CN110983320A - Preparation method of metal material with multi-scale nano-porous - Google Patents
Preparation method of metal material with multi-scale nano-porous Download PDFInfo
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- CN110983320A CN110983320A CN201911175864.6A CN201911175864A CN110983320A CN 110983320 A CN110983320 A CN 110983320A CN 201911175864 A CN201911175864 A CN 201911175864A CN 110983320 A CN110983320 A CN 110983320A
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- 239000007769 metal material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 3
- 229910001369 Brass Inorganic materials 0.000 description 10
- 239000010951 brass Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930003944 flavone Natural products 0.000 description 2
- 150000002212 flavone derivatives Chemical class 0.000 description 2
- 235000011949 flavones Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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Classifications
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a metal material with multi-scale nano-pores, which comprises the following steps: 1) carrying out oxidation treatment on the surface of the metal material to generate an oxide layer on a target surface area to be treated; 2) soaking the metal material with the oxidized surface in a sodium borohydride solution at room temperature; 3) and taking out the soaked metal material, washing the metal material by using alcohol and deionized water in turn for surface seconds, and then drying and storing the metal material to avoid the appearance change. The multi-scale nano porous structure is prepared by carrying out secondary processing on the existing surface on the metal surface, the method of oxidation before reduction is adopted, the requirements on the components of the metal material are low, only the oxidation characteristic of the metal material needs to be considered, and the process simplicity and the wide applicability are greatly improved.
Description
Technical Field
The invention belongs to the field of multi-scale nano-porous metal materials, and particularly relates to a preparation method of a multi-scale nano-porous metal material.
Background
The multi-scale nano porous structure material refers to a material with porous structures with different size orders, from nanometer to submicron to micron. Such structures are widely present in biological matrices, such as silk, charcoal, wood fibers, etc., and are most directly characterized by having particular optical properties. The artificial multi-scale nano porous structure material structure can be used in the fields of catalytic reaction, photocatalysis, energy storage, filtration/separation, drug release and the like.
The fabrication (synthesis) method of multi-scale nanoporous structural materials typically requires multiple steps, each of which produces an order of magnitude structure. The method used at present comprises the following steps: surfactant templating, replication, sol-gel, post-treatment, emulsion templating, phase separation, zeolitization, self-assembly, colloid templating, biomimetic, polymer templating, supercritical fluid, lyophilization, respiratory patterning, and selective extraction (dissolution). Although the synthetic methods are numerous, each is a "start-from-scratch" technique. The surface modification technology which can process the surface of the existing material is lacked. The "phase separation method" and the "selective extraction (dissolution) method" can be used to some extent for surface porous treatment of the existing material, but there are certain requirements (type of component, proportion of component, etc.) for the material components.
In the case of a metal material, the "phase separation method" corresponds to the "dealloying method" and the "ion crystal reduction method", which are techniques for producing a porous metal material by selectively dissolving a part of alloy components. Under certain technological parameters, the multi-scale nano porous structure can be realized through multiple phase separation. Similarly, both the dealloying method and the ion crystal reduction method have a large limitation on the composition of the raw material. Within the knowledge of the pen practitioner, there is no technique that can reprocess an existing surface on a metal surface to produce a multi-scale nanoporous structure.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a metal material with multi-scale nano-porosity.
The invention is realized by the following technical scheme:
the preparation method of the metal material with the multi-scale nano-pores is characterized by comprising the following steps of:
1) carrying out oxidation treatment on the surface of the metal material to generate an oxide layer on a target surface area to be treated;
2) soaking the metal material with the oxidized surface in a sodium borohydride solution at room temperature;
3) and taking out the soaked metal material, washing the metal material by using alcohol and deionized water in turn for surface seconds, and then drying and storing the metal material to avoid the appearance change.
The oxidation treatment in step 1) can adopt any process which causes surface/integral oxidation of the material, such as: high-temperature oxidation, liquid-phase reaction and vacuum plasma furnace.
The concentration of the sodium borohydride solution in the step 2) is 0.1-0.01 mol/L.
The soaking time in the step 2) is not less than 1min, stirring is carried out along with the soaking process, and the stirring speed is less than 500 r/min.
The metal material is copper, aluminum, nickel metal and alloy material.
The multi-scale nano porous structure is prepared by carrying out secondary processing on the existing surface on the metal surface, the method of oxidation before reduction is adopted, the requirements on the components of the metal material are low, only the oxidation characteristic of the metal material needs to be considered, and the process simplicity and the wide applicability are greatly improved.
Drawings
FIG. 1 shows the process of the brass surface from plane to multi-scale nano-porous through treatment;
(a) an original surface; (b) soaking the brass flocculent porous surface for 24 hours at 40 ℃ in 1 MNaOH; (c) 0.1M NaBH4Soaking for 1min to obtain a brass double-layer sheet-porous surface;
fig. 2 is a multi-scale nano-layer sheet-porous surface of brass after reduction;
FIG. 3 is a schematic flow chart of the preparation of the multi-scale nano-porous structure by a reduction method.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings, and specific embodiments are given.
Hair brushA process for preparing the multi-scale nano-porous metallic material includes such steps as oxidizing by high-temp oxidizing, liquid-phase reaction, and vacuum plasma furnace to generate a uniform oxide layer on the surface of metallic specimen to be treated for covering the target surface. The original surface topography of the metal sample can be retained or changed according to the oxidation mode. Then using sodium borohydride (NaBH)4) The water solution reduces the oxide layer on the surface of the porous metal, and then a secondary porous structure with the pore diameter of about 60nm is manufactured on the basis that most of the original oxidized morphology is reserved.
Examples
The brass will be specifically described as an example. And carrying out secondary processing on the basis of the original porous copper, and manufacturing a secondary porous structure on the basis of the original appearance. Compared with other manufacturing methods of multi-scale nano porous materials, the method is suitable for manufacturing the secondary porous structure with the size smaller than 100nm on the metal surface with the original surface structure size not smaller than 100 nm. The specific flow diagram is shown in fig. 3.
The preparation process comprises the following steps: performing surface oxidation treatment on brass as a sample, wherein the original surface of the flavone of the sample is shown in figure 1 (a), and an oxide layer is generated on the target surface area to be treated; the step adopts an oxidant oxidation method for oxidation treatment: placing the brass sample in 1M sodium hydroxide solution (40 ℃), soaking for 24h at room temperature without stirring, taking out and airing to obtain the flocculent porous surface of the flavone, as shown in figure 1 (b), soaking the oxidized brass sample in 0.1 mol/L sodium borohydride solution for 3 min at a stirring speed of less than 500r/min to obtain the two-layer laminar-porous surface of the brass, as shown in figure 1 (c), and the enlarged view of the two-layer laminar-porous surface of the brass is shown in figure 2.
Claims (5)
1. A preparation method of a metal material with multi-scale nano-porosity is characterized by comprising the following steps:
1) carrying out oxidation treatment on the surface of the metal material to generate an oxide layer on a target surface area to be treated;
2) soaking the metal material with the oxidized surface in a sodium borohydride solution at room temperature;
3) taking out the soaked metal material, washing the surface of the metal material by using alcohol and deionized water in turn, and then drying and storing the metal material.
2. The method for preparing a multi-scale porous metal material according to claim 1, wherein the oxidation treatment in step 1) can adopt any process that causes surface/bulk oxidation of the material, such as: high-temperature oxidation, liquid-phase reaction and vacuum plasma furnace.
3. The method for preparing a metal material with multi-scale porosity as claimed in claim 1, wherein the concentration of the sodium borohydride solution in the step 2) is 1-0.01 mol/L.
4. The method for preparing a multi-scale porous metal material according to claim 1, wherein the soaking time in the step 2) is not less than 1min, the soaking process is accompanied by stirring, and the stirring speed is less than 150 r/min.
5. The method according to claim 1, wherein the metal material is selected from the group consisting of copper, aluminum, nickel, and alloys.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911175864.6A CN110983320A (en) | 2019-11-26 | 2019-11-26 | Preparation method of metal material with multi-scale nano-porous |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911175864.6A CN110983320A (en) | 2019-11-26 | 2019-11-26 | Preparation method of metal material with multi-scale nano-porous |
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| CN110983320A true CN110983320A (en) | 2020-04-10 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880516A (en) * | 2006-04-30 | 2006-12-20 | 浙江工业大学 | Template for preparing nano materials and its preparation and application |
| DE102007032938A1 (en) * | 2007-07-14 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Method for the production of nanoscale porous metal or alloys, whose surface is equipped with an oxidation layer, comprises electrochemically oxidation an initial alloy in an oxidating- solution or electrolyte |
| CN105506336A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Method for preparing porous metal through high-temperature oxidation and reduction |
| CN106025302A (en) * | 2016-07-18 | 2016-10-12 | 天津理工大学 | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material |
| CN107904644A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of method for preparing tungsten nano surface porous active layer |
| CN108654531A (en) * | 2017-04-01 | 2018-10-16 | 江苏博恩尼科生物技术有限公司 | A kind of synthesis of artificial cell membrane nano silver coating reaction kettle |
-
2019
- 2019-11-26 CN CN201911175864.6A patent/CN110983320A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880516A (en) * | 2006-04-30 | 2006-12-20 | 浙江工业大学 | Template for preparing nano materials and its preparation and application |
| DE102007032938A1 (en) * | 2007-07-14 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Method for the production of nanoscale porous metal or alloys, whose surface is equipped with an oxidation layer, comprises electrochemically oxidation an initial alloy in an oxidating- solution or electrolyte |
| CN105506336A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Method for preparing porous metal through high-temperature oxidation and reduction |
| CN106025302A (en) * | 2016-07-18 | 2016-10-12 | 天津理工大学 | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material |
| CN108654531A (en) * | 2017-04-01 | 2018-10-16 | 江苏博恩尼科生物技术有限公司 | A kind of synthesis of artificial cell membrane nano silver coating reaction kettle |
| CN107904644A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of method for preparing tungsten nano surface porous active layer |
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