CN110000375B - Ultrahigh-porosity porous metal material and preparation method thereof - Google Patents
Ultrahigh-porosity porous metal material and preparation method thereof Download PDFInfo
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B22—CASTING; POWDER METALLURGY
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- 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
- B22F3/1134—Inorganic fillers
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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- 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
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- 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
Abstract
The invention provides a porous metal material with ultrahigh porosity and a preparation method thereof, belonging to the technical field of porous metal material preparation. The invention uses SiO2After the sensitization treatment of the microsphere powder, chemical plating is carried out on the powder, and SiO is carried out2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2Microsphere powder; the composite SiO2Sintering the microsphere powder, soaking the sintered molding material in HF solution, and drying to obtain the ultrahigh-porosity porous metal material; the porosity of the ultrahigh-porosity porous metal material is more than or equal to 98 percent. The invention can be applied to SiO2The control of the processes of microsphere powder, chemical plating and sintering conveniently obtains the ultrahigh-porosity porous metal material with porosity of more than or equal to 98 percent, different macroscopic appearances and excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of porous metal material preparation, in particular to a porous metal material with ultrahigh porosity and a preparation method thereof.
Background
The porous metal material is a low-density metal material with a microstructure like a sponge, generally consists of continuous or separated pores and continuous metal ligaments, and the pore diameter and ligament size of the porous metal material are generally required to be different from the macroscopic size of the material by more than two orders of magnitude. The porous metal material is widely applied to the fields of catalysis, batteries, trace detection, electromagnetic shielding, noise reduction, national defense research and the like.
Common preparation methods for porous metal materials include melt foaming, pore-forming, dealloying, powder metallurgy, template methods, and the like, but these methods generally cannot prepare bulk porous metals with porosity greater than 90%. With the rise of 3D printing technology, porous metal with porosity of more than 98% can be obtained by taking 3D printing organic matter framework material as a sacrificial template and combining with coating technologies such as chemical deposition, electrochemical deposition, atomic layer deposition and the like. However, at present, 3D printing technology cannot obtain porous materials with a cross-scale structure, wherein the pore diameter is less than 10 microns, and the macroscopic bulk size is in the centimeter level.
Disclosure of Invention
In view of the above, the present invention aims to provide a porous metal material with ultrahigh porosity and a preparation method thereof. The preparation method provided by the invention can conveniently obtain the ultrahigh-porosity porous metal material with the porosity of more than or equal to 98 percent, the pore diameter of less than or equal to 10 mu m, different macroscopic appearances and excellent mechanical properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous metal material with ultrahigh porosity, which comprises the following steps:
(1) mixing SiO2Sensitizing the microsphere powder in a sensitizing solution to obtain sensitized SiO2Microsphere powder;
(2) the sensitized SiO2The microsphere powder is chemically plated in chemical plating solution to form SiO2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2Microsphere powder;
(3) the composite SiO2Sintering the microsphere powder to obtain a molding material;
(4) soaking the molding material in HF solution and drying to obtain the ultrahigh-porosity porous metal material; the porosity of the ultrahigh-porosity porous metal material is more than or equal to 98 percent.
Preferably, SiO in the step (1)2The diameter of the microsphere powder is less than or equal to 10 μm.
Preferably, the sensitizing solution in the step (1) is SnCl2A hydrochloric acid solution; the SnCl2Hydrochloric acid solution prepared from SnCl2·2H2O, deionized water and hydrochloric acid, the SnCl2·2H2The dosage ratio of O, deionized water and hydrochloric acid is 2-10 g: 50-100 mL: 20-80 mL, and the mass concentration of the hydrochloric acid is 30-35%.
Preferably, the time of the sensitization treatment in the step (1) is 1-10 h.
Preferably, the material of the metal layer in the step (2) is gold, silver, copper, iron or nickel; the thickness of the metal layer is 100-200 nm.
Preferably, the time of the chemical plating in the step (2) is 1-10 h.
Preferably, the sintering in the step (3) is spark plasma sintering, the temperature of the spark plasma sintering is 300-500 ℃, the pressure is 20-40 KN, and the time is 60-120 s.
Preferably, the mass concentration of the HF solution in the step (4) is 10-30%, and the soaking time is 10-24 h.
Preferably, the drying in the step (4) is carbon dioxide supercritical drying.
The invention provides the ultrahigh-porosity porous metal material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a porous metal material with ultrahigh porosity, which comprises the following steps: mixing SiO2After the sensitization treatment of the microsphere powder, chemical plating is carried out on the powder, and SiO is carried out2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2Microsphere powder; the composite SiO2Sintering the microsphere powder, soaking the sintered molding material in HF solution, and drying to obtain the ultrahigh-porosity porous metal material; the porosity of the ultrahigh-porosity porous metal material is more than or equal to 98 percent. Book (I)The invention can be realized by the reaction of SiO2The control of the processes of microsphere powder, chemical plating and sintering can conveniently obtain the ultrahigh-porosity porous metal material with the porosity of more than or equal to 98 percent, the pore diameter of less than or equal to 10 mu m, different macroscopic appearances and excellent mechanical properties.
Drawings
FIG. 1 is a microstructure diagram of the ultrahigh-porosity porous gold material prepared in example 1.
Detailed Description
The invention provides a preparation method of a porous metal material with ultrahigh porosity, which comprises the following steps:
(1) mixing SiO2Sensitizing the microsphere powder to obtain sensitized SiO2Microsphere powder;
(2) the sensitized SiO2Chemical plating of the microsphere powder on SiO2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2Microsphere powder;
(3) the composite SiO2Sintering the microsphere powder to obtain a molding material;
(4) soaking the molding material in HF solution and drying to obtain the ultrahigh-porosity porous metal material; the porosity of the ultrahigh-porosity porous metal material is more than or equal to 98 percent.
The invention uses SiO2Sensitizing the microsphere powder to obtain sensitized SiO2And (3) microsphere powder. In the present invention, the SiO2The diameter of the microsphere powder is preferably less than or equal to 10 mu m. The invention can adjust SiO2The diameter of the microsphere powder is convenient to adjust the aperture of the ultrahigh-porosity porous metal material, so that the porous metal material with the aperture not more than 10 mu m is obtained. The invention is directed to the SiO2The source of the microsphere powder has no special requirement, and corresponding commercial products can be selected according to the pore diameter requirement.
In the present invention, the sensitizing solution for sensitization is preferably SnCl2A hydrochloric acid solution; the SnCl2The hydrochloric acid solution is preferably composed of SnCl2·2H2O, deionized water and hydrochloric acid, the SnCl2·2H2The dosage ratio of O, deionized water and hydrochloric acid is preferably2-10 g: 50-100 mL: 20-80 mL, more preferably 6-8 g: 60-80 ml: 50-60 ml, and the mass concentration of the hydrochloric acid is preferably 30-35%, and more preferably 35%. The invention is to the SnCl2·2H2The sources of O, deionized water and hydrochloric acid are not particularly required, and corresponding products sold on the market can be adopted. In the present invention, the sensitizing solution preferably further comprises tin particles; the diameter of the tin particles is preferably 3mm, and the using amount of the tin particles is preferably 2-5. The invention preferably prevents bivalent tin ions in the sensitizing solution from being oxidized into tetravalent tin ions by adding tin particles into the sensitizing solution, thereby influencing the sensitizing effect.
In the present invention, the time for the sensitization treatment is preferably 1 to 10 hours, and more preferably 2 to 8 hours. The SiO is preferably used in the invention2Dispersing the microsphere powder in a sensitizing solution, and carrying out sensitization treatment under the stirring condition; the stirring is preferably magnetic stirring; the rotating speed of the stirring is preferably 400-800 r/min, and more preferably 500-600 r/min; the invention has no special requirement on the stirring time, so that SiO2And uniformly dispersing the microsphere powder in the sensitizing solution. The invention is prepared on SiO by sensitization treatment2And forming a tin ion attachment layer on the surface of the microsphere powder to serve as an active point of chemical plating.
After sensitization, the invention preferably makes the sensitized SiO2Washing the microsphere powder with deionized water, wherein the washing is preferably carried out by adopting a centrifugal method; the invention has no special requirement on the cleaning times and ensures that the sensitized SiO2And cleaning the microsphere powder.
After the cleaning is finished, the invention enables the obtained sensitized SiO2Chemical plating of the microsphere powder on SiO2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2And (3) microsphere powder. In the invention, the material of the metal layer is preferably gold, silver, copper, iron or nickel; the thickness of the metal layer is preferably 100 to 200nm, and more preferably 120 to 180 nm.
In the present invention, when the material of the metal layer is gold, the composition of the electroless plating solution for electroless plating preferably includes the following components:
150-300 mL of deionized water;
0.2-0.8 g of hydroxylamine hydrochloride;
1-2 mL of chloroauric acid solution;
the concentration of the chloroauric acid solution is preferably 0.4 mol/L;
the electroless plating solution and SiO2The preferable dosage ratio of the microsphere powder is 300-500 mL: 1g of the total weight of the composition.
The invention preferably adds the deionized water into the sensitized SiO2And sequentially adding the hydroxylamine hydrochloride and the chloroauric acid solution into the microsphere powder for chemical plating. The invention takes hydroxylamine hydrochloride as a reducing agent to reduce chloroauric acid into metal gold which is deposited on sensitized SiO2And forming a compact gold plating layer on the surface of the microsphere powder.
In the present invention, when the material of the metal layer is silver, the composition of the electroless plating solution for electroless plating preferably includes the following components:
the electroless plating solution and SiO2The preferable dosage of the microsphere powder is 300-500 mL: 1g of the total weight of the composition.
According to the invention, preferably, the silver nitrate is added into ammonia water and part of deionized water to form silver ammonia solution, and then the rest deionized water is added into sensitized SiO2And sequentially adding the silver ammonia solution and glucose into the microsphere powder for chemical plating. The invention takes glucose as a reducing agent to reduce silver nitrate into metallic silver to be deposited on sensitized SiO2And forming a compact silver plating layer on the surface of the microsphere powder.
In the present invention, the material of the metal layer may also be copper, iron or nickel. When the material of the metal layer is copper, iron or nickel, the invention has no special requirement on the corresponding chemical plating solution for chemical plating, and the corresponding chemical plating solution which is well known in the field can be adopted.
In the invention, the time of the chemical plating is preferably 1-10 h, and more preferably 2 h. In the present invention, the electroless plating is performed for the time of each of the electroless plating solutionsAnd starting calculation after the addition of the components is finished. In the present invention, the electroless plating is preferably performed under stirring conditions; the stirring is preferably magnetic stirring; the rotating speed of the stirring is preferably 400-800 r/min. The invention can adjust the SiO in the chemical plating process by adjusting the addition amount of the metal compound in the chemical plating solution and the chemical plating time2The thickness of the metal layer formed on the surface of the microsphere further conveniently adjusts the porosity of the ultrahigh-porosity porous metal material.
After the chemical plating is finished, the invention preferably selects the composite SiO2And cleaning and drying the microsphere powder in sequence. In the invention, the cleaning is preferably centrifugal cleaning by using deionized water; the invention has no special requirement on the cleaning times, and ensures that the composite SiO is used2And cleaning the microsphere powder. In the invention, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 10-24 h.
After the drying is finished, the invention obtains the composite SiO2Sintering the microsphere powder to obtain the molding material. In the invention, the sintering is preferably spark plasma sintering, the temperature of the spark plasma sintering is preferably 300-500 ℃, more preferably 350-450 ℃, the pressure is preferably 20-40 KN, more preferably 25-35 KN, and the time is preferably 60-120 s, more preferably 80-100 s. The invention adopts spark plasma sintering to improve the mechanical properties of the porous metal material, such as strength, toughness and the like.
The invention preferably prepares the compound SiO2And sintering the microsphere powder in a mould. According to the invention, porous metal block materials with different macroscopic appearances can be conveniently obtained by designing different shapes of the inner cavity of the die, for example, when the inner cavity of the die is cylindrical, a cylindrical porous metal block can be obtained by sintering; meanwhile, as the sintering is dry powder sintering, the design of the appearance of the die has more freedom, and the special-shaped porous metal block material can be conveniently obtained according to the requirement.
After sintering, soaking the molding material in HF solution and drying to obtain the porous metal material with ultrahigh porosity; pores of the ultra-high porosity porous metal materialThe rate is more than or equal to 98 percent. In the invention, the mass concentration of the HF solution is preferably 10-30%, more preferably 15-25%, and the soaking time is preferably 10-24 h, more preferably 15-20 h. The invention removes SiO by soaking the molding material in HF solution2And (5) carrying out microsphere preparation to obtain the ultrahigh-porosity porous metal material with the open pore structure. After the soaking is completed, the invention preferably removes SiO2Cleaning the molding material of the microspheres; the cleaning is preferably performed by using deionized water, the cleaning frequency is not particularly required, and the HF solution remained on the surfaces of the microspheres can be cleaned.
In the present invention, the drying is preferably carbon dioxide supercritical drying; the carbon dioxide supercritical drying is preferably carried out in an acetone solution. The apparatus for supercritical carbon dioxide drying according to the present invention is not particularly required, and apparatuses known in the art may be used. The invention avoids the problems of large surface tension of water or other solvents, damage to the skeleton of the porous structure and volume contraction of the porous structure in the common drying process by supercritical drying of carbon dioxide.
The invention also provides the ultrahigh-porosity porous metal material prepared by the preparation method in the technical scheme. The porosity of the ultrahigh-porosity porous metal material is more than or equal to 98%, the pore diameter is less than or equal to 10 mu m, the ultrahigh-porosity porous metal material can have different macroscopic appearances, and the mechanical property is excellent.
The ultra-high porosity porous metal material and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Taking SiO with the diameter of 1000nm20.5g of microsphere powder in SnCl containing tin particles2Sensitizing treatment is carried out for 10h in hydrochloric acid solution. SnCl2·2H2The amount of O was 7.8g, the amount of deionized water was 75mL, the amount of 35% concentrated hydrochloric acid was 40mL, and 3 tin particles having a diameter of about 3mm were used. Magnetic stirring is kept during the sensitization process, the rotating speed is 600r/min, so that SiO is generated2The microsphere powder is uniformly dispersed in the solution.
(2) Sensitized SiO2And centrifugally cleaning the microsphere powder by using deionized water, and performing surface gold plating treatment. The sensitized SiO was diluted with 240mL of deionized water2The microspheres were pulverized, and 0.6g of hydroxylamine hydrochloride was added to the microspheres, followed by 1mL of a 0.4mol/L chloroauric acid solution. And reacting for 2 hours under the condition of magnetic stirring at 600r/min to finish the gold plating operation.
(3) SiO after gold plating2And centrifugally cleaning the microsphere powder by using deionized water, and drying to remove water to obtain the composite microsphere powder coated with a gold layer with the thickness of about 100 nm.
(4) Weighing 0.15g of the dried composite powder, placing into a stainless steel mold with an inner cavity diameter of 3mm, and performing discharge plasma sintering at 300 deg.C under 40KN for 60s to obtain the final product with SiO2A cylindrical block of microspheres.
(5) Placing the sintered block into HF solution with the concentration of 30%, soaking for 24 hours, and removing SiO2And (3) microspheres. And cleaning with deionized water, and performing supercritical drying with carbon dioxide in acetone solution to obtain the porous gold bulk material with ultrahigh porosity.
The microstructure of the obtained ultrahigh-porosity porous gold material is shown in figure 1, and the ultrahigh-porosity porous gold material is formed by stacking gold spherical shells with the inner diameter of about 1000nm and the thickness of about 100nm, and the pore diameter of the ultrahigh-porosity porous gold material is about the outer diameter of the spherical shells. As is evident from fig. 1, the outer diameter of the spherical shell is about 1200 nm. Porosity was measured by weighing and measuring volume, combined with the theoretical density of gold (19.3 g/cc). In this example, the porous metal block had a diameter of 3mm, a height of 5mm and a weight of 0.013 g; the density was 0.368g/cc and the porosity was 98.1%.
The mechanical property of the obtained ultrahigh-porosity porous gold material is characterized by a compressive stress-strain test. At normal temperature, a 4mm diameter indenter was pressed against a 3mm diameter, 5mm height cylindrical porous gold sample. The compression speed is 0.5mm/min, and the compression strength is 3.2 MPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a porous metal material with ultrahigh porosity is characterized by comprising the following steps:
(1) mixing SiO2Sensitizing the microsphere powder to obtain sensitized SiO2Microsphere powder; the SiO2The diameter of the microsphere powder is less than or equal to 10 mu m;
(2) the sensitized SiO2Chemical plating of the microsphere powder on SiO2Forming a metal layer on the surface of the microsphere to obtain the composite SiO2Microsphere powder; the thickness of the metal layer is 100-200 nm;
(3) the composite SiO2Sintering the microsphere powder to obtain a molding material; the sintering is discharge plasma sintering, the temperature of the discharge plasma sintering is 300-500 ℃, the pressure is 20-40 KN, and the time is 60-120 s;
(4) soaking the molding material in HF solution and drying to obtain the ultrahigh-porosity porous metal material; the porosity of the ultrahigh-porosity porous metal material is more than or equal to 98 percent.
2. The method according to claim 1, wherein the sensitizing solution used in the sensitization in the step (1) is SnCl2A hydrochloric acid solution; the SnCl2Hydrochloric acid solution prepared from SnCl2·2H2O, deionized water and hydrochloric acid, the SnCl2·2H2The dosage ratio of O, deionized water and hydrochloric acid is 2-10 g: 50-100 mL: 20-80 mL, and the mass concentration of the hydrochloric acid is 30-35%.
3. The method according to claim 1, wherein the time for the sensitization treatment in the step (1) is 1 to 10 hours.
4. The method according to claim 1, wherein the metal layer in step (2) is made of gold, silver, copper, iron or nickel.
5. The preparation method according to claim 1, wherein the electroless plating time in the step (2) is 1-10 h.
6. The preparation method according to claim 1, wherein the HF solution in the step (4) has a mass concentration of 10-30%, and the soaking time is 10-24 h.
7. The production method according to claim 1, wherein the drying in the step (4) is carbon dioxide supercritical drying.
8. The ultrahigh-porosity porous metal material prepared by the preparation method of any one of claims 1 to 7.
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