CN103147102A - Conic micro-grade and nano-grade array structure material and its preparation method - Google Patents
Conic micro-grade and nano-grade array structure material and its preparation method Download PDFInfo
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Abstract
The invention relates to a new material and its preparation method, and especially relates to a conic micro-grade and nano-grade array structure material and its preparation method. The conic micro-grade and nano-grade array structure material comprises micro-grade cones and nano-grade cones, the micro-grade cones vertically grow on the surface of a metal substrate, the nano-grade cones grow on the surfaces of micro-grade cones, and the nano-grade cones are arrayed in a radial manner. Compared with the prior art, the preparation method allows the conic dimension of the conic micro-grade and nano-grade array structure material to reach the nanometer scale, has the advantages of simplicity, low cost, no special requirements on the shape and the material of the substrate, and is in favor of the wide application and the large-scale production of the material.
Description
Technical field
The present invention relates to a kind of novel material and preparation method thereof, particularly a kind of pin cone micro-nano twin-stage array structure materials and preparation method thereof.
Background technology
at present, the method for preparing the brilliant array material of pin cone mainly contains photoetching technique (Tan B J Y, Sow C H, Koh T S, etal.Fabrication of size-tunable gold nanoparticles array with nanosphere lithography, reactive ion etching, and thermal annealing[J] .JournM of Physical Chemistry B, 2005, 109 (22): 11100-11109.), template (Cao H, Xu Z, Sang H, et a1.Template synthesis and magnetic behavior of an array of cobalt nanowires encapsulated in polyaniline nanotubules[J] .Advanced Materials, 2001, 13 (2): 121-122.), electron beam, ion beam machining (BaiA, Hu c C.Iron-cobah and iron-cobalt-nickel nanowires deposited by means of cyclic vohammetry and pulse reverse electroplating[J] .Electrochemical Commanications.2003.5 (1): 78-82.) method such as, but this several method technique is comparatively complicated, manufacturing cost is higher, and pin cone size can only reach micro-meter scale.
Summary of the invention
The object of the invention is to provide a kind of pin cone micro-nano twin-stage array structure materials, can only reach micro-meter scale to solve pin cone size of the prior art, and preparation technology is comparatively complicated, the technical matters that manufacturing cost is higher.
The preparation method of the pin cone micro-nano twin-stage array structure materials that another object of the present invention is to provide above-mentioned can only reach micro-meter scale to solve pin cone size of the prior art, and preparation technology is comparatively complicated, the technical matters that manufacturing cost is higher.
The object of the invention is achieved through the following technical solutions:
A kind of pin cone micro-nano twin-stage array structure materials comprises micron order pin cone and nano level pin cone, and described micron order pin cone is grown in metallic substrate surface, and described nano level pin cone is grown on described micron order pin poppet surface.
Preferably, described micron order pin cone vertical-growth is in metallic substrate surface, and described nano level pin cone vertical-growth is on described micron order pin poppet surface, and described nano level pin cone is radial arrangement at described micron order pin poppet surface.
Preferably, the height of described micron order pin cone is 1.0-10.0 μ m, and its base diameter is 0.1-1.0 μ m.
Preferably, the height of described nano level pin cone is 50.0-500.0nm, and its base diameter is 5.0-50nm.
A kind of preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 1 comprises the following steps:
(1) get metal base, described metal base is carried out surface degreasing, pickling, activation treatment;
(2) metal base of processing in step (1) is put into plating tank, as negative electrode, insoluble pole plate is anode with metal base, with wire, anode, negative electrode, electroplating power supply and electroplate liquid is consisted of current circuit;
(3) set the galvanic deposit parameter, namely set electroplating current density and electroplating time, carry out galvanic deposit, prepare micron order pin cone on metal base;
(4) deposit after adjustment galvanic deposit parameter and electroplate liquid parameter, growing nano grade pin cone on described micron order pin cone forms pin cone micro-nano twin-stage array structure materials again.
Preferably, described metal base is selected from the wherein a kind of of copper, aluminium, iron.
Preferably, the deoiling step in described step (1) refers to the treatment process with the greasy dirt organic substance removal of metallic substrate surface adhesion; Acid pickling step refers to treatment process that the oxide skin of metallic substrate surface is removed with acid solution.
Preferably, described step (1) further comprises: with the first electrolytic degreasing 30s-60s of metal base, pickling 15-25s is carried out in the distillation washing afterwards in 8-12% dilute hydrochloric acid, and activation treatment is carried out in the distillation washing afterwards in the 0.15-0.25g/L palladium chloride solution.
Preferably, the electroplate liquid in described step (2) comprises copper sulfate, complexing agent, boric acid and crystallization adjusting agent.
Preferably, described copper sulfate is 0.01-1mol/L, and described complexing agent is 0.1-2mol/L, and described boric acid is 0.1-1.0mol/L, and described crystallization adjusting agent is 1-1000ppm.
Preferably, described complexing agent be selected from fatty acid complexing agent, Sulfonates complexing agent or amino-contained, hydroxy functional group organic complexing agent wherein one or more.
Preferably, described fatty acid complexing agent be selected from Citrate trianion, malate wherein one or more; The organic complexing agent of described amino-contained, hydroxy functional group be selected from edetate, acetate, quadrol wherein one or more.
Preferably, described crystallization adjusting agent is selected from metal ion wherein a kind of of Cu, Ag, Pd, Au, Zn, Sn, Ca, Y, La, Ce, Eu.
Preferably, the temperature 25-60 of described electroplate liquid ℃, pH is 3.5-6.0.
Preferably, the current density in described step (3) is 1-10A/min, and electroplating time is 2-20min.
Preferably, the current density in described step (3) is 1-2A/min, and electroplating time is 5-10min.
Preferably, the adjustment galvanic deposit parameter in described step (4) and electroplate liquid parameter step further comprise: current density is tuned up to 10-20A/min, and electroplating time is reduced to 30s-60s, and concentration of copper sulfate is turned down to 0.01-0.1mol/L.
Compared with prior art, the present invention has following beneficial effect:
1, the pin cone size of pin of the present invention cone micro-nano twin-stage array structure materials can reach nanoscale, and the preparation method is simple, with low cost, and the shape of ground, material without particular requirement, are conducive to widespread use and the large-scale production of this material;
2, pin cone micro-nano twin-stage array structure materials provided by the invention has two-stage structure, and namely compound a kind of nanoscale structures on the micron order array structure, improve its surface-area greatly, thereby have higher surfactivity;
3, novel surface micro-nano twin-stage material of the present invention is due to its unique array structure, huge surface-area, the high surface under nanoscale, determined that it shows excellent functional performance in many aspects, as the field emission characteristic of excellence, remarkable thermal diffusivity, good support of the catalyst, can obtain high bonding strength etc. with other Material cladding the time, have broad application prospects in a lot of fields.
Description of drawings
Fig. 1 is the structural representation of pin cone micro-nano twin-stage array structure materials of the present invention.
Embodiment
Principle of the present invention is: in electrodeposition process, galvanic deposit is not simultaneous at every bit, and there are many instantaneous crystallization active sites in it.Active site is the deposition position of crystal, by adding the crystallization adjusting agent, control the quantity of active site and make electrocrystallization constantly rely on active site at each and extend in plating solution, make crystallization by the direction one-dimensional growth perpendicular to substrate surface, form taper micron pin array structure.Deposit after adjusting galvanic deposit parameter and electroplate liquid parameter again, make crystallization by the direction growth perpendicular to the micron pin, namely the pin cone of growing nano grade on micron-sized pin cone, form micro-nano twin-stage array structure.This material has unique array structure, huge surface-area, the high surface under nanoscale.
Prepare pin cone micro-nano twin-stage array structure materials take copper sheet as metal base, step is as follows.
Oil removing, pickling, activation treatment are carried out in the copper sheet surface of (1) needs being carried out hydrophobic treatment.Be about to the first electrolytic degreasing 60s of copper sheet, pickling 25s is carried out in the distillation washing afterwards in 8% dilute hydrochloric acid, and activation treatment is carried out in the distillation washing afterwards in the 0.15g/L palladium chloride solution.
(2) will be placed in electroplating solution through the good copper sheet of (1) step process, copper sheet is as negative electrode, and copper coin consists of current circuit by wire with copper sheet, copper coin, power supply and electroplate liquid as anode.Electroplate liquid consists of: copper sulfate 0.1mol/L, and citric acid tri-amonia 0.1mol/L, boric acid 0.1mol/L, cupric chloride 1ppm, solution temperature are 60 ℃, pH=6.
(3) adjust the galvanic deposit parameter, making current density is 1A/min, and electroplating time is 20min.
(4) will carry out secondary deposition through the copper sheet that step (3) are handled well, making current density is 10A/min, and copper sulfate is 0.1mol/L, and electroplating time is 60s.
Observe through SEM, electroplate gained pin cone array and have two-stage structure, as shown in Figure 1.Wherein, the height of micron order pin cone 2 is the 5.0-10.0 micron, and its base diameter is the 0.5-1.0 micron, and it is arranged closely perpendicular to copper sheet 1 growth; The height of nano level pin cone 3 is the 100.0-500.0 nanometer, and its base diameter is the 30.0-50.0 nanometer, and it is grown in the micron order pin and bores on 2 surfaces, is radial arrangement.
Prepare pin cone micro-nano twin-stage array structure materials take aluminium flake as metal base, step is as follows.
Oil removing, pickling, activation treatment are carried out in the aluminium flake surface of (1) needs being carried out hydrophobic treatment.Be about to the first electrolytic degreasing 30s of aluminium flake, pickling 15s is carried out in the distillation washing afterwards in 12% dilute hydrochloric acid, and activation treatment is carried out in the distillation washing afterwards in the 0.25g/L palladium chloride solution.
(2) will be placed in electroplating solution through the good aluminium flake of (1) step process, aluminium flake is as negative electrode, and copper coin consists of current circuit by wire with aluminium flake, copper coin, power supply and electroplate liquid as anode.Electroplate liquid consists of: copper sulfate 0.12mol/L, and Trisodium Citrate 2mol/L, boric acid 1mol/L, EDA500ppm, solution temperature are 25 ℃, pH=3.5.
(3) adjust the galvanic deposit parameter, making current density is 9.5A/min, and electroplating time is 2min.
(4) will carry out secondary deposition through the aluminium flake that step (3) are handled well, making current density is 20A/min, and copper sulfate is 0.01mol/L, and electroplating time is 30s.
Observe through SEM, electroplate gained pin cone array and have two-stage structure.Wherein, the height of micron order pin cone is the 1.5-8 micron, and its base diameter is the 0.2-0.8 micron, and it is grown perpendicular to aluminium flake, arranges closely; The height of nano level pin cone is the 60-400 nanometer, and its base diameter is the 8-40 nanometer, and it is grown on micron order pin poppet surface, is radial arrangement.
Embodiment 3
Prepare pin cone micro-nano twin-stage array structure materials take iron plate as metal base, step is as follows.
Oil removing, pickling, activation treatment are carried out in the iron plate surface of (1) needs being carried out hydrophobic treatment.Be about to the first electrolytic degreasing 45s of iron plate, pickling 20s is carried out in the distillation washing afterwards in 10% dilute hydrochloric acid, and activation treatment is carried out in the distillation washing afterwards in the 0.2g/L palladium chloride solution.
(2) will be placed in electroplating solution through the good iron plate of (1) step process, iron plate is as negative electrode, and copper coin consists of current circuit by wire with iron plate, copper coin, power supply and electroplate liquid as anode.Electroplate liquid consists of: copper sulfate 0.5mol/L, and Trisodium Citrate 1mol/L, boric acid 0.5mol/L, EDA1000ppm, solution temperature are 45 ℃, pH=4.7.
(3) adjust the galvanic deposit parameter, making current density is 5A/min, and electroplating time is 10min.
(4) will carry out secondary deposition through the iron plate that step (3) are handled well, making current density is 15A/min, and copper sulfate is 0.08mol/L, and electroplating time is 45s.
Observe through SEM, electroplate gained pin cone array and have two-stage structure.Wherein, the height of micron order pin cone is the 5.0-10.0 micron, and its base diameter is the 0.5-1.0 micron, and it is grown perpendicular to iron plate, arranges closely; The height of nano level pin cone is the 100.0-500.0 nanometer, and its base diameter is the 30.0-50.0 nanometer, and it is grown on micron order pin poppet surface, is radial arrangement.
Above disclosed be only several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of all should drop in the application's protection domain.
Claims (17)
1. a pin cone micro-nano twin-stage array structure materials, is characterized in that, comprise micron order pin cone and nano level pin cone, described micron order pin cone is grown in metallic substrate surface, and described nano level pin cone is grown on described micron order pin poppet surface.
2. pin as claimed in claim 1 is bored micro-nano twin-stage array structure materials, it is characterized in that, described micron order pin cone vertical-growth is in metallic substrate surface, described nano level pin cone vertical-growth is on described micron order pin poppet surface, and described nano level pin cone is radial arrangement at described micron order pin poppet surface.
3. pin cone micro-nano twin-stage array structure materials as claimed in claim 1, is characterized in that, the height of described micron order pin cone is 1.0-10.0 μ m, and its base diameter is 0.1-1.0 μ m.
4. pin cone micro-nano twin-stage array structure materials as claimed in claim 1, is characterized in that, the height of described nano level pin cone is 50.0-500.0nm, and its base diameter is 5.0-50nm.
5. the preparation method of a pin cone micro-nano twin-stage array structure materials as claimed in claim 1, is characterized in that, comprises the following steps:
(1) get metal base, described metal base is carried out surface degreasing, pickling, activation treatment;
(2) metal base of processing in step (1) is put into plating tank, as negative electrode, insoluble pole plate is anode with metal base, with wire, anode, negative electrode, electroplating power supply and electroplate liquid is consisted of current circuit;
(3) set the galvanic deposit parameter, namely set electroplating current density and electroplating time, carry out galvanic deposit, prepare micron order pin cone on metal base;
(4) deposit after adjustment galvanic deposit parameter and electroplate liquid parameter, growing nano grade pin cone on described micron order pin cone forms pin cone micro-nano twin-stage array structure materials again.
6. the preparation method of pin as claimed in claim 5 cone micro-nano twin-stage array structure materials, is characterized in that, described metal base is selected from the wherein a kind of of copper, aluminium, iron.
7. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5, is characterized in that, the deoiling step in described step (1) refers to the treatment process with the greasy dirt organic substance removal of metallic substrate surface adhesion; Acid pickling step refers to treatment process that the oxide skin of metallic substrate surface is removed with acid solution.
8. pin as claimed in claim 5 is bored the preparation method of micro-nano twin-stage array structure materials, it is characterized in that, described step (1) further comprises: with the first electrolytic degreasing 30s-60s of metal base, the distillation washing, carry out afterwards pickling 15-25s in 8-12% dilute hydrochloric acid, activation treatment is carried out in the distillation washing afterwards in the 0.15-0.25g/L palladium chloride solution.
9. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5, is characterized in that, the electroplate liquid in described step (2) comprises copper sulfate, complexing agent, boric acid and crystallization adjusting agent.
10. pin as claimed in claim 9 is bored the preparation method of micro-nano twin-stage array structure materials, it is characterized in that, described copper sulfate is 0.01-1mol/L, and described complexing agent is 0.1-2mol/L, described boric acid is 0.1-1.0mol/L, and described crystallization adjusting agent is 1-1000ppm.
11. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 9, it is characterized in that, described complexing agent be selected from fatty acid complexing agent, Sulfonates complexing agent or amino-contained, hydroxy functional group organic complexing agent wherein one or more.
12. the preparation method of cupric oxide pin as claimed in claim 11 cone micro-nano twin-stage array structure materials is characterized in that, described fatty acid complexing agent be selected from Citrate trianion, malate wherein one or more; The organic complexing agent of described amino-contained, hydroxy functional group be selected from edetate, acetate, quadrol wherein one or more.
13. the preparation method of pin as claimed in claim 9 cone micro-nano twin-stage array structure materials is characterized in that, described crystallization adjusting agent is selected from metal ion wherein a kind of of Cu, Ag, Pd, Au, Zn, Sn, Ca, Y, La, Ce, Eu.
14. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5 is characterized in that the temperature 25-60 of described electroplate liquid ℃, pH is 3.5-6.0.
15. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5 is characterized in that the current density in described step (3) is 1-10A/min, electroplating time is 2-20min.
16. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5 is characterized in that the current density in described step (3) is 1-2A/min, electroplating time is 5-10min.
17. the preparation method of pin cone micro-nano twin-stage array structure materials as claimed in claim 5, it is characterized in that, adjustment galvanic deposit parameter in described step (4) and electroplate liquid parameter step further comprise: current density is tuned up to 10-20A/min, electroplating time is reduced to 30s-60s, and concentration of copper sulfate is turned down to 0.01-0.1mol/L.
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| CN103603020A (en) * | 2013-10-17 | 2014-02-26 | 上海交通大学 | Method for preparing micro-nano needle conical structure for copper interconnection by electrochemical deposition |
| CN103603015A (en) * | 2013-10-17 | 2014-02-26 | 上海交通大学 | Electrochemistry preparation method for micro-nano conical needle structure for copper interconnection |
| CN103668367A (en) * | 2013-12-06 | 2014-03-26 | 宁波微极电子科技有限公司 | Manufacture method for micro-nano-structure array radiating fin |
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| CN109722683A (en) * | 2019-01-04 | 2019-05-07 | 中国科学院合肥物质科学研究院 | Gold nano structure and its preparation method and application with cone spiked surface |
| CN110117802A (en) * | 2019-05-06 | 2019-08-13 | 浙江大学 | A kind of preparation method of multistage three-dimensional microstructures |
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| CN103668367A (en) * | 2013-12-06 | 2014-03-26 | 宁波微极电子科技有限公司 | Manufacture method for micro-nano-structure array radiating fin |
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| CN108346633A (en) * | 2017-11-08 | 2018-07-31 | 中电普瑞电力工程有限公司 | A kind of micro-nano structure array heat-delivery surface and preparation method thereof |
| CN109722683A (en) * | 2019-01-04 | 2019-05-07 | 中国科学院合肥物质科学研究院 | Gold nano structure and its preparation method and application with cone spiked surface |
| CN110117802A (en) * | 2019-05-06 | 2019-08-13 | 浙江大学 | A kind of preparation method of multistage three-dimensional microstructures |
| CN110777403A (en) * | 2019-08-08 | 2020-02-11 | 安徽德诠新材料科技有限公司 | Preparation method of foam metal coating with high specific surface area for heat dissipation |
| CN110777403B (en) * | 2019-08-08 | 2021-05-25 | 安徽德诠新材料科技有限公司 | Preparation method of foam metal coating with high specific surface area for heat dissipation |
| CN115354368A (en) * | 2022-07-07 | 2022-11-18 | 广东工业大学 | Fractional distribution microstructure and preparation method and application thereof |
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