CN102191489B - Method for preparing metal material with biomorphic fine hierarchical structural morphology - Google Patents
Method for preparing metal material with biomorphic fine hierarchical structural morphology Download PDFInfo
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Abstract
The invention discloses a method for preparing a metal material with biomorphic fine hierarchical structural morphology, and belongs to the technical field of nanometer materials. Wings of an organism are taken as a template, and the metal material with a biomorphic fine hierarchical structure is prepared by the following steps of: performing amination treatment in solution of ethylenediamine, activating by adopting solution of chloroauric acid, neutralizing by using sodium borohydride, cleaning, dipping into chemical plating solution for chemical plating, and dripping phosphoric acid into the template. The prepared metal material with a micro/nano structure inherits and copies a multi-scale hierarchical fine structure of a natural organism; and the preparation process is simple and flexible, and is low in cost.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is a kind of metallic substance preparation method with biological fine hiberarchy form.
Background technology
Metallic substance with micro nano structure has caused concern widely in nanotechnology and porous material scientific domain in recent years.Excellent properties such as the high thermal conductivity that metallic substance has, high conductivity, anticorrosive, antifatigue, optically-coupled; Thereby make it at light;; Magnetic, scientific domains such as heat and catalysis have important use, detect like surface enhanced Raman scattering and are bringing into play important effect in scientific domains such as environment, medical biotechnology, Materials science.The surface effects that metallic substance showed and the dimensional effect of micro nano structure make it at aspects such as electronics, optics, microfluid and micromechanics great application prospect arranged in addition.For example: metallic substance has negative dielectric coefficient, and based on this characteristic, scientists observes the negative refraction under the optical frequencies in two dimension or metallic pattern array structure.This negative refractive index material will demonstrate and the complete different light transmission properties of traditional positive refraction material, can promote brand-new photoelectricity sciemtifec and technical sphere, like stealth material and technology.Utilize the characteristic of metallic pattern array structure surface plasmons in addition; Can obtain effects such as light converges, light distribution, optical waveguides, light enhancing; Promoted the development of integrated scientific and technological basis of light and applied research greatly; Like surface raman enhancement, senser element, nanophotonics, LHM, sub-wavelength optics, and other some applied technical fields.
In recent years; General using electron beam, DUV and multiple beam coherence technique; Be aided with reactive ion beam etching (RIBE) technology simultaneously; Perhaps utilize artificial template---self assembling process prepares the metallic substance with micro nano structure, like " the solution method preparation of metal photonic crystal " of one Chinese patent application numbers 200910078572.0 records, this technology mainly through successively in substrate spin coating photoresist material, interference lithography method prepare one dimension or two-dimensional nano optical grating construction; Through spin coating metal nanoparticle colloidal sol and subzero treatment, obtain metal photonic crystal.Yet these technical matters are complicated, cost an arm and a leg, and are simple in structure and single, are difficult to satisfy the demand of modern high technology development.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of metallic substance preparation method with biological fine hiberarchy form is provided; Make metallic substance succession with micro-nano structure and multiple dimensioned classification fine structure and preparation technology's simple and flexible of having duplicated the natural biological body, with low cost.
The present invention realizes through following technical scheme; The present invention passes through biological wing as template; Through ethylenediamine solution carry out amination handle the back adopt chlorauric acid solution carry out activation and with in the Peng Qinghuana with clean; Immerse then and carry out electroless plating in the chemical plating fluid, in template, splash into phosphoric acid at last, obtain the metallic substance of biomorph fine hiberarchy.
Described biological wing is meant: soak 1-5h through the acid solution demineralization of 8-20wt% at normal temperatures, clean with zero(ppm) water then, place the wing of butterfly, dragonfly Yan or the moth class of air drying.
Described acid solution is that concentration is the hydrochloric acid (HCl) of 8-20wt%, the sulfuric acid (H that concentration is 8-20wt%
2SO
4) or concentration be the nitric acid (HNO of 8-20wt%
3) in one or more.
The concentration of described ethylenediamine solution is 5-50wt%.
Described amination is handled and is meant: in ethylenediamine solution, soaked 6-24 hour, use alcohol wash, drying then.
Described chlorauric acid solution is meant: concentration is the HAuCl of 0.1-1wt%
4The aqueous solution.
Described activation is meant: in chlorauric acid solution, soaking 2-6 hour, use alcohol wash then.
Described Peng Qinghuana is meant: concentration is the NaBH of 1-5wt%
4The aqueous solution.
Described neutralization is cleaned and is meant: adopt Peng Qinghuana to soak 2-10 minute, use washed with de-ionized water then, drying.
The described phosphoric acid that splashes into is meant: the template after the electroless plating is placed on the clean silicon chip, remove template after splashing into phosphoric acid then and leaving standstill 72-80h, and then clean with zero(ppm) water, again dried in vacuum.
The present invention relates to the metallic substance that method for preparing obtains with biological fine hiberarchy form; Its component/content/physical chemistry structure/condition is: the fine hiberarchy that has kept the primeval life template. the organic molecule that phosphoric acid solution can the degradation biological template; Under suitable temperature, can prepare hollow metallic substance; Relative primeval life template; Its shrinking percentage is in about 6-14% scope; Through the concrete processing parameter and plating time, plating bath solubility, temperature etc. of regulating electroless plating, can further control the thickness of metal deposition layer, so the multiple dimensioned classification fine structure metallic substance that can controlled preparation has different biomorph structures.
It is template that there is the biology with fine hiberarchy in the present invention in a large number with nature; Utilize electroless plating technology to realize the preparation of the metallic substance of fine hiberarchy, created a kind of fast, simple, cheap, effectively prepare the novel method of fine hiberarchy metallic substance.Prepared metallic substance has been inherited the fine structure characteristic of primeval life template, is with a wide range of applications in fields such as photoelectron, photochemical catalysis, magnetic properties.
Description of drawings
Fig. 1 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal A g material of biomorph hierarchy among the embodiment 1;
Fig. 2 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal A u material of biomorph hierarchy among the embodiment 2;
Fig. 3 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal Cu material of biomorph hierarchy among the embodiment 3;
Fig. 4 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal Ni material of biomorph hierarchy among the embodiment 4;
Fig. 5 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal Co material of biomorph hierarchy among the embodiment 5;
Fig. 6 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal Pd material of biomorph hierarchy among the embodiment 6;
Fig. 7 is sem (SEM) figure and the ability spectrogram (EDS) that has the metal Pt material of biomorph hierarchy among the embodiment 7.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into chemical plating liquid and carried out electroless plating 20-30 minute, chemical plating liquid is by the 1g Silver Nitrate, 2mL ammoniacal liquor, and the 5g rocchelle's salt, the 100mL deionized water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 1).
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into chemical gold plating liquid and carried out electroless plating 10-20 minute, chemical gold plating liquid is by the 1g hydrochloro-auric acid, 0.5g sodium-chlor, and 1.125g tartrate, 15g sodium hydroxide, 150mL water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 2).
Embodiment 3
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into chemical bronze plating liquid and carried out electroless plating 10-20 minute, Electroless Cu Plating liquid is by 1.5g copper sulfate, 2g sodium hydroxide, and the 7g sodium-potassium tartrate, the 50mL deionized water, 5mL formaldehyde (37%) is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 3).
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into chemical nickel-plating liquid and carried out electroless plating 20-30 minute, chemical nickel-plating liquid is by the 4g single nickel salt, the 2g trisodium citrate, and 1g lactic acid, 0.2g dimethylin borane 100mL deionized water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 4).
Embodiment 5
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into electroless cobalt plating liquid and carried out electroless plating 20-30 minute, electroless cobalt plating liquid is by the 2.5g rose vitriol, the 2.5g Soduxin, and 0.4g dimethylin borane, the 100mL deionized water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 5).
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the aqueous solution 5 minutes, cleaning-drying.Further put into chemical palladium plating solution and carried out electroless plating 20-30 minute, chemical palladium plating solution is by the 0.5g Palladous chloride, 10g EDTA Disodium sodium, and 50mL ammoniacal liquor, the 1.5mL Hydrazine Hydrate 80, the 250mL deionized water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 6).
Embodiment 7
Choosing natural special-shaped purple plague purpura butterfly is template, and 2 hours after drying of dipping in 10% rare nitric acid utilize 15% ethylenediamine solution that its dipping after 2 hours, is put into 0.5%HAuCl
4The aqueous solution 4 hours, alcohol wash is put into 2%NaBH subsequently
4In the s aqueous solution 5 minutes, cleaning-drying.Further put into chemically plating platinum liquid and carried out electroless plating 120-180 minute, chemically plating platinum liquid is by the 0.2g Platinic chloride, the 3.2g oxammonium hydrochloride, and 24mL ammoniacal liquor, the 60mL deionized water is formed.The butterfly wing that further will metallize takes out single scale and is positioned on the clean silicon chip under opticmicroscope; On scale, drip phosphoric acid then; Soaked 72 hours, and used washed with de-ionized water again, obtain having the metallic substance of biomophic fine hiberarchy after the dried in vacuum.(see figure 7).
Claims (9)
1. metallic substance preparation method with biological fine hiberarchy form; It is characterized in that; Through with biological wing as template, through ethylenediamine solution carry out amination handle the back adopt chlorauric acid solution carry out activation and with in the Peng Qinghuana with clean, immerse then and carry out electroless plating in the chemical plating fluid; In template, splash into phosphoric acid at last, obtain the metallic substance of biomorph fine hiberarchy;
Described biological wing is meant: soak 1-5h through the acid solution demineralization of 8-20wt% at normal temperatures, clean with zero(ppm) water then, place the wing of butterfly, dragonfly or the moth class of air drying.
2. the metallic substance preparation method with biological fine hiberarchy form according to claim 1; It is characterized in that; Described acid solution is that concentration is the hydrochloric acid of 8-20wt%, and concentration is one or more in the sulfuric acid of 8-20wt% or the nitric acid that concentration is 8-20wt%.
3. the metallic substance preparation method with biological fine hiberarchy form according to claim 1 is characterized in that, described amination is handled and is meant: in ethylenediamine solution, soaked 6-24 hour, use alcohol wash, drying then.
4. according to claim 1 or 3 described metallic substance preparing methods, it is characterized in that the concentration of described ethylenediamine solution is 5-50wt% with biological fine hiberarchy form.
5. the metallic substance preparation method with biological fine hiberarchy form according to claim 1 is characterized in that described activation is meant: in chlorauric acid solution, soaking 2-6 hour, use alcohol wash then.
6. according to claim 1 or 5 described metallic substance preparing methods with biological fine hiberarchy form, it is characterized in that described chlorauric acid solution is meant: concentration is the HAuCl of 0.1-1wt%
4The aqueous solution.
7. the metallic substance preparation method with biological fine hiberarchy form according to claim 1 is characterized in that, described neutralization is cleaned and is meant: adopt Peng Qinghuana to soak 2-10 minute, use washed with de-ionized water then, drying.
8. according to claim 1 or 7 described metallic substance preparing methods with biological fine hiberarchy form, it is characterized in that described Peng Qinghuana is meant: concentration is the NaBH of 1-5wt%
4The aqueous solution.
9. the metallic substance preparation method with biological fine hiberarchy form according to claim 1; It is characterized in that; The described phosphoric acid that splashes into is meant: the template after the electroless plating is placed on the clean silicon chip; Remove template after splashing into phosphoric acid then and leaving standstill 72-80h, and then clean, again dried in vacuum with zero(ppm) water.
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| CN102384904A (en) * | 2011-10-10 | 2012-03-21 | 上海交通大学 | Metal surface enhanced Raman scattering substrate with three-dimensional period structure and preparation method thereof |
| CN102717613B (en) * | 2012-03-31 | 2016-06-01 | 上海交通大学 | There is the preparation method of material of butterfly wing microstructure, seal and Embosser |
| CN103567457B (en) * | 2013-10-11 | 2015-07-08 | 上海交通大学 | Nano-particle system and preparation system and application of nano-particle system |
| CN106282982B (en) * | 2016-08-26 | 2018-11-20 | 上海交通大学 | A method of preparing three-dimensional order micro-nano hierarchical structure noble metal composite-material |
| CN108914150B (en) * | 2018-06-11 | 2020-01-10 | 江苏科技大学 | Preparation method of ultrathin Ni-P composite electrode material with ordered micro-nano-pore array structure |
| CN109972093B (en) * | 2019-03-22 | 2021-06-15 | 中车工业研究院有限公司 | High polymer bionic configuration photothermal conversion material and preparation method and application thereof |
| CN110369707B (en) * | 2019-06-13 | 2020-07-14 | 上海交通大学 | Preparation method of nanoparticle superstructure material with butterfly wing micro-nano configuration |
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| CN100402200C (en) * | 2005-11-21 | 2008-07-16 | 谢广文 | Method for preparing nano metal pipe by template chemical plating process |
| CN101664675B (en) * | 2009-09-04 | 2013-03-20 | 上海交通大学 | Preparation method of photocatalysis materials of biomorphic fine hiberarchy |
| CN102021622A (en) * | 2010-12-09 | 2011-04-20 | 北京航空航天大学 | Method and device for plating cladding magnetic material on microorganism surface |
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| 李小丽,谢广文.化学镀蜘蛛丝模板法制备金属微管.< * |
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