WO2015164994A1 - 一种多孔金属材料的制备方法及其应用 - Google Patents

一种多孔金属材料的制备方法及其应用 Download PDF

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WO2015164994A1
WO2015164994A1 PCT/CN2014/000890 CN2014000890W WO2015164994A1 WO 2015164994 A1 WO2015164994 A1 WO 2015164994A1 CN 2014000890 W CN2014000890 W CN 2014000890W WO 2015164994 A1 WO2015164994 A1 WO 2015164994A1
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alloy
metal material
porous
porous metal
volatile
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PCT/CN2014/000890
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English (en)
French (fr)
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任伊宾
孙玉霞
肖克沈
杨柯
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中国科学院金属研究所
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Priority to US15/307,768 priority Critical patent/US20170043399A1/en
Publication of WO2015164994A1 publication Critical patent/WO2015164994A1/zh

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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
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1103—Making porous workpieces or articles with particular physical characteristics
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
    • 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
    • C22C1/088—Foaming process with solid metal other than by powder metallurgy

Definitions

  • the invention belongs to the field of metal material processing and preparation, and particularly provides a preparation method and application of a novel porous metal material.
  • porous metal has a large number of pores inside. These internal pores make the porous metal material have many excellent characteristics, such as small specific gravity, large specific surface area, good energy absorption, high heat dissipation and heat dissipation, and good sound absorption. Excellent permeability, good electromagnetic wave absorption, etc. Porous organic polymer materials have low strength and are not resistant to high temperatures, and porous ceramics are brittle and resistant to thermal shock. Therefore, porous metal materials are widely used in aerospace, atomic energy, electrochemistry, petrochemical, metallurgy, machinery, medicine, environmental protection, Filters, catalysts and catalyst carriers, porous electrodes, energy absorbers, silencers, shock absorbers, etc. in processes such as separation, filtration, catalysis, electrochemical processes, silencing, shock absorption, shielding, and heat exchange in industries such as construction , electromagnetic shielding devices, electromagnetic compatibility devices, heat exchangers and flame retardants.
  • the preparation methods of metal porous materials include melt foaming method, solid-gas eutectic solidification method, powder foaming method, melt casting method, spray foaming method, metal powder or fiber sintering method, sponge dipping sintering method, electricity Deposition, vapor deposition, and the like.
  • the dealloying method has also become a method for preparing nanoporous materials, and nanoporous platinum, nanoporous palladium, nanoporous titanium, and nanoporous copper can be prepared mainly by selective etching.
  • this method belongs to dealloying corrosion, and the porous metal materials are generally used on the surface of metal materials. It is difficult to prepare a bulk material.
  • the object of the present invention is to provide a preparation process for preparing a porous metal material having a three-dimensional through-hole structure, and the porous metal material prepared by the method can be widely applied to separation filtration, catalysis, noise reduction and noise reduction, battery current collector, capacitor, Energy absorption and vibration reduction, optical film, electromagnetic shielding, heat exchange and medical plastic repair.
  • the invention specifically provides a method for preparing a porous metal material, characterized in that one or more volatile alloying elements in the alloy are volatilized in a vacuum environment to finally form a porous pure metal or a porous alloy.
  • the basic principle of the present invention is to utilize a relatively high vapor pressure (at least three orders of magnitude higher than the same processing temperature) by using one or more volatile alloying elements (porosity elements) in the alloy at a specific temperature interval.
  • the vacuum gradually volatilizes and eventually forms a porous pure metal or alloy.
  • the raw material used must be an alloy, and at least one of the pore-forming elements, the pore-forming element has a relatively high vapor pressure relative to the matrix element in the alloy, and the pore-forming element can form a uniform alloy, solid solution or matrix alloy element
  • the content of pore-forming elements in the alloy needs to be controlled at 20at.%-80at.% to form different porosity, and finally the pore-forming elements are volatilized below the melting point temperature of the alloy and under high vacuum. .
  • the method for preparing a porous metal material according to the present invention is characterized in that, in order to save energy and improve efficiency, the thickness of the alloy used is preferably controlled between 0.005 and 1000 mm, and the alloy is in the range of 200 to 1200 ° C and the degree of vacuum is less than 500 Pa. Under the thickness of the alloy for more than 0.1 hours, the volatile alloy elements are gradually volatilized, the lower the vacuum, the better, preferably Below 10pa.
  • the method for preparing a porous metal material according to the present invention is characterized in that the treatment temperature is lower than the melting point of the alloy, and the treatment temperature is not lower than the temperature at which the vapor pressure of the volatile alloy element in the alloy is greater than or equal to 0.1 Pascal, and not higher than the melting point of the alloy.
  • the temperature is 0.85 times (for example, 62 brass melting point is 930 ° C, the processing temperature needs to be less than or equal to 790.5 ° C, otherwise it will cause the micropore to close).
  • the method for preparing a porous metal material according to the present invention is characterized in that the preparation process is: using a commercially available alloy or a self-made alloy, the alloy is required to contain at least one or more volatile alloying elements; according to the melting point of the different alloys and The vapor pressure characteristics of different volatile alloy elements, the alloy is released from the alloy by a high vacuum at a temperature lower than the melting point of the alloy. The vacuum is recommended to be kept below 10 Pa, and finally a porous pure metal or porous alloy is formed.
  • the volatile alloying element requires a vapor pressure higher than a vapor pressure of the matrix element in the alloy (at least three orders of magnitude higher than the same processing temperature), and is capable of forming a uniform alloy or solid solution with the matrix alloying element.
  • the powder of several alloying elements is uniformly mixed by a powder metallurgy method, and then pressed into a metal mixture of a desired shape.
  • the alloy or metal mixture of the invention is characterized in that it must be relatively uniform, the uniformity of the commercial alloy can meet the preparation requirements, and the uniformity of the self-made alloy needs to increase the agitation or multiple remelting during the alloy smelting to improve the uniformity of the alloy.
  • the metal mixture needs to be thoroughly stirred before pressing.
  • the alloy of the invention is an iron-based alloy, a nickel-based alloy, a titanium alloy, a cobalt-based alloy, a copper alloy, a precious metal alloy, a silicon alloy, an aluminum alloy or a magnesium alloy, and the pore-forming element is volatilizable. Alloying elements, preferably manganese, zinc, arsenic, cadmium, antimony, antimony, selenium, tellurium, antimony, magnesium, calcium, strontium, barium, strontium, potassium, lead, sulfur, phosphorus, sodium, lithium, etc. Pressed alloying elements.
  • the alloy may also be a precious metal alloy based on gold, platinum, rhodium, palladium or iridium, and selected from manganese, zinc, arsenic, cadmium, antimony, bismuth, selenium, tellurium, antimony, magnesium, calcium, strontium, barium, strontium, strontium
  • One or more elements of potassium, lead, sulfur, phosphorus, sodium, and lithium are used as volatile alloying elements;
  • the pore-forming elements must be selected according to the characteristics of the prepared porous metal.
  • alloys such as iron-based alloys, titanium alloys, cobalt-based alloys or silicon alloys are preferably made of manganese as a pore-forming element
  • copper alloys are preferably made of zinc, lanthanum and cadmium.
  • Element, aluminum alloy or magnesium alloy, zinc, cadmium, arsenic, antimony, potassium, sulfur, phosphorus, sodium, antimony, bismuth, selenium and antimony are selected as the pore-forming elements.
  • the original alloy material for preparing the porous metal material can be prepared by smelting, powder metallurgy, etc., and the surface of the alloy needs to be polished and descaled before use, or the surface treatment by surface ion plating or spraying can be used to prepare the above-mentioned surface on a common alloy surface.
  • the alloy layer is obtained by the present process to obtain a surface porous gradient material.
  • the alloy powder having a particle size of more than 10 ⁇ m or more may also be prepared into a porous alloy powder or sphere by the treatment process of the present invention.
  • the porous metal material prepared by the method of the invention has a wide pore size distribution range of 0.01-100 micrometers (usually 0.01-20 micrometers), and the average pore diameter is mainly between 2-5 micrometers, very Evenly.
  • the method of the invention can be applied to separation, filtration, catalysis, electrochemical process, silencing, shock absorption, shielding, heat exchange in aerospace, atomic energy, electrochemistry, petrochemical, metallurgy, machinery, medicine, optics, environmental protection or construction.
  • the vacuum heat treatment process is mature, can be scaled production, not only can prepare large-sized blocks, but also is particularly suitable for preparing ultra-thin metal foil and powder or sphere, and various metal tubes, among which ultra-thin metal foil
  • the film has the characteristics of light transmission and ventilation, and can be used for filtration.
  • the three-dimensional porous pure metal or alloy prepared by the process has a through-hole structure, and the porosity can be adjusted according to the proportion of the alloy.
  • Fig. 1 is a three-dimensional porous pure copper picture (2 ⁇ m) obtained in Example 1.
  • Figure 3 is a three-dimensional porous nickel alloy picture (5 ⁇ m) obtained in Example 4.
  • Figure 4 is a three-dimensional porous stainless steel alloy picture (10 ⁇ m) obtained in Example 5.
  • Figure 7 is a three-dimensional porous pure copper foil picture (5 ⁇ m) obtained in Example 8.
  • Figure 8 shows the results of the charge and discharge test.
  • Figure 9 is a picture of a porous copper wire (20 ⁇ m) obtained in Example 9.
  • Figure 10 is a picture (5 ⁇ m) of a porous copper tube obtained in Example 10.
  • the self-made nickel-manganese alloy (70% manganese content) is smelted in a vacuum induction furnace.
  • the raw materials are pure nickel and electrolytic manganese, and the shielding gas is argon. Considering the volatilization of manganese, the manganese content of the compound is 72%, and the rest is nickel. The manganese content is 69.5%.
  • After casting, it is directly cut into 10 ⁇ 15 ⁇ 1mm thin slices from the ingot.
  • the sandpaper is polished to 0.8mm thick, suspended in a small vacuum heat treatment furnace in the laboratory, and kept at 900°C for 1 hour. Vacuum degree control. Within 10 Pa, three-dimensional porous pure nickel (Fig. 3) was obtained, having a pore diameter of 2 to 10 ⁇ m and a porosity of about 40%.
  • 316 stainless steel made of self-made high manganese 316 stainless steel (50% manganese content), 316 stainless steel and electrolytic manganese were prepared by vacuum induction furnace. Considering the volatilization of manganese, the manganese content of the compound was 51%, and the rest was 316 stainless steel. The measured manganese content was 50.5. %, after casting, cut directly into the 10 ⁇ 15 ⁇ 1mm sheet from the ingot, sand the paper to 0.8mm thick, and hang it in the laboratory small vacuum heat treatment furnace, keep it at 1000°C for 1 hour, and control the vacuum within 5Pa. A three-dimensional porous stainless steel (Fig. 4) was obtained, having a pore diameter of 2-15 ⁇ m and a porosity of about 50%.
  • the self-made silicon-manganese alloy (manganese content 60%) was used to melt the prepared pure silicon and electrolytic manganese by vacuum induction furnace. Considering the volatilization of manganese, the manganese content of the compound was 63%, and the rest was silicon. The measured manganese content was 60.2%. After casting, it is directly cut from the ingot to prepare 10 ⁇ 5 ⁇ 1mm pieces, suspended in a small vacuum heat treatment furnace in the laboratory, kept at a high vacuum for 2 hours at 900 °C, and the vacuum is controlled within 10 Pa to obtain three-dimensional porous silicon. 5), the pore diameter is 2-10 microns, and the porosity is about 15%.
  • the vacuum is maintained within 10Pa, to obtain three-dimensional porous pure copper foil
  • the pore size is 2-10 microns, as shown in Fig. 7, then the porous copper foil is used as the current collector, the positive electrode material is LiCoO 2 , the negative electrode material is made of composite graphite, and the electrolyte is made of commercial electrolyte 1 mol/L LiPF 6 /EC+ DMC+EMC (1:1:1 mass ratio) was pressed into a button cell in an argon atmosphere glove box.
  • the charge and discharge test results are shown in Fig. 8.
  • a porous copper wire was obtained by using a commercially available 62 brass wire, 0.1 mm diameter, in a laboratory vacuum heat treatment furnace, holding at 550 ° C for 1 hour, and keeping the vacuum within 10 Pa, as shown in FIG.

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Abstract

一种多孔金属材料的制备方法，包括：在真空环境中，使合金中一种或一种以上易挥发合金元素挥发，最终形成多孔纯金属或多孔合金。该工艺方法可广泛应用于航空航天、原子能、电化学、石油化工、冶金、机械、医药、环保或建筑等领域。

Description

一种多孔金属材料的制备方法及其应用 技术领域
本发明属于金属材料加工制备领域，具体提供一种新型多孔金属材料的制备方法及应用。
背景技术
多孔金属的显著特征是其内部具有大量的孔隙，这些内部孔隙使多孔金属材料具有诸多优异的特性，如比重小、比表面大、能量吸收性好、换热散热能力高、吸声性好、渗透性优、电磁波吸收性好等等。多孔有机高分子材料强度低且不耐高温，多孔陶瓷则质脆且不抗热震，因此多孔金属材料被广泛应用于航空航天、原子能、电化学、石油化工、冶金、机械、医药、环保、建筑等行业的分离、过滤、催化、电化学过程、消音、吸震、屏蔽、热交换等工艺过程中，制作过滤器、催化剂及催化剂载体、多孔电极、能量吸收器、消音器、减震缓冲器、电磁屏蔽器件、电磁兼容器件、换热器和阻燃器等。
目前金属多孔材料的制备方法有熔体发泡法，固体-气体共晶凝固法，粉体发泡法，熔铸法，喷雾发泡法，金属粉末或纤维烧结法，海绵浸浆烧结法，电沉积法，气相沉积法等等。近些年脱合金法也成为一种制备纳米多孔材料的方法，主要通过选择性腐蚀，可以制备出纳米多孔铂、纳米多孔钯、纳米多孔钛以及纳米多孔铜等。但是此方法属于脱合金腐蚀，用于制备多孔金属材料一般都是在金属材料表层 进行，难以制备大块材料。
发明内容
本发明的目的在于提供一种制备具有三维通孔结构的多孔金属材料的制备工艺，采用该工艺制备的多孔金属材料可广泛应用于分离过滤、催化、消音减噪、电池集电体、电容器、吸能减振、光学薄膜、电磁屏蔽、热交换和医学整形修复等领域。
本发明具体提供了一种多孔金属材料的制备方法，其特征在于：在真空环境中，使合金中一种或一种以上易挥发合金元素挥发，最终形成多孔纯金属或多孔合金。
本发明的基本原理是利用合金中一种或一种以上易挥发合金元素(造孔元素)在特定的温度区间相对较高的蒸汽压(至少同一处理温度下高三个数量级以上)，通过持续高真空使其逐渐挥发，最终形成多孔纯金属或合金。因此，采用的原材料必须是合金，而且其中至少有一种造孔元素，造孔元素相对合金中基体元素具有相对较高的蒸汽压，且造孔元素能够和基体合金元素形成均匀的合金、固溶体或通过粉末冶金加工的混合物，合金中造孔元素的含量需要控制在20at.％-80at.％以形成不同的孔隙率，最后使造孔元素在低于合金熔点温度以及持续高真空的条件下挥发。
本发明所述多孔金属材料的制备方法，其特征在于，为了节约能源和提高效率，所用合金的厚度最好控制在0.005-1000mm之间，将合金在200℃-1200℃、真空度小于500Pa条件下根据合金厚度保温0.1小时以上，使易挥发合金元素逐渐挥发，真空度越低越好，优选 10pa以下。
本发明所述多孔金属材料的制备方法，其特征在于，处理温度低于合金熔点，优选处理温度不低于合金中易挥发合金元素蒸气压大于等于0.1帕斯卡时的温度，同时不高于合金熔点温度的0.85倍(例如62黄铜熔点为930℃，则处理温度需小于等于790.5℃，否则会导致微孔闭合)。
本发明所述多孔金属材料的制备方法，其特征在于，制备过程为：采用市售合金或自制合金，要求该合金中至少含有一种或一种以上易挥发合金元素；根据不同合金的熔点以及不同易挥发合金元素的蒸汽压特点，将合金在低于合金熔点温度下，通过持续高真空使易挥发合金元素从合金中脱出，真空度建议保持在10Pa以下，最终形成多孔纯金属或多孔合金；其中，所述易挥发合金元素要求其蒸汽压比合金中基体元素的蒸汽压高(在同一处理温度下至少高三个数量级以上)，且能够与基体合金元素形成均匀的合金或固溶体。或通过粉末冶金的方法把几种合金元素的粉末均匀混合后，通过压制成所需形状的金属混合物。
本发明所述合金或金属混合物，其特征在于必须是相对均匀的，商用合金的均匀性可以满足制备要求，自制合金的均匀性需要在合金熔炼时增加搅拌或多次重熔来提高合金的均匀性，金属混合物在压制前需要充分搅拌。
本发明所述合金为铁基合金、镍基合金、钛合金、钴基合金、铜合金、贵金属合金、硅合金、铝合金或镁合金，造孔元素使用可挥发 性合金元素，优选锰、锌、砷、镉、锑、碲、硒、锶、镱、镁、钙、铊、钡、铋、钾、铅、硫、磷、钠、锂等具有较高饱和蒸汽压的合金元素。所述合金也可为以金、铂、铑、钯或铱为基础的贵金属合金，选择锰、锌、砷、镉、锑、碲、硒、锶、镱、镁、钙、铊、钡、铋、钾、铅、硫、磷、钠、锂元素中的一种或多种元素作为易挥发合金元素；
造孔元素必须根据所制备多孔金属的特点选择，例如铁基合金、钛合金、钴基合金或硅合金等合金均优选锰元素作为造孔元素，铜合金优选锌、锶、镉元素作为造孔元素，铝合金或镁合金，选择锌、镉、砷、铋、钾、硫、磷、钠、锑、碲、硒、锶元素作为造孔元素。
制备多孔金属材料的原始合金材料可以采用熔炼、粉末冶金等方法制备，使用前需将合金表面抛光去氧化皮，也可以通过表面离子镀、喷涂等表面处理方法在普通合金表面制备以上所述的合金层，通过本工艺获得表面多孔的梯度材料。也可以采用本发明处理工艺将粒度大于10微米以上的合金粉末制备成多孔合金粉末或球体。
采用本发明所述方法制备的多孔金属材料，其孔径分布范围较广，可达0.01-100微米(通常应用较多的为0.01-20微米)，平均孔径主要介于在2-5微米，非常均匀。
本发明所述方法可应用于航空航天、原子能、电化学、石油化工、冶金、机械、医药、光学、环保或建筑领域的分离、过滤、催化、电化学过程、消音、吸震、屏蔽、热交换工艺过程中，用于制作过滤器、催化剂及催化剂载体、多孔电极、能量吸收器、消音器、减震缓冲器、 电磁屏蔽器件、电磁兼容器件、换热器和阻燃器等。
本发明的优点在于：
(1)、真空热处理工艺成熟，可以进行规模化生产，不仅可以制备大尺寸块体，还特别适用于制备超薄金属箔片和粉体或球体，以及各种金属管，其中超薄金属箔片具有透光、透气的特点，可以用于过滤。
(2)、采用本工艺制备的三维多孔纯金属或合金具有通孔结构，孔隙率可以根据合金比例调节。
(3)、采用本工艺也可以制备表面多孔的梯度材料或多孔粉体材料。
(4)、本发明制备的多孔纯金属或合金，可以用于电池集电体、分离、过滤、催化、消音、吸震、屏蔽、热交换等领域。
附图说明
图1实施例1获得的三维多孔纯铜图片(2μm)。
图2实施例3获得的三维多孔铜合金图片(5μm)。
图3实施例4获得的三维多孔镍合金图片(5μm)。
图4实施例5获得的三维多孔不锈钢合金图片(10μm)。
图5实施例6获得的三维多孔硅合金图片(5μm)。
图6实施例7获得的三维多孔纯铜粉图片(50μm)。
图7实施例8获得的三维多孔纯铜箔图片(5μm)。
图8充放电测试结果图。
图9实施例9获得的多孔铜丝图片(20μm)。
图10实施例10获得的多孔铜管图片(5μm)。
图11比较例获得的铜片(10μm)。
具体实施方式
以下实施例将对本发明予以进一步的说明，但并不因此而限制本发明。
如无特殊说明，本实施例中所有百分数均表示原子百分比。
实施例1
采用市售62黄铜，制备成20×20×1mm小片，悬挂在实验室小型真空热处理炉内，在600℃保温持续高真空3小时，真空度控制在10Pa以内，获得三维多孔纯铜(图1)，孔径为1-3微米，孔隙率为20％左右。
实施例2：
采用市售62黄铜，制备成20×20×1mm小片，悬挂在实验室小型真空热处理炉内，在800℃保温持续高真空2小时，真空度控制在10Pa以内，没有获得多孔纯铜，经能谱分析发现，尽管黄铜中锌已被完全脱掉，但是样品表面仅有很少量小孔，分析原因为处理温度过高，铜合金表面形成的小孔经过扩散逐渐融合，因此制备多孔金属必须根据不同的合金选择合适的处理温度。
实施例3
采用自制的40硅黄铜(含锌60％，含硅3％)，采用石墨坩埚在 热处理炉内熔化配制好的纯铜，纯锌和纯硅，考虑到锌的挥发，配料时特意补充2％锌含量，浇铸后锻造成块体，然后线切割成10×15×1mm薄片，砂纸磨光到0.8mm厚，悬挂在实验室小型真空热处理炉内，在500℃保温1小时，真空度控制在10Pa以内，获得三维多孔铜硅合金(图2)，孔径为1-8微米，孔隙率为40％左右。
实施例4
采用自制镍锰合金(70％锰含量)，采用真空感应炉熔炼，原料为纯镍和电解锰，保护气为氩气，考虑到锰的挥发，配料锰含量为72％，其余为镍，实测锰含量为69.5％，浇铸后直接从铸锭上线切割成10×15×1mm薄片，砂纸磨光到0.8mm厚，悬挂在实验室小型真空热处理炉内，在900℃保温1小时，真空度控制在10Pa以内，获得三维多孔纯镍(图3)，孔径为2-10微米，孔隙率为40％左右。
实施例5
采用自制高锰316不锈钢(50％锰含量)，采用真空感应炉熔炼配制好的316不锈钢和电解锰，考虑到锰的挥发，配料锰含量为51％，其余为316不锈钢，实测锰含量为50.5％，浇铸后直接从铸锭上线切割成10×15×1mm薄片，砂纸磨光到0.8mm厚，悬挂在实验室小型真空热处理炉内，在1000℃保温1小时，真空度控制在5Pa以内，获得三维多孔不锈钢(图4)，孔径为2-15微米，孔隙率为50％左右。
实施例6
采用自制硅锰合金(锰含量60％)，采用真空感应炉熔炼配制好的纯硅和电解锰，考虑到锰的挥发，配料锰含量为63％，其余为硅，实测锰含量为60.2％，浇铸后直接从铸锭上线切割制备成10×5×1mm小片，悬挂在实验室小型真空热处理炉内，在900℃保温持续高真空2小时，真空度控制在10Pa以内，获得三维多孔硅(图5)，孔径为2-10微米，孔隙率为15％左右。
实施例7
采用市售62黄铜粉，粉尺寸为100目，在实验室真空热处理炉内，在550℃保温持续高真空1小时，真空度保持在10Pa以内，获得三维多孔纯铜粉，孔径为2-10微米，如图6所示。
实施例8
采用市售62黄铜箔片，厚度为20微米，裁剪成100mm正方形，在实验室真空热处理炉内，在550℃保温持续高真空1小时，真空度保持在10Pa以内，获得三维多孔纯铜箔，孔径为2-10微米，如图7所示，然后将多孔铜箔作为集电体，正极材料选择LiCoO2，负极材料采用复合石墨，电解液采用商用电解液1mol/L LiPF6/EC+DMC+EMC(1∶1∶1质量比)，在氩气气氛手套箱中压制成扣式电池，充放电测试结果如图8所示。
实施例9
采用市售62黄铜丝，0.1mm直径，在实验室真空热处理炉内，在550℃保温持续高真空1小时，真空度保持在10Pa以内，获得多孔铜丝，如图9所示。
实施例10
采用市售62黄铜管，2mm外径，壁厚0.1mm，在实验室真空热处理炉内，在600℃保温持续高真空2小时，真空度保持在10Pa以内，获得多孔铜管，如图10所示。
比较例
采用市售62黄铜，制备成20×20×1mm小片，悬挂在实验室小型真空热处理炉内，在800℃(温度偏高，超过熔点930℃的85％)保温持续高真空3小时，持续高真空，真空度保持在10Pa以内，获得的铜片表面大部分微孔闭合，仅保留少量小孔，如图11所示。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种多孔金属材料的制备方法，其特征在于：在真空环境中，使合金中一种或一种以上易挥发合金元素挥发，最终形成多孔纯金属或多孔合金，其中所述合金中至少含有一种易挥发合金元素，要求易挥发合金元素蒸汽压比合金中基体元素的蒸汽压高，且易挥发合金元素能够和合金中基体元素形成均匀的合金、固溶体或通过粉末冶金加工的混合物。
  2. 按照权利要求1所述多孔金属材料的制备方法，其特征在于：使合金中易挥发合金元素在低于合金熔点温度以及持续高真空的条件下挥发。
  3. 按照权利要求1所述多孔金属材料的制备方法，其特征在于，制备过程为：采用市售合金或自制合金，将合金在低于合金熔点温度下，通过持续高真空，真空度小于500Pa，使易挥发合金元素逐渐挥发，最终形成多孔纯金属或多孔合金；
    其中，所述易挥发合金元素要求其蒸汽压在同一处理温度下比合金中基体元素的蒸汽压高三个数量级以上。
  4. 按照权利要求1～3任一所述多孔金属材料的制备方法，其特征在于：所述易挥发合金元素占合金的原子百分比控制在20％-80％之间。
  5. 按照权利要求1～3任一所述多孔金属材料的制备方法，其特征在于：所用合金的厚度控制在0.005-1000mm，将合金在200℃-1200℃、真空度小于10Pa条件下根据合金厚度保温0.1小时以上， 使易挥发合金元素逐渐挥发。
  6. 按照权利要求1～3任一所述多孔金属材料的制备方法，其特征在于：所述合金为铁基合金、镍基合金、钛合金、钴基合金、硅合金或铜合金，选择锰、锌、砷、镉、锑、碲、硒、锶、镱、镁、钙、铊、钡、铋、钾、铅、硫、磷、钠、锂元素中的一种或多种元素作为易挥发合金元素；
    或所述合金为贵金属合金，选择锰、锌、砷、镉、锑、碲、硒、锶、镱、镁、钙、铊、钡、铋、钾、铅、硫、磷、钠、锂元素中的一种或多种元素作为易挥发合金元素，其中贵金属合金以金、铂、铑、钯或铱为基础；
    或所述合金为铝合金或镁合金，选择锌、镉、砷、铋、钾、硫、磷、钠、锑、碲、硒、锶元素中的一种或多种元素作为易挥发合金元素；
    所述合金采用熔炼或粉末冶金方法制备，使用前将合金表面抛光去氧化皮。
  7. 按照权利要求1～3任一所述多孔金属材料的制备方法，其特征在于：处理温度不低于合金中易挥发合金元素蒸气压大于等于0.1帕斯卡时的温度，同时不高于合金熔点温度的0.85倍。
  8. 一种按照权利要求1所述多孔金属材料的制备方法制备的多孔金属材料，其特征在于：所述多孔金属材料的孔径分布为0.1-20微米。
  9. 一种按照权利要求1所述多孔金属材料的制备方法的应用， 其特征在于：该方法可应用于航空航天、原子能、电化学、石油化工、冶金、机械、医药、光学、环保或建筑领域。
  10. 一种按照权利要求1所述多孔金属材料的制备方法的应用，其特征在于：采用该方法制备的多孔金属用于分离过滤、催化、消音减噪、电池集电体、电容器、吸能减振、光学薄膜、电磁屏蔽、热交换和医学整形修复。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106636717A (zh) * 2016-12-29 2017-05-10 天津理工大学 一种用蒸发差异纯化纳米多孔金属的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US11469358B1 (en) * 2019-02-19 2022-10-11 Meta Platforms Technologies, Llc Formation of nanoporous copper interconnect for electrical connection
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CN112553495B (zh) * 2019-09-25 2022-03-29 中国科学院金属研究所 一种铜铬双连续相材料的制备方法及铜铬双连续相材料
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CN111154997B (zh) * 2020-01-13 2021-05-11 中国工程物理研究院材料研究所 铜铁合金、铜铁合金微纳米复合多孔材料及其制备方法
CN111293296A (zh) * 2020-02-25 2020-06-16 山东大学 一种自支撑多孔硅合金及其制备方法与应用
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CN116516268A (zh) * 2023-04-14 2023-08-01 常熟市普华电工材料有限公司 一种合金铜丝退火工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124568A (ja) * 1997-10-24 1999-05-11 Shin Etsu Chem Co Ltd 蓄冷材及びその製造方法
CN101838754A (zh) * 2010-05-28 2010-09-22 昆明理工大学 一种锌蒸发发泡制备泡沫铝/铝合金的方法
CN101838753A (zh) * 2010-05-28 2010-09-22 昆明理工大学 一种镁蒸发发泡制备泡沫铝/铝合金的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5567336A (en) * 1978-11-16 1980-05-21 Mitsubishi Heavy Ind Ltd Preparation of catalyst
CN102534283A (zh) * 2010-12-10 2012-07-04 北京有色金属研究总院 一种多元合金泡沫材料及其制备方法
CN102864323B (zh) * 2012-09-25 2014-07-02 中国科学院金属研究所 一种结构可控的Ni-Al合金多孔材料制备方法
CN103627920B (zh) * 2013-11-11 2015-10-28 江苏大学 一种多孔镍的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124568A (ja) * 1997-10-24 1999-05-11 Shin Etsu Chem Co Ltd 蓄冷材及びその製造方法
CN101838754A (zh) * 2010-05-28 2010-09-22 昆明理工大学 一种锌蒸发发泡制备泡沫铝/铝合金的方法
CN101838753A (zh) * 2010-05-28 2010-09-22 昆明理工大学 一种镁蒸发发泡制备泡沫铝/铝合金的方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106636717A (zh) * 2016-12-29 2017-05-10 天津理工大学 一种用蒸发差异纯化纳米多孔金属的方法

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