CN106620836B - Preparation method of hierarchical porous metal - Google Patents
Preparation method of hierarchical porous metal Download PDFInfo
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- CN106620836B CN106620836B CN201510508455.9A CN201510508455A CN106620836B CN 106620836 B CN106620836 B CN 106620836B CN 201510508455 A CN201510508455 A CN 201510508455A CN 106620836 B CN106620836 B CN 106620836B
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Abstract
The invention discloses a preparation method of hierarchical porous metal, which comprises the following steps: selecting polystyrene spheres with the same or equivalent particle size to the minimum primary pore diameter of the to-be-prepared hierarchical pore metal, assembling the polystyrene spheres to form a colloid template in three-dimensional ordered arrangement, introducing a metal nanocrystalline solution into the three-dimensional colloid template prepared from the polystyrene spheres, and drying and crushing the metal nanocrystalline solution into particles with the particle size 8-40 times of the average value of the minimum primary pore diameter of the to-be-prepared hierarchical pore metal; preparing the particles into slurry, and uniformly soaking the slurry on an organic high polymer material bracket with a superior hole larger than the smallest primary hole of the to-be-prepared hierarchical hole metal; sintering in vacuum or protective atmosphere, and performing conventional subsequent treatment according to the metal material process to obtain the hierarchical porous metal. The method can effectively control the aperture size, the arrangement and the connectivity of the holes, the prepared material has good connectivity, all levels of holes are respectively interconnected, all levels of holes are also interconnected, the holes can be used as various materials such as biological materials, filtering materials and the like, various functional requirements can be met, and the preparation method is simple and convenient and is easy to realize.
Description
Technical Field
The invention relates to a porous metal, in particular to a preparation method of a hierarchical porous metal.
Background
The porous metal is a novel functional composite material, and due to the porous structure and the metal material, the porous metal has various excellent performances of light weight, air permeability, sound absorption, heat insulation, vibration reduction, no combustion, no pollution, high specific strength, reusability, easy recovery and the like, becomes a material without substitution under some special conditions, has a very wide application range, and comprises a plurality of aspects of light structural materials, sound absorption materials, filtering materials, building decoration materials, heat exchange materials, biomedical materials and the like. The traditional method for preparing porous metal at present mainly comprises a powder metallurgy method, a fiber sintering method, a melt foaming method, a melt blowing method, a seepage casting method, a metal deposition method, a hollow ball sintering method, a self-propagating high-temperature synthesis method, a foam impregnation method and the like; taking a foam impregnation method as an example, a preparation method of a medical metal implant material porous tantalum disclosed in patent CN 102451911B is as follows: preparing tantalum powder slurry by using a solution prepared by using starch as an organic binder and water as a dispersing agent and tantalum powder, pouring the tantalum powder slurry into an organic foam, dipping until pores of the organic foam are filled with the tantalum powder slurry, drying to remove the dispersing agent in the organic foam, removing the organic binder and the organic foam by degreasing treatment under the protection of inert gas, sintering under vacuum to prepare a porous sintered body, and annealing under vacuum and performing conventional post-treatment to prepare the porous tantalum. The main defects of the methods are that the prepared material has a single pore structure, the pore size and the connectivity are difficult to accurately control, the single pore structure causes the material not to meet the requirements of various functions, and the pore size and the connectivity are difficult to accurately control, so that the material cannot fully and accurately complete the required functions.
In recent decades, a new material, a hierarchical porous material, in porous materials has been paid attention to in a large number of fields, such as biotechnology, biomedicine, catalysis, energy, optics, separation and the like, due to its unique properties, and its preparation and application have become a very active leading-edge research field in the world. In the preparation method, the research on the nonmetal hierarchical porous material is more, the preparation of the metal hierarchical porous material is more difficult, and the research is less.
The Wangjun introduced the preparation of porous niobium biomaterials by organic foam impregnation in its academic paper "preparation of porous niobium biomaterials by foam impregnation and their properties". Firstly, preparing a polyvinyl alcohol solution, preparing a porous niobium blank by using polyurethane organic foam as a template, and then sintering the porous niobium blank, wherein although a researcher does not intend to make a multi-level pore material, the researcher claims to obtain porous niobium with two types of pores, the first type of pores are 300-type pores and 500 mu m, the pores are communicated with each other, and a large number of micropores are formed in the wall of the first type of pores, but the pore diameter of the porous material obtained by the preparation method is uncontrollable, and the arrangement and the connectivity of the pores are also uncontrollable.
The invention content is as follows:
the invention aims to provide an effective and controllable preparation method of hierarchical pore metal with a hierarchical pore structure.
The inventor believes that if the metal material with the next level hole is prepared first and then is used as the cavity wall to form the previous level hole, the metal material with the two levels of holes can be prepared, and the like, the metal material with more than two levels of holes can be prepared.
The purpose of the invention is realized by the following technical scheme:
a preparation method of multilevel pore metal comprises the following steps:
(1) material preparation
Selecting polystyrene spheres with the same or equivalent particle size to the smallest primary pore diameter of the multi-level pore metal to be prepared, and assembling the polystyrene spheres to form a three-dimensional orderly-arranged colloid template; preparing a metal nanocrystalline solution, introducing the metal nanocrystalline solution into a three-dimensional colloid template prepared from polystyrene spheres, drying the mixture of the three-dimensional colloid template and the metal nanocrystalline solution, and then crushing the mixture into particles with the particle size 8-40 times of the average value of the minimum primary pore diameter of the multi-level pore metal to be prepared;
(2) preparing the particles into slurry, and uniformly soaking the slurry on an organic high polymer material bracket with a superior hole larger than the minimum primary hole of the to-be-prepared multilevel hole metal;
(3) sintering the organic high polymer material support in vacuum or protective atmosphere, and then carrying out conventional subsequent treatment according to the raw material metal material process used by the multilevel pore metal to be prepared to prepare the multilevel pore metal.
After sintering, the polystyrene spheres and the organic polymer material bracket volatilize to form two-stage holes with different pore sizes.
Further, if the particles prepared in the step (1) of the above preparation method are uniformly mixed with a pore-forming agent for preparing pores one-step larger than the smallest one-step pore of the multi-step pore metal to be prepared before impregnation to prepare a slurry, and then the slurry is uniformly impregnated on an organic polymer material support having pores two-step larger than the smallest one-step pore of the multi-step pore metal to be prepared, so that the multi-step pore metal material having three-step pores can be prepared after sintering. By analogy, porous materials with more hierarchical pores can be prepared.
More specifically, according to the method for preparing the hierarchical porous metal, the pores serving as the polymer material scaffold are three-dimensionally through-connected, so that the pores for preparing the hierarchical porous metal are also three-dimensionally through-connected.
More specifically, in the preparation method of the hierarchical porous metal, the metal can be one or more of tantalum, niobium, titanium alloy, stainless steel, cobalt-based alloy, nickel alloy, copper and copper alloy.
More specifically, in the preparation method of the hierarchical porous metal, the pore-forming agent can be one or more of urea, ammonium sulfate, ammonium chloride, methyl cellulose, sodium bicarbonate, ethyl cellulose, ammonium bicarbonate, sodium carbonate, starch or flour.
The invention has the beneficial effects that:
(1) the invention provides a method for effectively preparing multi-level pore metal with more than two levels, which comprises the steps of taking polystyrene spheres with the same or equivalent particle size to the minimum first-level pore diameter of the multi-level pore metal to be prepared, assembling the polystyrene spheres to form a colloid template in three-dimensional ordered arrangement, introducing a prepared metal nanocrystalline solution into the three-dimensional colloid template prepared from the polystyrene spheres, drying and crushing the polystyrene spheres into particles with the particle size 8-40 times of the average value of the minimum first-level pore diameter of the multi-level pore metal to be prepared, preparing the particles into slurry, uniformly soaking the slurry on the wall of an organic polymer material support pore with a higher-level pore larger than the minimum first-level pore diameter of the multi-level pore metal to be prepared, volatilizing the organic polymer material support after sintering to form a first-level pore, volatilizing the polystyrene spheres in the particles on the wall of the first-level pore cavity to form the minimum first-level pore. If the particles obtained by crushing are uniformly mixed with the pore-forming agent for preparing the pores which are larger than the minimum primary pore of the multi-level pore metal to be prepared to prepare slurry before impregnation, and then the slurry is uniformly impregnated on the organic polymer material support with the pores which are larger than the minimum primary pore of the multi-level pore metal to be prepared to a secondary size, after sintering, the organic polymer material, the pore-forming agent and polystyrene spheres volatilize to form a three-level pore structure, namely, a secondary pore formed by the pore-forming agent is arranged on the wall of the maximum primary pore formed by volatilization of the organic polymer material support, a tertiary pore formed by polystyrene is arranged on the wall of the secondary pore, the pores of all levels are graded, and the pore sizes and the pore arrangement of all levels are effectively controlled by controlling the material, the processing sequence and the parameters.
(2) The preparation method of the multilevel pore metal provided by the invention can realize three-dimensional through of pores, including three-dimensional through of each level of pores and three-dimensional through of each level of pores. The colloid templates which are arranged in a three-dimensional ordered manner ensure the interpenetration of the smallest primary hole, the three-dimensional communicated high polymer material support ensures the interpenetration of the large primary hole formed by the high polymer material support, and the crushed particles are arranged on the wall of the large primary hole formed by the organic high polymer material support, so that the smallest primary hole is interpenetrated with the large primary hole formed by the organic high polymer material support; when the pore-forming agent is adopted, the particles obtained by crushing are uniformly mixed with the pore-forming agent for preparing the pores which are one-level larger than the minimum one-level pore of the multi-level pore metal to be prepared, the mixture is prepared into slurry, the slurry is uniformly impregnated on the organic polymer material bracket with the pores which are two-level larger than the minimum one-level pore of the multi-level pore metal to be prepared, and substances used for preparing the slurry are volatilized, so that the second-level pores (middle-level pores) formed by the pore-forming agent are mutually communicated, and the second-level pores are mutually communicated with the macropores formed by the organic polymer material bracket.
(3) The polystyrene spheres with uniform sizes are selected and assembled to form a three-dimensional orderly-arranged colloid template, so that the uniformity of the smallest primary holes can be ensured, the uniformity of the large primary holes can be ensured by controlling the uniformity and sintering parameters of the organic polymer material support holes, and the uniformity of the middle primary holes can be ensured by controlling the size uniformity of the pore-forming agent and uniformly mixing the pore-forming agent with the crushed particles.
(4) The preparation method of the hierarchical pore metal provided by the invention is simple and convenient, is easy to realize, and is easy to adjust and control parameters.
Drawings
The invention will be further elucidated with reference to the embodiments and drawings.
FIG. 1 is a flow chart of the preparation method of the present invention;
FIG. 2 is a schematic view of a porous metal prepared according to the present invention;
fig. 3 is an enlarged view of a portion of fig. 2.
Detailed Description
The following description will be made in conjunction with the accompanying drawings, which are provided to explain the embodiments of the present invention in detail and to explain the detailed embodiments and the specific operation procedures based on the technical solutions of the present invention, but the scope of the present invention is not limited to the following embodiments.
As shown in fig. 1, the figure shows a preparation flow of multilevel pore metal: firstly, preparing materials, selecting polystyrene spheres with the same particle size as or more properly equal to or basically equal to the size of the smallest primary pore of the multi-level pore metal to be prepared, assembling the polystyrene spheres to form a three-dimensional orderly arranged colloid template, introducing the prepared metal nanocrystalline solution into the three-dimensional colloid template prepared from the polystyrene spheres, drying and crushing the metal nanocrystalline solution into particles with the particle size 8-40 times of the average value of the smallest primary pore of the multi-level pore metal to be prepared; preparing the particles into slurry, and uniformly soaking the slurry on an organic high polymer material bracket with a superior hole larger than the smallest primary hole of the to-be-prepared hierarchical hole metal; sintering in vacuum or protective atmosphere, and performing conventional subsequent treatment according to the metal material process of the raw material adopted by the multilevel pore metal to be prepared to prepare the multilevel pore metal.
As shown in fig. 2 and fig. 3, fig. 2 shows a hierarchical porous metal material structure, which is a two-level porous material, 1 is a large pore, 2 is a cavity wall of the large pore, and 3 is a small pore on the wall 2 of the large pore, as shown in fig. 3, the small pore 3 is communicated with other small pores through a channel 4, and 5 is a cavity wall of the small pore 3, and it can be seen from the figure that the large pore 1 and the small pore 3 are also communicated with each other.
Examples of the invention are given in detail below:
example 1:
in this embodiment, porous titanium with secondary pores is prepared by the following steps:
(1) material preparation
Selecting polystyrene pellets with the particle size of 300nm-400nm, assembling the polystyrene pellets to form a colloid template which is arranged in a three-dimensional order, preparing a titanium nanocrystalline solution, introducing the titanium nanocrystalline solution into the three-dimensional colloid template made of the polystyrene pellets, drying the mixture of the three-dimensional colloid template/the titanium nanocrystalline solution, and then crushing the mixture into particles with the particle size of 8 mu m-10 mu m;
(2) mixing polyvinyl alcohol and distilled water according to the weight ratio of 1: 19, heating, dissolving the polyvinyl alcohol, mixing the particles with a mixed solution of the polyvinyl alcohol and distilled water according to a weight ratio of 2: 5 preparing slurry, and uniformly dipping the slurry on polyurethane foam with the aperture of 280-360 mu m;
(3) sintering the soaked polyurethane foam in vacuum or protective atmosphere, and then carrying out conventional subsequent treatment according to a titanium process to obtain porous titanium with two-stage pores, wherein the mutually communicated macropores are 240-320 mu m, the walls of the macropores are provided with mutually communicated 260-350 nm pores, the two-stage pores are also mutually communicated, and the total porosity is 76%.
The particle size of the crushed particles is 22-33 times of the average value of the pore diameter of the smallest primary pore.
Such materials may be used in bone implants.
Example 2:
in the embodiment, porous nickel with secondary pores is prepared, the preparation method is similar to that of the embodiment 1, wherein the particle size of the polystyrene pellets is 1.2-1.5 μm, the pore size of the polyurethane foam is 180-260 μm, and the crushed particles and the mixed solution of polyvinyl alcohol and distilled water are mixed according to the weight ratio of 1: 5, preparing slurry and impregnating again to prepare porous nickel with two-stage holes, wherein the interpenetrated macropores of the porous nickel are 130-200 mu m, the wall of each macropore is provided with interpenetrated small holes of 900-1100 nm, the two-stage holes are also interpenetrated, and the total porosity is 65%.
The particle size of the crushed particles is 8-10 times of the average value of the pore diameter of the smallest primary pore.
The material can be used for filter materials.
Example 3:
in this embodiment, porous tantalum having three-level pores is prepared by the following steps:
(1) material preparation
Selecting polystyrene pellets with the particle size of 200nm-300nm, assembling the polystyrene pellets to form a colloid template which is arranged in a three-dimensional order, preparing a tantalum nanocrystalline solution, introducing the tantalum nanocrystalline solution into the three-dimensional colloid template made of the polystyrene pellets, drying the three-dimensional colloid template/tantalum nanocrystalline solution mixture, and then crushing the mixture into particles with the particle size of 5 mu m-8 mu m;
(2) taking starch with the particle size of 200nm-300nm, and mixing the starch with the starch according to the weight ratio of 1: 40, mixing the particles with distilled water to prepare a starch solution, and mixing the particles, the methylcellulose with the particle size of 30-60 mu m and the starch solution according to a weight ratio of 13: 1: 8, preparing slurry, and uniformly dipping the slurry on polyester foam with the pore size of 230-450 mu m;
(3) sintering the soaked polyester foam in vacuum or protective atmosphere, and then carrying out conventional subsequent treatment according to a tantalum process to obtain porous tantalum with three-level holes, wherein the mutually communicated large holes are 200-400 mu m, the walls of the large holes are provided with mutually communicated secondary holes of 25-50 mu m, the walls of the secondary holes are provided with mutually communicated tertiary holes of 170-260 nm, all levels of holes are also communicated with each other, and the total porosity is 82%.
The particle size of the crushed particles is 23-37 times of the average value of the pore diameter of the smallest primary pore.
The porous tantalum can be used as a bone regeneration material, and the size of the first-level pore is particularly suitable for meeting the requirements of the ingrowth of living tissues such as blood vessels and the like; the second level of pores is particularly suitable for the colonisation of a wide variety of cells; the third-level hole is particularly favorable for meeting the requirements of cell adhesion and differentiation due to a large number of nano holes, has a large specific surface area, can load a large number of growth factors, has good hole penetration performance, can fully meet the infiltration and transmission of blood and tissue fluid and realize the discharge of protein degradation products and metabolic products, and is a real bone regeneration material.
Example 4:
in this embodiment, a porous niobium having three-level pores is prepared by the following steps:
(1) material preparation
Selecting polystyrene pellets with the particle size of 400nm-500nm, assembling the polystyrene pellets to form a colloid template which is arranged in a three-dimensional order, preparing a niobium nanocrystalline solution, introducing the niobium nanocrystalline solution into the three-dimensional colloid template made of the polystyrene pellets, drying the mixture of the three-dimensional colloid template/niobium nanocrystalline solution, and then crushing the mixture into particles with the particle size of 10 mu m-16 mu m;
(2) taking starch with the grain diameter of 400nm-500nm, and mixing the starch with the starch according to the weight ratio of 1: 40, mixing the particles with distilled water to prepare a starch solution, and mixing the particles, ammonium chloride with the particle size of 50-80 mu m and the starch solution according to the weight ratio of 6: 1: 4, preparing slurry, and uniformly dipping the slurry on polyester foam with the aperture of 330-580 mu m;
(3) sintering the soaked polyester foam in vacuum or protective atmosphere, and then carrying out conventional subsequent treatment according to a niobium process to obtain porous niobium with three-level holes, wherein the mutually communicated large holes are 300-530 mu m, the walls of the large holes are provided with mutually communicated second-level holes of 45-80 mu m, the walls of the second-level holes are provided with mutually communicated third-level holes of 360-440 nm, all the levels of the holes are also communicated with each other, and the total porosity is 85%.
The particle size of the crushed particles is 25-40 times of the average value of the pore diameter of the smallest primary pore.
This material can be used for bone regeneration material with similar advantages as example 4.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the structure of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of multilevel pore metal is characterized by comprising the following steps:
(1) material preparation
Selecting polystyrene spheres with the same or equivalent particle size to the smallest primary pore diameter of the multi-level pore metal to be prepared, and assembling the polystyrene spheres to form a three-dimensional orderly-arranged colloid template; preparing a metal nanocrystalline solution, introducing the metal nanocrystalline solution into a three-dimensional colloid template prepared from polystyrene spheres, drying the mixture of the three-dimensional colloid template and the metal nanocrystalline solution, and then crushing the mixture into particles with the particle size 8-40 times of the average value of the minimum primary pore diameter of the multi-level pore metal to be prepared;
(2) preparing the particles into slurry, and uniformly soaking the slurry on an organic high polymer material bracket with a superior hole larger than the minimum primary hole of the to-be-prepared multilevel hole metal;
(3) sintering the organic high polymer material bracket in vacuum or protective atmosphere, and then carrying out conventional subsequent treatment according to the metal material process of the multilevel pore metal to be prepared to prepare the multilevel pore metal.
2. The method of preparing a hierarchical pore metal of claim 1, wherein: and (2) before impregnation, uniformly mixing the particles prepared in the step (1) with a pore-forming agent for preparing pores which are one-level larger than the smallest one-level pores of the to-be-prepared multi-level pore metal to prepare slurry, and uniformly impregnating the slurry on an organic polymer material support with pores which are two-level larger than the smallest one-level pores of the to-be-prepared multi-level pore metal.
3. The method for preparing a hierarchical pore metal according to claim 1 or 2, wherein: the holes of the high polymer material bracket are three-dimensionally communicated.
4. The method for preparing a hierarchical pore metal according to claim 1 or 2, wherein: the metal is one or more of tantalum, niobium, titanium alloy, stainless steel, cobalt-based alloy, nickel alloy, copper or copper alloy.
5. The method of preparing a hierarchical pore metal of claim 3, wherein: the metal is one or more of tantalum, niobium, titanium alloy, stainless steel, cobalt-based alloy, nickel alloy, copper and copper or alloy.
6. The method of preparing a hierarchical pore metal of claim 2, wherein: the pore-forming agent is one or more of urea, ammonium sulfate, ammonium chloride, methyl cellulose, sodium bicarbonate, ethyl cellulose, ammonium bicarbonate, sodium carbonate, starch or flour.
7. The method of preparing a hierarchical pore metal of claim 2, wherein: the pore-forming agent is one or more of urea, ammonium sulfate, ammonium chloride, methyl cellulose, sodium bicarbonate, ethyl cellulose, ammonium bicarbonate, sodium carbonate, starch or flour, and the pores of the high polymer material support are three-dimensionally communicated.
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| CN100359030C (en) * | 2003-07-28 | 2008-01-02 | 南京大学 | Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process |
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