CN109482882B - Foam metal with micro-oriented pore structure and preparation method thereof - Google Patents
Foam metal with micro-oriented pore structure and preparation method thereof Download PDFInfo
- Publication number
- CN109482882B CN109482882B CN201811227307.XA CN201811227307A CN109482882B CN 109482882 B CN109482882 B CN 109482882B CN 201811227307 A CN201811227307 A CN 201811227307A CN 109482882 B CN109482882 B CN 109482882B
- Authority
- CN
- China
- Prior art keywords
- metal
- water
- foam metal
- carbon material
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 111
- 239000002184 metal Substances 0.000 title claims abstract description 111
- 239000006260 foam Substances 0.000 title claims abstract description 71
- 239000011148 porous material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 238000007710 freezing Methods 0.000 claims abstract description 23
- 230000008014 freezing Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000005266 casting Methods 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- -1 polydimethylsiloxane Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 238000009413 insulation Methods 0.000 abstract description 7
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 9
- 229960004793 sucrose Drugs 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Images
Classifications
-
- 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
- B22F3/1109—Inhomogenous pore distribution
-
- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/222—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by freeze-casting or in a supercritical fluid
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to the field of foam metal materials, in particular to a foam metal with a microcosmic directional pore structure and a preparation method thereof. The foam metal has a directional pore structure microscopically, the metal framework and pores are directionally arranged in a lamellar mode along the freezing direction in the preparation process, the porosity of the foam metal is 10-90%, the pore diameter of the foam metal is 0.3-600 mu m, the framework of the foam metal can be enhanced by adding a nano carbon material, the content of the nano carbon material is 0-10% in percentage by mass, the rest is metal, and the added nano carbon material is preferentially oriented in the matrix of the metal framework along the arrangement direction of the framework. The foam metal is prepared by the processes of preparing water-based slurry, freezing and casting, vacuum freezing and drying, removing organic matters and sintering. The foam metal has the excellent performances of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like, and the preparation method has the advantages of simple process, low cost, energy conservation, environmental protection and suitability for large-scale production.
Description
Technical Field
The invention relates to the field of foam metal materials, in particular to a foam metal with a microcosmic directional pore structure and a preparation method thereof.
Background
As a structural functional material, the foam metal is widely applied in the fields of chemical engineering, transportation, energy, buildings and the like, plays an extremely important role, and simultaneously, the rapid development and new application requirements of all the fields continuously put forward higher and higher requirements on the mechanical property and the function of the foam metal. The foam metal is optimally designed and prepared to obtain excellent mechanical properties such as lighter weight, high specific strength, high energy absorption rate and the like and certain functional characteristics, and has important significance for promoting the foam metal to better meet engineering application requirements.
The cellular structure of the foam metal prepared by the traditional method usually has the characteristics of isotropy and disorder, the mechanical strength is low, and the functions of sound absorption, heat insulation and the like are limited to a certain extent. The design and control of the microstructure of the foam metal are important ways for improving the performance of the foam metal. In this regard, many natural biomaterials with porous structures can provide important insights. For example, the porous structures in the wood are microscopically arranged in an oriented manner along the growth direction, so that the wood shows anisotropic performance characteristics, particularly has excellent mechanical properties such as high strength and high rigidity along the stress direction, and the oriented porous structures are also beneficial to the efficient transportation of moisture and nutrient substances. The foam metal with the microcosmic directional pore structure is designed and prepared by simulating the microcosmic structure of a natural biological material, and is expected to solve the problems of low strength, poor energy absorption efficiency and the like of the traditional foam metal, so that the requirement of engineering application is better met.
In addition, the mechanical properties and functions of the metal foam can be further improved by introducing a second or reinforcing phase into the metal matrix of its skeleton. Graphene, as a novel two-dimensional nanomaterial, exhibits extremely high modulus and strength and excellent electrical and thermal conductivity along the lamellar direction due to its small size with few defects and strong covalent bonding between atoms in the layer, and is flexible, flexible and stable in structure and chemical properties. The carbon nano tube is a unique one-dimensional nano material, is similar to graphene, and has excellent mechanical, physical and chemical properties. As a unique property nanocarbon material, graphene and carbon nanotubes can be used as ideal reinforcing components of the foamed metal skeleton to improve its properties.
Disclosure of Invention
One of the purposes of the invention is to provide a nano carbon material reinforced foam metal with a micro oriented pore structure, and the foam metal achieves excellent performances of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like through the micro structure design; the second objective of the present invention is to provide a method for preparing the foamed metal with the micro-oriented pore structure, so as to realize the structural design and control of the micro-oriented pores of the foamed metal, and realize the uniform distribution and oriented arrangement of the nano carbon material in the metal skeleton matrix.
In order to achieve the above object, the technical solution adopted by the present invention is as follows:
a foam metal with a microcosmic oriented pore structure is provided with an oriented pore structure on the microcosmic surface, and is characterized in that a metal framework and pores are directionally arranged in a lamellar form along a freezing direction in the preparation process, the porosity of the foam metal is 10-90%, and the pore diameter of the foam metal is 0.3-600 mu m; the skeleton of the foam metal is reinforced by adding a nano carbon material, the content of the nano carbon material is 0-10% by mass percent, the balance is metal, and the added nano carbon material is preferentially oriented in the arrangement direction of the skeleton in a metal skeleton matrix.
The metal is nickel, aluminum, palladium, silver, copper metal simple substance or alloy taking the metal as a matrix, and the nano carbon material is graphene, carbon nano tubes or the combination of the graphene and the carbon nano tubes.
The preparation method of the foam metal with the micro-oriented pore structure comprises the following steps:
(A) preparing water-based slurry: weighing metal powder, nano carbon material powder, water and an additive, and uniformly mixing to obtain water-based slurry containing the metal powder;
(B) freezing and casting: pouring the water-based slurry into a mold, and directionally freezing to directionally solidify water in the mold along a freezing direction, so that the metal powder, the nano carbon material powder and the additive are extruded among directionally grown ice layers to be directionally arranged on a microscopic scale;
(C) vacuum freeze drying: after demoulding the solidified water-based slurry, carrying out vacuum freeze drying treatment to remove water contained in the water-based slurry, thus obtaining a porous blank with a microcosmic oriented lamellar structure;
(D) organic matter removal and sintering: and carrying out high-temperature treatment on the green body to remove organic matters contained in the green body, and then carrying out high-temperature sintering on the green body after the organic matters are removed to obtain the foam metal with the microcosmic directional pore structure.
In the step (A), the mass ratio range of the metal powder, the nano carbon material powder, the additive and the water is 1: (0-0.12): (0.001-0.5): (0.05-10); the additive comprises a dispersant and an organic binder, wherein the dispersant is one or more of sodium dodecyl sulfate, polyacrylic acid, polyethyleneimine, sodium dodecyl benzene sulfonate or Darvan CN, the addition amount of the dispersant is 0-12% of the mass of the metal powder, the organic binder is one or more of polyvinyl alcohol, polyethylene glycol, sucrose, hydroxypropyl methylcellulose or guar gum, and the addition amount of the organic binder is 0.5-15% of the mass of deionized water; the mixing process of the water-based slurry is one or any combination of ultrasonic, stirring, vibration and ball milling.
In the step (B), the freezing casting process comprises the following steps: pouring the uniformly mixed slurry into a mold, cooling one end of the mold to ensure that water in the slurry is directionally solidified along the cooling direction, and gradually squeezing the metal powder, the nano carbon material powder and the additive in the slurry to be among ice layers by ice crystals growing along the solidification direction, thereby realizing the microscopic directional arrangement; the cooling of the mold is realized by connecting the mold with a copper plate with one end immersed in a coolant, wherein the coolant is liquid nitrogen or dry ice.
In the step (C), the vacuum freeze drying process comprises the following steps: and (3) demolding the solidified slurry, and placing the slurry in a vacuum environment with the cold trap temperature lower than-30 ℃ and the vacuum degree not more than 10Pa for more than 10 h.
In the step (D), the green body is subjected to high-temperature treatment to remove organic matters contained in the green body, and the porous green body is subjected to high-temperature treatment in vacuum or protective atmosphere, wherein the treatment temperature is 350-800 ℃, and the protective atmosphere is one of nitrogen, argon and helium or any mixed gas thereof; the organic matter removed blank is sintered at high temperature and is finished in vacuum, protective atmosphere or reducing atmosphere, wherein the protective atmosphere is one of nitrogen, argon and helium or any mixed gas of the nitrogen, the argon and the helium, and the reducing atmosphere is hydrogen or mixed gas of hydrogen and argon; when the metal is nickel or nickel-based alloy, the sintering temperature is 900-1400 ℃, when the metal is aluminum or aluminum-based alloy, the sintering temperature is 450-650 ℃, when the metal is palladium or palladium-based alloy, the sintering temperature is 1000-1500 ℃, when the metal is silver or silver-based alloy, the sintering temperature is 750-930 ℃, and when the metal is copper or copper-based alloy, the sintering temperature is 700-1000 ℃.
The design idea of the invention is as follows:
the invention designs and prepares the foam metal with the microcosmic oriented pore structure by simulating the microcosmic structure of natural biological materials such as wood, and the like, and because the metal framework and the pores on the microcosmic surface are oriented and arranged in a lamellar form along the freezing direction in the preparation process, the foam metal has the excellent performances of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like, and particularly the strength and the rigidity of the foam metal are obviously improved compared with the foam metal with the isotropic pore structure along the arrangement direction of the framework. The microcosmic directional pore structure of the foam metal is mainly realized based on a freezing casting process, wherein the freezing casting process utilizes ice crystals growing along the solidification direction in the water-based slurry to extrude powder and additives in the slurry between adjacent ice layers in the directional solidification process of water contained in the water-based slurry, so that microcosmic directional arrangement of the powder and the additives is realized. In the foam metal prepared by the process, characteristic structures such as micro-nano scale cross overlapping, bulges, bridging and the like can be formed between the sheet layers of adjacent metal frameworks, and the structures such as porosity, pore diameter and the like can be effectively controlled by adjusting the concentration, cooling speed, additive type, content and the like of slurry. In the directional solidification process of the slurry, the graphene and the carbon nano tubes tend to be preferentially oriented along the growth direction of the ice crystals due to the anisotropic appearance and the large diameter-thickness ratio (or length-diameter ratio), so that the preferred orientation and directional arrangement of the nano carbon material in the matrix of the foam metal framework are finally realized, the reinforcing effect of the nano carbon material is effectively exerted, and the mechanical property of the nano carbon material is remarkably improved on the premise of further reducing the density of the foam metal.
Compared with the prior materials and technologies, the invention has the following advantages and beneficial effects:
(A) the foam metal has excellent properties of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like due to the microcosmic directional pore structure, so the foam metal has considerable application prospect as a structural function integrated material.
(B) The preparation method of the foam metal can realize effective construction and control of a microscopic directional pore structure and uniform distribution and directional arrangement of the nano carbon material in the foam metal skeleton matrix, has simple preparation process, energy conservation and environmental protection, is convenient for batch production, is suitable for various metal material systems, and is easy to popularize.
Drawings
FIG. 1 is a scanning electron micrograph of the nickel foam having a microscopically oriented pore structure prepared in example 1.
Fig. 2 is a scanning electron micrograph of graphene-reinforced nickel foam having a micro-oriented pore structure prepared in example 2, wherein a shows the micro-oriented pore structure of the nickel foam, and b shows graphene in a nickel skeleton.
FIG. 3 is a scanning electron micrograph of the aluminum foam with a microscopically oriented pore structure prepared in example 3.
Fig. 4 is a scanning electron micrograph of graphene-reinforced palladium foam having a micro-oriented pore structure prepared in example 4, wherein a shows the micro-oriented pore structure of the palladium foam, and b shows graphene in the palladium skeleton.
Detailed Description
In the specific implementation process, the foamed metal with the microcosmic oriented pore structure consists of 0-10% (preferably 0.2-5%) of the nano carbon material and the metal by mass percent, and has the microcosmic oriented pore structure, wherein the metal framework and the pores are oriented and arranged in a lamellar form along the freezing direction in the preparation process, the porosity of the foamed metal is 10-90% (preferably 25-80%), and the pore diameter of the foamed metal is 0.3-600 μm (preferably 2-350 μm). The metal is nickel, aluminum, palladium, silver, copper metal simple substance or alloy taking the metal as a matrix, and the nano carbon material is graphene, carbon nano tubes or the combination of the graphene and the carbon nano tubes. The foam metal is prepared by the processes of preparing water-based slurry, freezing and casting, vacuum freezing and drying, removing organic matters and sintering, the obtained foam metal has excellent properties of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like, and the preparation method has the advantages of simple process, low cost, energy conservation, environmental protection and suitability for large-scale production.
The invention will be further elucidated with reference to the following specific examples and the drawing, which are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
in this example, a nickel foam having a micro-oriented pore structure was prepared using raw materials including metallic nickel powder (average particle size 50nm), water, hydroxypropylmethylcellulose powder (average particle size 180 μm), polyvinyl alcohol, sucrose, and polyacrylic acid. The preparation process comprises the following steps:
(A) formulating water-based slurries
Weighing 440g of water, adding the water into a 2L plastic wide-mouth bottle, sequentially adding 2.2g of hydroxypropyl methyl cellulose powder, 80g of metal nickel powder, 4g of sucrose, 4g of polyvinyl alcohol and 2g of polyacrylic acid into the wide-mouth bottle, continuously stirring until slurry is uniformly dispersed, adding 6 zirconia grinding balls with the diameters of 3mm, 6mm and 10mm into the slurry, and dripping 5 drops of defoaming agent (about 0.35mL), wherein the defoaming agent is XPM-120 defoaming agent produced by Nanjing Huaxing defoaming agent Limited company, sealing a bottle cap on the wide-mouth bottle cap, placing the bottle cap on a roller type ball mill for ball milling, and the ball milling speed is 240rpm and the ball milling time is 40 h.
(B) Chill casting
Pouring the uniformly mixed slurry into a rectangular polymethyl methacrylate mould with the inner cavity size of 20mm multiplied by 70mm, sealing the lower end of the mould by a polydimethylsiloxane base with the inclination angle of 25 degrees, placing the mould on a copper plate, connecting the other side of the copper plate with a copper rod with one end immersed in liquid nitrogen, cooling the copper plate to enable water in the slurry to be directionally solidified from bottom to top along the mould at the cooling rate of 10 ℃/min, gradually extruding the metallic nickel powder and the additives in the slurry between ice layers by ice crystals growing along the solidification direction to enable the metallic nickel powder and the additives to be directionally arranged microscopically to form a lamellar structure, and demoulding after the slurry is completely solidified.
(C) Vacuum freeze drying
And placing the demoulded and solidified slurry into a vacuum freeze dryer for vacuum freeze drying treatment to remove water contained in the slurry, setting the temperature of a cold trap at minus 50 ℃, the vacuum degree at 0.5Pa and the processing time at 100h, and taking out the slurry to obtain a porous blank body with a micro-oriented structure, wherein the porous blank body is formed by sheet layers consisting of metal nickel powder and additives, the average spacing of the sheet layers of the blank body is about 40 mu m, and the porosity is about 62%.
(D) Organic matter removal and sintering
Placing the freeze-dried porous blank in a heat treatment furnace, heating the porous blank from room temperature to 550 ℃ at the speed of 3 ℃/min under the condition of argon, preserving heat for 3h, cooling the porous blank to room temperature at the speed of 5 ℃/min so as to remove organic matters contained in the blank, placing the blank without the organic matters in a sintering furnace, heating the blank to 900 ℃ from the room temperature at the speed of 8 ℃/min, heating the blank to 1150 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and cooling the blank to the room temperature at the speed of 5 ℃/min under the vacuum condition, wherein the adoption of the step-type heating and cooling is beneficial to shortening of sintering time, improvement of sintering efficiency and reduction of internal stress.
The foamed nickel with the micro-oriented pore structure can be prepared by the process, and the micro-structure of the foamed nickel is shown in figure 1. As can be seen from FIG. 1, the nickel foam has a skeleton and pores oriented in a lamellar form at a microscopic level in the freezing direction during the preparation process, and has a porosity of 65% and a pore size of 12 μm.
Example 2:
in this example, a graphene-reinforced nickel foam having a micro-oriented pore structure is prepared, and the raw materials used include graphene (diameter 5-10 μm and thickness 3-10 nm), metallic nickel powder (average particle size 50nm), water, sodium dodecyl sulfate, hydroxypropyl methylcellulose (average particle size 180 μm), polyvinyl alcohol, sucrose, and polyacrylic acid. The preparation process comprises the following steps:
(A) formulating water-based slurries
The difference between the step (a) and the step (a) in example 1 is the type and amount of raw materials, specifically: 48g of metal nickel powder, 120g of water, 0.24g of sodium dodecyl sulfate, 0.12g of graphene, 1.8g of hydroxypropyl methyl cellulose, 1.44g of cane sugar, 1.44g of polyvinyl alcohol and 0.72g of polyacrylic acid. The rest of the operation was the same as in step (A) in example 1.
(B) Chill casting
This step was performed in the same manner as in step (B) of example 1.
(C) Vacuum freeze drying
This step was performed in the same manner as in step (C) of example 1.
(D) Organic matter removal and sintering
This step was performed in the same manner as in step (D) in example 1.
The graphene-reinforced foamed nickel with the micro-oriented pore structure can be prepared by the process, and the microstructure of the graphene-reinforced foamed nickel is shown in figure 2. As can be seen from fig. 2, the skeleton and pores of the nickel foam are microscopically arranged in a lamellar manner in an oriented manner along the freezing direction in the preparation process, the porosity of the nickel foam is 72%, the pore diameter of the nickel foam is 15 μm, and graphene is uniformly distributed in the skeleton of the nickel foam and is arranged in a lamellar manner in a skeletal matrix in an oriented manner.
Example 3:
in this embodiment, the foamed aluminum with a micro-oriented pore structure is prepared by using raw materials including graphene (diameter 5-10 μm and thickness 3-10 nm), sheet metal aluminum powder (average sheet diameter 10 μm), water, sodium dodecyl sulfate, polyvinyl alcohol, sucrose and polyacrylic acid. The preparation process comprises the following steps:
(A) formulating water-based slurries
The difference between the step (a) and the step (a) in example 1 is the type and amount of raw materials, specifically: 40g of sheet metal aluminum powder, 200g of water, 0.4g of sodium dodecyl sulfate, 0.336g of graphene, 2g of cane sugar, 2g of polyvinyl alcohol and 0.8g of polyacrylic acid. The rest of the operation was the same as in step (A) in example 1.
(B) Chill casting
This step was performed in the same manner as in step (B) of example 1.
(C) Vacuum freeze drying
This step was performed in the same manner as in step (C) of example 1.
(D) Organic matter removal and sintering
The operation of this step differs from step (D) in example 1 in the sintering process of the green body after removal of organic matter, specifically: under the condition of argon, the temperature is increased from room temperature to 500 ℃ at the speed of 8 ℃/min, then the temperature is increased to 620 ℃ at the speed of 3 ℃/min, the temperature is kept for 2h, and then the temperature is reduced to the room temperature at the speed of 5 ℃/min.
The foamed aluminum with the micro-oriented pore structure can be prepared by the process, and the micro-structure of the foamed aluminum is shown in figure 3. As can be seen from FIG. 3, the skeleton and pores of the foamed aluminum are microscopically arranged in a sheet form oriented in the freezing direction of the preparation process, and the foamed aluminum has a porosity of 54% and a pore size of 8 μm.
Example 4:
in the embodiment, the graphene-reinforced palladium foam with the microscopic oriented pore structure is prepared, and the raw materials include graphene (with a diameter of 5-10 μm and a thickness of 3-10 nm), nano palladium powder (with an average particle size of 100nm), water, sodium dodecyl sulfate, hydroxypropyl methyl cellulose (with an average particle size of 180 μm), polyvinyl alcohol, sucrose and polyacrylic acid. The preparation process comprises the following steps:
(A) formulating water-based slurries
The difference between the step (a) and the step (a) in example 1 is the type and amount of raw materials, specifically: 66.6g of nano palladium powder, 200g of water, 0.4g of sodium dodecyl sulfate, 0.126g of graphene, 3g of hydroxypropyl methyl cellulose powder, 2g of cane sugar, 2g of polyvinyl alcohol and 1g of polyacrylic acid. The rest of the operation was the same as in step (A) in example 1.
(B) Chill casting
This step was performed in the same manner as in step (B) of example 1.
(C) Vacuum freeze drying
This step was performed in the same manner as in step (C) of example 1.
(D) Organic matter removal and sintering
The difference between the step (D) in example 1 and the sintering process of the green body after organic matter removal is as follows: under the vacuum condition, the temperature is increased from the room temperature to 900 ℃ at the speed of 5 ℃/min, then the temperature is increased to 1050 ℃ at the speed of 3 ℃/min, the temperature is kept for 1h, and then the temperature is reduced to the room temperature at the speed of 5 ℃/min.
The foamed palladium reinforced by graphene with a micro-oriented pore structure can be prepared by the process, and the microstructure of the foamed palladium is shown in figure 4. As can be seen from fig. 4, the framework and pores of the palladium foam are microscopically arranged in a lamellar manner in an oriented manner along the freezing direction in the preparation process, the porosity is 52%, the pore diameter is 6 μm, and the graphene is uniformly distributed in the framework of the palladium foam and is arranged in a lamellar manner in the matrix of the framework.
The embodiment result shows that the preparation method can be used for preparing the foam metal with the microcosmic oriented pore structure, realizes the effective construction and control of the microcosmic oriented pore structure and the uniform distribution and oriented arrangement of the nano carbon material in the foam metal skeleton matrix, has simple preparation process, energy conservation and environmental protection, and is suitable for various metal material systems. The foam metal has a micro-oriented pore structure, so that the foam metal has excellent properties of light weight, high specific strength, high energy absorption rate, sound absorption, heat insulation and the like, and has considerable application prospect as a structural function integrated material.
Claims (4)
1. The preparation method of the foam metal with the microcosmic oriented pore structure is characterized in that the foam metal microcosmically has the oriented pore structure, the metal framework and pores are oriented and arranged in a lamellar form along the freezing direction in the preparation process, the porosity of the foam metal is 52-80%, and the pore diameter of the foam metal is 6-350 mu m; the metal framework of the foam metal is reinforced by adding a nano carbon material, wherein in the foam metal, the content of the nano carbon material is 0.2-5% by mass percent, the balance is metal, and the added nano carbon material is preferentially oriented in the metal framework matrix along the arrangement direction of the metal framework;
the preparation method of the foam metal with the micro-oriented pore structure comprises the following steps:
(A) preparing water-based slurry: weighing metal powder, nano carbon material powder, water and an additive, and uniformly mixing to obtain water-based slurry containing the metal powder;
(B) freezing and casting: pouring the water-based slurry into a mold, and directionally freezing to directionally solidify water in the mold along a freezing direction, so that the metal powder, the nano carbon material powder and the additive are extruded among directionally grown ice layers to be directionally arranged on a microscopic scale;
(C) vacuum freeze drying: after demoulding the solidified water-based slurry, carrying out vacuum freeze drying treatment to remove water contained in the water-based slurry, thus obtaining a porous blank with a microcosmic oriented lamellar structure;
(D) organic matter removal and sintering: carrying out high-temperature treatment on the porous green body to remove organic matters contained in the porous green body, and then carrying out high-temperature sintering on the porous green body after the organic matters are removed to obtain the foam metal with a microcosmic directional pore structure;
in the step (A), the mass ratio range of the metal powder, the nano carbon material powder, the additive and the water is 1: (0-0.12): (0.001-0.5): (0.05-10); the additive comprises a dispersant and an organic binder, wherein the dispersant is one or more of sodium dodecyl sulfate, polyacrylic acid, polyethyleneimine, sodium dodecyl benzene sulfonate or Darvan C-N, the addition amount of the dispersant is 2-12% of the mass of the metal powder, the organic binder is one or more of polyvinyl alcohol, polyethylene glycol, sucrose, hydroxypropyl methylcellulose or guar gum, and the addition amount of the organic binder is 2-15% of the mass of deionized water; the mixing process of the water-based slurry is one or any combination of ultrasonic, stirring, vibration and ball milling;
in the step (B), the freezing and casting process comprises the following steps: pouring the uniformly mixed water-based slurry into a polymethyl methacrylate mould, sealing the lower end of the mould by a polydimethylsiloxane base with an inclination angle of 25 degrees, placing the mould on a copper plate, connecting one side of the copper plate with a copper rod with one end immersed in liquid nitrogen, so that water in the water-based slurry is directionally solidified from bottom to top along the mould, and gradually squeezing metal powder, nano carbon material powder and additives in the water-based slurry to ice layers by ice crystals growing along the solidification direction, thereby realizing the microscopic directional arrangement.
2. The method according to claim 1, wherein the metal is nickel, aluminum, palladium, silver, copper, or an alloy based on the above metal, and the nanocarbon material is graphene, carbon nanotubes, or a combination thereof.
3. The method of claim 1, wherein the step (C) comprises the following steps: and (3) demolding the solidified water-based slurry, and placing the water-based slurry in a vacuum environment with the cold trap temperature lower than-30 ℃ and the vacuum degree not more than 10Pa for more than 10 h.
4. The method according to claim 1, wherein in step (D), the porous body is subjected to a high temperature treatment to remove organic substances contained therein: carrying out high-temperature treatment on the porous blank in vacuum or protective atmosphere, wherein the treatment temperature is 350-800 ℃, and the protective atmosphere is one of nitrogen, argon and helium or any mixed gas thereof; the porous blank after organic matter removal is sintered at high temperature and is finished in vacuum, protective atmosphere or reducing atmosphere, wherein the protective atmosphere is one of nitrogen, argon and helium or any mixed gas of the nitrogen, the argon and the helium, and the reducing atmosphere is hydrogen or mixed gas of hydrogen and argon; when the metal is nickel or nickel-based alloy, the sintering temperature is 900-1400 ℃, when the metal is aluminum or aluminum-based alloy, the sintering temperature is 450-650 ℃, when the metal is palladium or palladium-based alloy, the sintering temperature is 1000-1500 ℃, when the metal is silver or silver-based alloy, the sintering temperature is 750-930 ℃, and when the metal is copper or copper-based alloy, the sintering temperature is 700-1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811227307.XA CN109482882B (en) | 2018-10-22 | 2018-10-22 | Foam metal with micro-oriented pore structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811227307.XA CN109482882B (en) | 2018-10-22 | 2018-10-22 | Foam metal with micro-oriented pore structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109482882A CN109482882A (en) | 2019-03-19 |
| CN109482882B true CN109482882B (en) | 2021-05-18 |
Family
ID=65692363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811227307.XA Active CN109482882B (en) | 2018-10-22 | 2018-10-22 | Foam metal with micro-oriented pore structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109482882B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109940162B (en) * | 2019-04-30 | 2020-05-22 | 西安理工大学 | Preparation method of titanium carbide in-situ reinforced titanium and titanium alloy stent |
| CN110385437B (en) * | 2019-07-03 | 2021-09-10 | 西安理工大学 | Preparation method of directional fiber in-situ reinforced titanium and alloy bracket thereof |
| CN110280766B (en) * | 2019-07-23 | 2020-08-04 | 中南大学 | Hierarchical pore structure nickel-based alloy and preparation method and application thereof |
| CN110714140A (en) * | 2019-11-20 | 2020-01-21 | 中南大学 | Nickel or nickel alloy porous material with directional holes, preparation method thereof and application thereof in hydrogen evolution electrode |
| CN114597360B (en) * | 2022-03-02 | 2023-12-08 | 江西省纳米技术研究院 | Composite positive electrode material with array orientation hole structure, preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0771737B2 (en) * | 1988-02-08 | 1995-08-02 | 三菱自動車工業株式会社 | Casting method |
| CN101423380B (en) * | 2008-11-12 | 2011-11-09 | 东南大学 | Method for preparing directional arrangement pore structure porous ceramic |
| CN101785877B (en) * | 2010-04-07 | 2013-02-27 | 华中科技大学 | Method for preparing bionic composite material with lamellar multilevel structure |
| CN101817084B (en) * | 2010-04-29 | 2011-05-04 | 上海交通大学 | Preparation method of micro-nano lamination metal base composite material |
| CN102807391B (en) * | 2012-08-29 | 2013-09-25 | 哈尔滨工业大学 | Method for preparing porous silicon carbide ceramic |
| CN105903969B (en) * | 2016-06-30 | 2018-09-11 | 中南大学 | A kind of porous copper material and preparation method thereof with oriented laminated hole |
| CN108484213B (en) * | 2018-06-14 | 2020-06-30 | 哈尔滨工业大学 | Ceramic metal porous composite material and preparation method thereof |
-
2018
- 2018-10-22 CN CN201811227307.XA patent/CN109482882B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109482882A (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109482882B (en) | Foam metal with micro-oriented pore structure and preparation method thereof | |
| CN108994301B (en) | Metal-based bionic composite material reinforced by nano carbon material and preparation method thereof | |
| Liu et al. | A review of fabrication strategies and applications of porous ceramics prepared by freeze-casting method | |
| Sofie | Fabrication of functionally graded and aligned porosity in thin ceramic substrates with the novel freeze–tape‐casting process | |
| Park et al. | Microstructure and compressive behavior of ice-templated copper foams with directional, lamellar pores | |
| CN105624455B (en) | A kind of porous high-entropy alloy and preparation method thereof | |
| CN108396163B (en) | Preparation method of carbon nano tube reinforced foamed aluminum-based composite material | |
| CN103881278B (en) | The preparation method of a kind of graphene oxide-water-soluble polymers three-dimensional porous nano matrix material | |
| Yu et al. | Study on particle-stabilized Si3N4 ceramic foams | |
| CN112011151B (en) | Preparation method of honeycomb-shaped resin material | |
| CN104945005B (en) | A kind of porous material with centrosymmetric structure and preparation method thereof | |
| CN108994300B (en) | Carbon/metal composite material with micro-oriented structure for electric contact and preparation method thereof | |
| CN105506341B (en) | Mg alloys/Al2O3Composite material and preparation method | |
| CN112553494B (en) | Refrigeration device and method for preparing high-strength and high-toughness layered porous titanium alloy material by using same | |
| CN111995422B (en) | Preparation method of honeycomb ceramic material | |
| CN103924172B (en) | A kind of preparation method of reinforced aluminum matrix composites | |
| CN106435241A (en) | Preparation method for metal-matrix composite enhanced by porous Si3N4/SiC multiphase ceramic | |
| CN108840671A (en) | The preparation method and product of silica heat-barrier material with Multi-scale model | |
| CN106187308A (en) | A kind of porous silicon diatomaceous earth pottery and preparation method thereof | |
| Wang et al. | Porous SiC ceramics fabricated by quick freeze casting and solid state sintering | |
| CN101698605B (en) | Preparation method of gradient porous alumina ceramics | |
| CN101844934A (en) | Preparation method of porous Al2O3 ceramic | |
| Sun et al. | Fabrication and characterization of robust freeze-cast alumina scaffolds with dense ceramic walls and controllable pore sizes | |
| CN111020264B (en) | Three-dimensional accumulation body reinforced titanium-based composite material and preparation method thereof | |
| CN102617182B (en) | Rare earth zirconate porous ceramic with hierarchical pore structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |