cm 3 and a specific surface area of 6500 cm 2 /cm 3 .
  • the foamed nickel was subjected to heat treatment at 800 ° C for 1.5 hours in a hydrogen atmosphere to remove the polyurethane.
  • metal iron was vapor-deposited on the heat-treated foamed nickel to obtain a foamed nickel-iron alloy having a 100 PPI bulk density of 0.22 g/cm 3 .
  • the foamed nickel-iron alloy was subjected to a diffusion heat treatment at a temperature of 950 ° C and a vacuum of less than 1*10 -2 Pa for 10 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain a specific surface area of 15000 cm.
  • the 2 /cm 3 ultra-high specific surface area foamed nickel-iron alloy has more than doubled the specific surface area compared to the original metal foam.
  • the surface topography of the foamed nickel-iron alloy obtained in this example was similar to that of Example 1.
  • Conductive treatment was carried out on a 120 PPI polyurethane foam, and a copper metal element was electrodeposited to obtain a foamed copper having a bulk density of 0.18 g/cm 3 of 120 PPI and a specific surface area of 6000 cm 2 /cm 3 .
  • the heat treatment was carried out for 3 hours at a temperature of 700 ° C in a hydrogen atmosphere to remove the polyurethane.
  • metal iron was electrodeposited on the heat-treated copper foam to obtain a foamed copper-iron alloy having a 120 PPI bulk density of 0.24 g/cm 3 .
  • the foamed copper-iron alloy was subjected to a diffusion heat treatment at a temperature of 980 ° C and a vacuum of less than 1*10 -1 Pa for 14 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain a specific surface area of 18,500 cm.
  • the 2 /cm 3 ultra-high specific surface area foamed copper-iron alloy has a specific surface area that is more than three times greater than that of the original metal foam.
  • the surface topography of the foamed copper-iron alloy obtained in this example was similar to that of Example 1.

Abstract

Provided is a method for preparing a foam metal. The method comprises: carrying out a conductive treatment on a polyurethane foam, and electrodepositing at least one metal to obtain a foam metal substrate; carrying out a heat treatment on the resulting foam metal substrate in a hydrogen atmosphere to remove the polyurethane; depositing a metal material different from the metal foam substrate on the foam metal substrate to obtain a foam metal alloy; and carrying out a diffusion heat treatment on the foam metal alloy under a reduction atmosphere of hydrogen gas, and rapidly cooling the foam metal alloy after the diffusion heat treatment, thereby finally obtaining a foam metal alloy having an ultrahigh specific surface area. On the basis of the difference in diffusion rate of dissimilar metals in the process of high temperature interdiffusion, the diffusion reaction can be quickly stopped by rapid cooling at the highest point of diffusion. Therefore, defects such as vacancies and holes left by incomplete diffusion are retained to form the ultra-high specific surface area foam metal.

Description

一种泡沫金属制备方法Method for preparing foam metal 技术领域Technical field
本发明涉及泡沫金属制备技术领域，具体涉及一种泡沫金属制备方法。The invention relates to the technical field of foam metal preparation, and in particular to a method for preparing a metal foam.
背景技术Background technique
泡沫金属材料是一种优异的功能化环保材料，它集力学、热学、电学、声学等性能于一体，在材料领域拥有不可替代的重要地位。高孔隙率及高比表面积是泡沫金属的结构特征和重要特性，也是决定泡沫金属在吸声吸能、阻尼降噪、电磁屏蔽、过滤分离等领域具有明显应用优势的关键性能。目前，三维网状的开孔泡沫金属制备主要采用电沉积和气相沉积的方法，所制备的泡沫金属纤维表面为光滑或接近光滑状态，如图1-2所示。这导致泡沫金属的高比表面积难以进一步的提高，限制了其更广泛的应用。Foam metal is an excellent functional environmentally friendly material. It combines the functions of mechanics, thermals, electricity, and acoustics, and has an irreplaceable important position in the field of materials. High porosity and high specific surface area are the structural characteristics and important characteristics of foam metal. They are also the key properties that determine the application advantages of foam metal in the fields of sound absorption, damping, electromagnetic shielding, filtration separation and so on. At present, the three-dimensional network of open-cell foam metal is mainly prepared by electrodeposition and vapor deposition, and the surface of the prepared foam metal fiber is smooth or nearly smooth, as shown in Fig. 1-2. This results in a difficulty in further increasing the high specific surface area of the metal foam, which limits its wider application.
发明内容Summary of the invention
针对现有技术的不足，本发明旨在提供一种泡沫金属制备方法，基于异种金属在高温互扩散过程中的扩散速率差异，在扩散进行最为剧烈的时候快速降温让扩散反应迅速停止，从而将因扩散不完全所留下来的空位、孔洞等缺陷保留下来，形成超高比表面积泡沫金属。In view of the deficiencies of the prior art, the present invention aims to provide a method for preparing a metal foam based on the difference in diffusion rate of a dissimilar metal in a high temperature interdiffusion process, and rapidly lowering the temperature during the most vigorous diffusion to allow the diffusion reaction to stop rapidly, thereby Defects such as vacancies and holes remaining due to incomplete diffusion remain, forming an ultra-high specific surface area foam metal.
为了实现上述目的，本发明采用如下其中一技术方案：In order to achieve the above object, the present invention adopts one of the following technical solutions:
一种泡沫金属制备方法，包括如下步骤：A method for preparing a metal foam, comprising the steps of:
S1、在聚氨酯泡沫上进行导电处理，电沉积至少一种金属，得到泡沫金属基体；S1, conducting a conductive treatment on the polyurethane foam, and electrodepositing at least one metal to obtain a foam metal substrate;
S2、将步骤S1中所得的泡沫金属基体在氢气气氛下进行热处理以去除聚氨酯，所述热处理的温度为400℃-1000℃；S2, the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
S3、在经过热处理后的泡沫金属基体上沉积与步骤S1中所电沉积的金属不相同的另一种金属材质，得到泡沫金属合金；S3, depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy;
S4、对步骤S3中得到的泡沫金属合金在氢气的还原气氛下进行扩散热处理，所述扩散热处理的温度为600℃-1000℃；扩散热处理结束后快速冷却至室温，冷却速率大于10℃/min，最终得到超高比表面积的泡沫金属合金。S4, performing a diffusion heat treatment on the metal foam obtained in step S3 under a reducing atmosphere of hydrogen gas, the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the diffusion heat treatment is finished, rapidly cooling to room temperature, the cooling rate is greater than 10 ° C / min Finally, a foam metal alloy with an ultra-high specific surface area is obtained.
需要说明的是，步骤S1中的金属为镍、铜或铁。It should be noted that the metal in step S1 is nickel, copper or iron.
需要说明的是，步骤S1中，所述泡沫金属基体的规格为5PPI-200PPI。It should be noted that, in step S1, the specification of the foam metal substrate is 5PPI-200PPI.
需要说明的是，步骤S2中，所述热处理的时间为10min-300min。It should be noted that, in step S2, the heat treatment time is from 10 min to 300 min.
需要说明的是，步骤S3中，所述沉积采用电沉积或气相沉积的方式。It should be noted that, in step S3, the deposition is performed by electrodeposition or vapor deposition.
需要说明的是，步骤S3中，所述金属材质为镍、铜或铁。It should be noted that, in step S3, the metal material is nickel, copper or iron.
需要说明的是，步骤S4中，所述扩散热处理的时间为1h-20h。It should be noted that, in step S4, the diffusion heat treatment time is 1 h-20 h.
为了实现上述目的，本发明采用如下另一技术方案：In order to achieve the above object, the present invention adopts the following other technical solutions:
一种泡沫金属制备方法，包括如下步骤：A method for preparing a metal foam, comprising the steps of:
S1、在聚氨酯泡沫上进行导电处理，电沉积至少一种金属，得到 泡沫金属基体；S1, conducting a conductive treatment on the polyurethane foam, and electrodepositing at least one metal to obtain a foam metal substrate;
S2、将步骤S1中所得的泡沫金属基体在氢气气氛下进行热处理以去除聚氨酯，所述热处理的温度为400℃-1000℃；S2, the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
S3、在经过热处理后的泡沫金属基体上沉积与步骤S1中所电沉积的金属不相同的另一种金属材质，得到泡沫金属合金；S3, depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy;
S4、对步骤S3中得到的泡沫金属合金在氮气、氩气或氦气的保护气氛下，或在真空度小于1*10 -1Pa的真空条件下进行扩散热处理，所述扩散热处理的温度为600℃-1000℃；扩散热处理结束后快速冷却至室温，冷却速率大于10℃/min，最终得到超高比表面积的泡沫金属合金。 S4, performing a diffusion heat treatment on the metal foam alloy obtained in the step S3 under a protective atmosphere of nitrogen, argon or helium, or under a vacuum condition of a vacuum degree of less than 1*10 -1 Pa, the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the end of the diffusion heat treatment, rapid cooling to room temperature, the cooling rate is greater than 10 ° C / min, and finally obtain a foam metal alloy with ultra-high specific surface area.
需要说明的是，步骤S1中的金属为镍、铜或铁。It should be noted that the metal in step S1 is nickel, copper or iron.
需要说明的是，步骤S1中，所述泡沫金属基体的规格为5PPI-200PPI。It should be noted that, in step S1, the specification of the foam metal substrate is 5PPI-200PPI.
需要说明的是，步骤S2中，所述热处理的时间为10min-300min。It should be noted that, in step S2, the heat treatment time is from 10 min to 300 min.
需要说明的是，步骤S3中，所述沉积采用电沉积或气相沉积的方式。It should be noted that, in step S3, the deposition is performed by electrodeposition or vapor deposition.
需要说明的是，步骤S3中，所述金属材质为镍、铜或铁。It should be noted that, in step S3, the metal material is nickel, copper or iron.
需要说明的是，步骤S4中，所述扩散热处理的时间为1h-20h。It should be noted that, in step S4, the diffusion heat treatment time is 1 h-20 h.
本发明的有益效果在于：The beneficial effects of the invention are:
本发明基于异种金属在高温互扩散过程中的扩散速率差异，在扩散进行最为剧烈时快速降温让扩散反应迅速停止，从而将因扩散不完全所留下来的空位、孔洞等缺陷保留下来，形成了超高比表面积泡沫 金属。The invention is based on the difference of diffusion rate of dissimilar metals in the process of high temperature interdiffusion, and the rapid cooling down when the diffusion is most intense causes the diffusion reaction to stop rapidly, thereby retaining defects such as vacancies and holes left by incomplete diffusion, and forming a defect. Ultra high specific surface area foam metal.
附图说明DRAWINGS
图1为现有技术制备得到的泡沫金属表面形貌示意图；1 is a schematic view showing the surface morphology of a foam metal prepared by the prior art;
图2为图1的放大示意图；Figure 2 is an enlarged schematic view of Figure 1;
图3为本发明其中一方法制备得到的泡沫金属表面形貌示意图；3 is a schematic view showing the surface morphology of a metal foam prepared by one of the methods of the present invention;
图4为图3的放大示意图；Figure 4 is an enlarged schematic view of Figure 3;
图5为本发明另一方法制备得到的泡沫金属表面形貌示意图；Figure 5 is a schematic view showing the surface morphology of a metal foam prepared by another method of the present invention;
图6为图5的放大示意图。Figure 6 is an enlarged schematic view of Figure 5.
具体实施方式detailed description
以下将结合附图对本发明作进一步的描述，需要说明的是，以下实施例以本技术方案为前提，给出了详细的实施方式和具体的操作过程，但本发明的保护范围并不限于本实施例。The present invention will be further described with reference to the accompanying drawings. It should be noted that the following embodiments are based on the technical solutions, and the detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the present invention. Example.
实施例1Example 1
在45PPI的聚氨酯泡沫上进行导电处理，实现电沉积镍金属单质，得到45PPI体密度为0.3g/cm 3的泡沫镍，比表面积为2000cm 2/cm 3。将泡沫镍在900℃下、氢气气氛中进行1小时的热处理以去除聚氨酯。然后在经过热处理的泡沫镍上电沉积金属铜，得到45PPI体密度为0.6g/cm 3的泡沫镍铜合金，在氢气还原气氛、800℃的条件下进行8小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温， 得到45PPI比表面积为6300cm 2/cm 3的超高比表面积的泡沫镍铜合金，与原始泡沫金属相比比表面积提高了超过三倍。 Conductive treatment was carried out on a 45 PPI polyurethane foam to realize electrodeposition of a nickel metal element, and a foamed nickel having a bulk density of 0.3 Pg/cm 3 of 45 PPI was obtained, and the specific surface area was 2000 cm 2 /cm 3 . The foamed nickel was heat-treated at 900 ° C for 1 hour in a hydrogen atmosphere to remove the polyurethane. Then, metal copper was electrodeposited on the heat-treated foamed nickel to obtain a foamed nickel-copper alloy having a bulk density of 0.6 P/cm 3 of 45 PPI, and subjected to diffusion heat treatment for 8 hours under a hydrogen reducing atmosphere at 800 ° C, and then at 10 ° C. The cooling rate of /min was rapidly cooled to room temperature to obtain an ultrahigh specific surface area foamed nickel-copper alloy having a 45 PPI specific surface area of 6300 cm 2 /cm 3 , which increased the specific surface area by more than three times compared with the original metal foam.
本实施例中得到泡沫镍铜合金的表面形貌示意图如图3-4所示，从图3-4中可见其表面带有微孔结构。The surface topography of the foamed nickel-copper alloy obtained in this embodiment is shown in Figs. 3-4, and the surface thereof has a microporous structure as seen from Fig. 3-4.
实施例2Example 2
在100PPI的聚氨酯泡沫上进行导电处理，电沉积镍金属单质，得到100PPI体密度为0.15g/cm 3的泡沫镍，比表面积为6500cm 2/cm 3。将泡沫镍在800℃下、氢气气氛中进行1.5小时的热处理以去除聚氨酯。然后在经过热处理的泡沫镍上气相沉积金属铁，得到100PPI体密度为0.22g/cm 3的泡沫镍铁合金。将泡沫镍铁合金在氢气气氛中、950℃的温度下进行10小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温，得到比表面积为15000cm 2/cm 3的超高比表面积的泡沫镍铁合金，与原始泡沫金属相比比表面积提高超过了两倍。本实施例中制得的泡沫镍铁合金的表面形貌与实施例1类似。 Conductive treatment was carried out on a 100 PPI polyurethane foam, and a nickel metal element was electrodeposited to obtain a foamed nickel having a 100 PPI bulk density of 0.15 g/cm 3 and a specific surface area of 6500 cm 2 /cm 3 . The foamed nickel was subjected to heat treatment at 800 ° C for 1.5 hours in a hydrogen atmosphere to remove the polyurethane. Then, metal iron was vapor-deposited on the heat-treated foamed nickel to obtain a foamed nickel-iron alloy having a 100 PPI bulk density of 0.22 g/cm 3 . The foamed nickel-iron alloy was subjected to diffusion heat treatment in a hydrogen atmosphere at a temperature of 950 ° C for 10 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain an ultrahigh specific surface area having a specific surface area of 15000 cm 2 /cm 3 . Foamed nickel-iron alloy, which has more than doubled the specific surface area compared to the original metal foam. The surface topography of the foamed nickel-iron alloy obtained in this example was similar to that of Example 1.
实施例3Example 3
在120PPI的聚氨酯泡沫上进行导电处理，电沉积铜金属单质，得到120PPI体密度为0.18g/cm 3的泡沫铜，比表面积为6000cm 2/cm 3。在700℃的温度下、氢气气氛中进行3小时的热处理以去除聚氨酯。然后在经过热处理的泡沫铜上电沉积金属铁，得到120PPI体密度为0.24g/cm 3的泡沫铜铁合金。将泡沫铜铁合金在氢气气氛中、温度为980℃的条件下进行14小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温，得到比表面积为18500cm 2/cm 3的超高比表面 积的泡沫铜铁合金，与原始泡沫金属相比比表面积提高了超过三倍。本实施例中制得的泡沫铜铁合金的表面形貌与实施例1类似。 Conductive treatment was carried out on a 120 PPI polyurethane foam, and a copper metal element was electrodeposited to obtain a foamed copper having a bulk density of 0.18 g/cm 3 of 120 PPI and a specific surface area of 6000 cm 2 /cm 3 . The heat treatment was carried out for 3 hours at a temperature of 700 ° C in a hydrogen atmosphere to remove the polyurethane. Then, metal iron was electrodeposited on the heat-treated copper foam to obtain a foamed copper-iron alloy having a 120 PPI bulk density of 0.24 g/cm 3 . The foamed copper-iron alloy was subjected to a diffusion heat treatment in a hydrogen atmosphere at a temperature of 980 ° C for 14 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain an ultra-high ratio of a specific surface area of 18,500 cm 2 /cm 3 . The surface area of the foamed copper-iron alloy increases the specific surface area by more than three times compared to the original metal foam. The surface topography of the foamed copper-iron alloy obtained in this example was similar to that of Example 1.
实施例4Example 4
在45PPI的聚氨酯泡沫上进行导电处理，实现电沉积镍金属单质，得到45PPI体密度为0.3g/cm 3的泡沫镍，比表面积为2000cm 2/cm 3。将泡沫镍在900℃下、氢气气氛中进行1小时的热处理以去除聚氨酯。然后在经过热处理的泡沫镍上电沉积金属铜，得到45PPI体密度为0.6g/cm 3的泡沫镍铜合金，在氮气、氩气或氦气的保护气氛下、800℃的条件下进行8小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温，得到45PPI比表面积为6800cm 2/cm 3的超高比表面积的泡沫镍铜合金，与原始泡沫金属相比比表面积提高了超过三倍。 Conductive treatment was carried out on a 45 PPI polyurethane foam to realize electrodeposition of a nickel metal element, and a foamed nickel having a bulk density of 0.3 Pg/cm 3 of 45 PPI was obtained, and the specific surface area was 2000 cm 2 /cm 3 . The foamed nickel was heat-treated at 900 ° C for 1 hour in a hydrogen atmosphere to remove the polyurethane. Then, metal copper is electrodeposited on the heat-treated foamed nickel to obtain a foamed nickel-copper alloy having a bulk density of 0.6 P/cm 3 of 45 PPI, and is subjected to a protective atmosphere of nitrogen, argon or helium at 800 ° C for 8 hours. Diffusion heat treatment, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min, to obtain a foamed nickel-copper alloy with an ultra-high specific surface area of 45 PPI and a specific surface area of 6800 cm 2 /cm 3 , which has a specific surface area increased by more than three compared with the original metal foam. Times.
本实施例中得到泡沫镍铜合金的表面形貌示意图如图5-6所示，从图5-6中可见其表面带有微孔结构。The surface topography of the foamed nickel-copper alloy obtained in this embodiment is shown in Fig. 5-6. It can be seen from Fig. 5-6 that the surface has a microporous structure.
实施例5Example 5
在100PPI的聚氨酯泡沫上进行导电处理，电沉积镍金属单质，得到100PPI体密度为0.15g/cm 3的泡沫镍，比表面积为6500cm 2/cm 3。将泡沫镍在800℃下、氢气气氛中进行1.5小时的热处理以去除聚氨酯。然后在经过热处理的泡沫镍上气相沉积金属铁，得到100PPI体密度为0.22g/cm 3的泡沫镍铁合金。将泡沫镍铁合金在950℃的温度、真空度小于1*10 -2Pa的高真空条件下进行10小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温，得到比表面积为15000cm 2/cm 3的超高比表面积的泡沫镍铁合金，与原始泡沫金属相比 比表面积提高超过了两倍。本实施例中制得的泡沫镍铁合金的表面形貌与实施例1类似。 Conductive treatment was carried out on a 100 PPI polyurethane foam, and a nickel metal element was electrodeposited to obtain a foamed nickel having a 100 PPI bulk density of 0.15 g/cm 3 and a specific surface area of 6500 cm 2 /cm 3 . The foamed nickel was subjected to heat treatment at 800 ° C for 1.5 hours in a hydrogen atmosphere to remove the polyurethane. Then, metal iron was vapor-deposited on the heat-treated foamed nickel to obtain a foamed nickel-iron alloy having a 100 PPI bulk density of 0.22 g/cm 3 . The foamed nickel-iron alloy was subjected to a diffusion heat treatment at a temperature of 950 ° C and a vacuum of less than 1*10 -2 Pa for 10 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain a specific surface area of 15000 cm. The 2 /cm 3 ultra-high specific surface area foamed nickel-iron alloy has more than doubled the specific surface area compared to the original metal foam. The surface topography of the foamed nickel-iron alloy obtained in this example was similar to that of Example 1.
实施例6Example 6
在120PPI的聚氨酯泡沫上进行导电处理，电沉积铜金属单质，得到120PPI体密度为0.18g/cm 3的泡沫铜，比表面积为6000cm 2/cm 3。在700℃的温度下、氢气气氛中进行3小时的热处理以去除聚氨酯。然后在经过热处理的泡沫铜上电沉积金属铁，得到120PPI体密度为0.24g/cm 3的泡沫铜铁合金。将泡沫铜铁合金在温度为980℃、真空度小于1*10 -1Pa的高真空条件下进行14小时的扩散热处理，然后以10℃/min的冷却速率快速冷却至室温，得到比表面积为18500cm 2/cm 3的超高比表面积的泡沫铜铁合金，与原始泡沫金属相比比表面积提高了超过三倍。本实施例中制得的泡沫铜铁合金的表面形貌与实施例1类似。 Conductive treatment was carried out on a 120 PPI polyurethane foam, and a copper metal element was electrodeposited to obtain a foamed copper having a bulk density of 0.18 g/cm 3 of 120 PPI and a specific surface area of 6000 cm 2 /cm 3 . The heat treatment was carried out for 3 hours at a temperature of 700 ° C in a hydrogen atmosphere to remove the polyurethane. Then, metal iron was electrodeposited on the heat-treated copper foam to obtain a foamed copper-iron alloy having a 120 PPI bulk density of 0.24 g/cm 3 . The foamed copper-iron alloy was subjected to a diffusion heat treatment at a temperature of 980 ° C and a vacuum of less than 1*10 -1 Pa for 14 hours, and then rapidly cooled to room temperature at a cooling rate of 10 ° C / min to obtain a specific surface area of 18,500 cm. The 2 /cm 3 ultra-high specific surface area foamed copper-iron alloy has a specific surface area that is more than three times greater than that of the original metal foam. The surface topography of the foamed copper-iron alloy obtained in this example was similar to that of Example 1.
对于本领域的技术人员来说，可以根据以上的技术方案和构思，给出各种相应的改变和变形，而所有的这些改变和变形，都应该包括在本发明权利要求的保护范围之内。A person skilled in the art can make various changes and modifications in accordance with the above technical solutions and concepts, and all such changes and modifications are intended to be included within the scope of the appended claims.

Claims (14)

  1. 一种泡沫金属制备方法，其特征在于，包括如下步骤：A method for preparing a metal foam, comprising the steps of:
    S1、在聚氨酯泡沫上进行导电处理，电沉积至少一种金属，得到泡沫金属基体；S1, conducting a conductive treatment on the polyurethane foam, and electrodepositing at least one metal to obtain a foam metal substrate;
    S2、将步骤S1中所得的泡沫金属基体在氢气气氛下进行热处理以去除聚氨酯，所述热处理的温度为400℃-1000℃；S2, the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
    S3、在经过热处理后的泡沫金属基体上沉积与步骤S1中所电沉积的金属不相同的另一种金属材质，得到泡沫金属合金；S3, depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy;
    S4、对步骤S3中得到的泡沫金属合金在氢气的还原气氛下进行扩散热处理，所述扩散热处理的温度为600℃-1000℃；扩散热处理结束后快速冷却至室温，冷却速率大于10℃/min，最终得到超高比表面积的泡沫金属合金。S4, performing a diffusion heat treatment on the metal foam obtained in step S3 under a reducing atmosphere of hydrogen gas, the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the diffusion heat treatment is finished, rapidly cooling to room temperature, the cooling rate is greater than 10 ° C / min Finally, a foam metal alloy with an ultra-high specific surface area is obtained.
  2. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步骤S1中的金属为镍、铜或铁。The method of preparing a metal foam according to claim 1, wherein the metal in step S1 is nickel, copper or iron.
  3. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步骤S1中，所述泡沫金属基体的规格为5PPI-200PPI。The method for preparing a metal foam according to claim 1, wherein in the step S1, the foam metal substrate has a specification of 5 PPI-200 PPI.
  4. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步骤S2中，所述热处理的时间为10min-300min。The method for preparing a metal foam according to claim 1, wherein in the step S2, the heat treatment time is from 10 min to 300 min.
  5. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步骤S3中，所述沉积采用电沉积或气相沉积的方式。The method for preparing a metal foam according to claim 1, wherein in the step S3, the depositing is performed by electrodeposition or vapor deposition.
  6. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步骤S3中，所述金属材质为镍、铜或铁。The method for preparing a metal foam according to claim 1, wherein in the step S3, the metal material is nickel, copper or iron.
  7. 根据权利要求1所述的泡沫金属制备方法，其特征在于，步 骤S4中，所述扩散热处理的时间为1h-20h。The method of preparing a metal foam according to claim 1, wherein in the step S4, the diffusion heat treatment is performed for a period of from 1 h to 20 h.
  8. 一种泡沫金属制备方法，其特征在于，包括如下步骤：A method for preparing a metal foam, comprising the steps of:
    S1、在聚氨酯泡沫上进行导电处理，电沉积至少一种金属，得到泡沫金属基体；S1, conducting a conductive treatment on the polyurethane foam, and electrodepositing at least one metal to obtain a foam metal substrate;
    S2、将步骤S1中所得的泡沫金属基体在氢气气氛下进行热处理以去除聚氨酯，所述热处理的温度为400℃-1000℃；S2, the foam metal substrate obtained in step S1 is heat-treated under a hydrogen atmosphere to remove the polyurethane, the heat treatment temperature is 400 ° C -1000 ° C;
    S3、在经过热处理后的泡沫金属基体上沉积与步骤S1中所电沉积的金属不相同的另一种金属材质，得到泡沫金属合金；S3, depositing another metal material different from the metal electrodeposited in step S1 on the heat-treated metal foam substrate to obtain a foam metal alloy;
    S4、对步骤S3中得到的泡沫金属合金在氮气、氩气或氦气的保护气氛下，或在真空度小于1*10 -1Pa的真空条件下进行扩散热处理，所述扩散热处理的温度为600℃-1000℃；扩散热处理结束后快速冷却至室温，冷却速率大于10℃/min；最终得到超高比表面积的泡沫金属合金。 S4, performing a diffusion heat treatment on the metal foam alloy obtained in the step S3 under a protective atmosphere of nitrogen, argon or helium, or under a vacuum condition of a vacuum degree of less than 1*10 -1 Pa, the temperature of the diffusion heat treatment is 600 ° C - 1000 ° C; after the end of the diffusion heat treatment, rapidly cooled to room temperature, the cooling rate is greater than 10 ° C / min; finally obtained a super high specific surface area of the foam metal alloy.
  9. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步骤S1中的金属为镍、铜或铁。The method of preparing a metal foam according to claim 8, wherein the metal in the step S1 is nickel, copper or iron.
  10. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步骤S1中，所述泡沫金属基体的规格为5PPI-200PPI。The method for preparing a metal foam according to claim 8, wherein in the step S1, the foam metal substrate has a specification of 5 PPI-200 PPI.
  11. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步骤S2中，所述热处理的时间为10min-300min。The method for preparing a metal foam according to claim 8, wherein in the step S2, the heat treatment time is from 10 min to 300 min.
  12. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步骤S3中，所述沉积采用电沉积或气相沉积的方式。The method for preparing a metal foam according to claim 8, wherein in the step S3, the depositing is performed by electrodeposition or vapor deposition.
  13. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步 骤S3中，所述金属材质为镍、铜或铁。The method for preparing a metal foam according to claim 8, wherein in the step S3, the metal material is nickel, copper or iron.
  14. 根据权利要求8所述的泡沫金属制备方法，其特征在于，步骤S4中，所述扩散热处理的时间为1h-20h。The method for preparing a metal foam according to claim 8, wherein in the step S4, the diffusion heat treatment time is from 1 h to 20 h.
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CN106103808A (en) * 2014-03-06 2016-11-09 住友电气工业株式会社 Metal porous body and the manufacture method of metal porous body
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CN1355097A (en) * 2000-11-30 2002-06-26 北京有色金属研究总院 Composite foam metal and its preparing process
CN1480542A (en) * 2002-09-02 2004-03-10 北京有色金属研究总院 Porous body of composite metal and its preparing method
EP1477578A1 (en) * 2003-05-15 2004-11-17 Efoam S.A. Method for producing a metal coated heavy metal foam
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