CN101603176B - Preparation method of surface metal base nano array ball distributing structure - Google Patents
Preparation method of surface metal base nano array ball distributing structure Download PDFInfo
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- CN101603176B CN101603176B CN200910054908XA CN200910054908A CN101603176B CN 101603176 B CN101603176 B CN 101603176B CN 200910054908X A CN200910054908X A CN 200910054908XA CN 200910054908 A CN200910054908 A CN 200910054908A CN 101603176 B CN101603176 B CN 101603176B
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Abstract
The invention relates to a preparation method of a surface metal base nano array ball distributing structure, belonging to the technical field of nano materials. The preparation method comprises the following steps: carrying out surface degreasing treatment, surface derusting treatment and acid pickling treatment to the metal base material in sequence; implementing plating to the metal base material; carrying out chemical plating to the metal base material; then obtaining the surface metal base nano array ball distributing structure. In the process of electro-deposition of the invention, the preparation method controls the quantity of active points by adding a crystal adjusting agent, leads the electrocrystallization to extend in the plating solution by being dependent on the active points at any time, leads crystal to grow in the direction vertical to the surface of the metal base material, namely one-dimensional longitudinal direction and forms a micronano needle-shaped crystal distributing structure. Then a chemical plating method is utilized, a reducing agent and a buffering agent are added so as to grow nano balls with a similar scale on the nano needle. The largest advantages of the method lies in no need of using any template, no need of any complex equipment and no special requirements for material and shape of the base material, thus being suitable for industrial batch production.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of nano material, specifically is a kind of preparation method of surface metal base nano array ball distributing structure.
Background technology
This nanometer array structure is meant that metal or nonmetallic surface have the complex ordered array structure of micro-nano-scale, has vertical acicular structure in the bottom, is ball-like structure on the top of pin, i.e. long ball on the pin.Because this structure real surface is long-pending big, has high reaction activity, its Chinese checkers formula structure can produce many new characteristics, so range of application is very wide.For example: (1) microelectronics Packaging field, utilize its special construction, the bonding strength of framework and plastic packaging interlaminar resin is strengthened greatly.(2) can be used for metal and metal, the matrix material between metal and the pottery.(3) the surface-area increase makes it have good light scattering characteristic and absorption characteristic, can be used as optical material, laser camouflage material, optical-thermal conversion material.(4) nanometer ball is made the material of special construction as mould (plate).(5) can produce lotus leaf effect, excellent hydrophobic property can be used as hydrophobic material.At present, mostly micro-nano array structure is to study from device angles, and stock size is mostly between micron and millimeter.About the preparation method mainly is mould (plate) method and LIGA (soft X-ray deep layer photoetching electrotyping process technology) method.Find through retrieval prior art, Ma Di etc. are at " AAO original mold method electric deposition nickel nano wire characterizes and electrochemical behavior research " (functional materials, 1001-9731 (2004) supplementary issue-2836-03) mention template in the literary composition, specifically be as template with porous oxide film, electrodeposit metals particulate on template then, thereby prepare nano-array, more a kind of method that template is dissolved away by chemical process.In addition, Wu Guangfeng etc. are in " LIGA technology basis and development trend thereof " (electromechanical engineering technology, 1009-9492 (2007) 12-0089-04) mentions the LIGA method in, promptly adopt photoetching plate-making, electrotyping forming, go complex steps such as template to carry out the microstructure method for processing.But all there is complex process in two kinds of prior aries, and efficient is low, the cost height, and facility investment is big, and substrate sizes and shape are had shortcomings such as strict demand.Therefore, only be applicable to micro element manufacturing or research purpose.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of surface metal base nano array ball distributing structure is provided, utilize the electrochemical deposition principle, the conductive metal base material is placed the electroplating solution that contains crystallization adjustment agent as negative electrode, and apply curtage, make electrocrystallization by perpendicular to the vertical one-dimensional growth of the direction on surface, form the nano-array of similar acicular structure then in the metallic surface.Again metal base is placed chemical plating solution, then deposition one deck globular crystal structure on nano-array.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step, choose suitable metal base, metal base is carried out successively surface degreasing is handled, surface derusting is handled and cleanup acid treatment.
Described surface degreasing is handled and is meant: the adherent greasy dirt organic substance of metallic substrate surface is removed.
Described surface derusting is handled and is meant: the zone of oxidation inorganic substance of metallic substrate surface are removed.
Described cleanup acid treatment is meant metal base is soaked in having corrosive solution.
Second step, metal base is put into plating tank as negative electrode, nickel tinsel or insoluble pole plate be as anode, and with lead anode, negative electrode, electroplating power supply and electroplate liquid series connection are constituted the loop, by electroplating power supply metal base implemented to electroplate then.
The component of described electroplate liquid and concentration are: agent 1-1000PPM, the solution temperature 25-60 of this electroplate liquid ℃, pH3.5-6.0 are adjusted in metal ion 0.1-2.5mol/L, complexing agent 0.1-2mol/L, boric acid 0.5mol/L and crystallization.
Described metal ion is meant: a kind of or its combination in nickel, copper, iron or the aluminium.
Described complexing agent is meant: a kind of or its combination in Citrate trianion, malate, edetate, acetate, the quadrol.
Agent is adjusted in described crystallization, is made of Cu, Ag, Pd, Au, Zn, Sn, Ca and Y, La, Ce, Eu rare earth ion.
Described enforcement is electroplated and is direct current electrode position, monopulse plating or the plating of two pulse electric current.
The 3rd step, the metal base after will electroplating are put into the coating bath 2min that another contains chemical plating fluid, carry out making surface metal base nano array ball distributing structure after the electroless plating.
The component of described chemical plating fluid and concentration are: metal refining ion 0.1-2.5mol/L, reductive agent 0.1-2.5mol/L, trisodium citrate 0.1-2.5mol/L and the sodium acetate 0.1-2.5mol/L of metal and alloy thereof, 5 ℃-150 ℃ of the solution temperatures of this chemical plating fluid, pH3.5-6.0.
Described metal ion is meant: a kind of or its combination in nickel, copper, iron or the aluminium.
Described reductive agent is meant sodium dihydrogen phosphite.
The present invention is in electrodeposition process, adjust agent by adding crystallization, control the quantity of active site and make electrocrystallization constantly all rely on active site and in plating bath, extend, make crystallization, form micro-nano needle crystal array structure by direction one dimension longitudinal growth perpendicular to metallic substrate surface at each.Utilize chemical plating method afterwards, add reductive agent and buffer reagent, make the nanometer ball that grows close yardstick on the nanoneedle.This method biggest advantage is need not need not complex apparatus by any masterplate, and ground shape material is not had particular requirement, is suitable for industrialized mass production.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) oil removing, rust cleaning and cleanup acid treatment are carried out in the copper sheet surface of needs being carried out hydrophobic treatment.
(2) will place electroplating solution through the good metal base of (1) step process, metal base is as negative electrode, and the nickel plate is as anode, by lead both and power supply, electroplate liquid constituted the loop.Electroplate liquid consists of: nickelous chloride 0.1mol/L, and citric acid tri-amonia 0.1mol/L, boric acid 0.5mol/L, agent cupric chloride 1ppm, 60 ℃ of solution temperatures, pH6 are adjusted in crystallization.
(3) adjust current density 1A/min, electroplate 20min.
(4) will place chemical plating solution through the good metal base of (3) step process, solution composition is: six hydration nickel sulfate 0.1mol/L, sodium dihydrogen phosphite 0.1mol/L, trisodium citrate 0.1mol/L, sodium acetate 0.2mol/L, 60 ℃ of solution temperatures, pH7.5, time 2min.
Result: observe nanometer plating pin height 0.05-0.4 micron, base diameter 0.05-0.2 micron, nanometer ball diameter 0.05-0.2 micron through SEM.
Embodiment 2
(1) oil removing, rust cleaning and cleanup acid treatment are carried out in the copper sheet surface of needs being carried out hydrophobic treatment.
(2) will place electroplating solution through the good metal base of (1) step process, metal base is as negative electrode, and the nickel plate is as anode, by lead both and power supply, electroplate liquid constituted the loop.Electroplate liquid consists of: nickelous chloride 2.5mol/L, and citric acid tri-amonia 2mol/L, boric acid 0.5mol/L, agent cupric chloride 1000ppm, 25 ℃ of solution temperatures, Ph3.5 are adjusted in crystallization.
(3) adjust current density 1A/min, electroplate 20min.
(4) will place chemical plating solution through the good metal base of (3) step process, solution composition is: six hydration nickel sulfate 0.5mol/L, sodium dihydrogen phosphite 0.5mol/L, trisodium citrate 0.5mol/L, sodium acetate 1.5mol/L, 80 ℃ of solution temperatures, pH8, time 2min.
Result: observe nanometer plating pin height 0.05-0.4 micron, base diameter 0.05-0.2 micron, nanometer ball diameter 0.05-0.2 micron through SEM.
Embodiment 3
(1) oil removing, rust cleaning and cleanup acid treatment are carried out in the copper sheet surface of needs being carried out hydrophobic treatment.
(2) will place electroplating solution through the good metal base of (1) step process, metal base is as negative electrode, and the nickel plate is as anode, by lead both and power supply, electroplate liquid constituted the loop.Electroplate liquid consists of: nickelous chloride 1.3mol/L, and citric acid tri-amonia 1mol/L, boric acid 0.5mol/L, agent cupric chloride 500ppm, 40 ℃ of solution temperatures, pH4 are adjusted in crystallization.
(3) adjust current density 1A/min, electroplate 20min.
(4) will place chemical plating solution through the good metal base of (3) step process, solution composition is: six hydration nickel sulfate 2.5mol/L, sodium dihydrogen phosphite 1.3mol/L, trisodium citrate 1.3mol/L, sodium acetate 1.3mol/L, 40 ℃ of solution temperatures, pH9.5, time 2min.
Result: observe nanometer plating pin height 0.05-0.4 micron, base diameter 0.05-0.2 micron, nanometer ball diameter 0.05-0.2 micron through SEM.
Embodiment 4
(1) oil removing, rust cleaning and cleanup acid treatment are carried out in the copper sheet surface of needs being carried out hydrophobic treatment.
(2) will place electroplating solution through the good metal base of (1) step process, metal base is as negative electrode, and the nickel plate is as anode, by lead both and power supply, electroplate liquid constituted the loop.Electroplate liquid consists of: nickelous chloride 0.7mol/L, and citric acid tri-amonia 0.5mol/L, boric acid 0.5mol/L, agent cupric chloride 100ppm, 30 ℃ of solution temperatures, pH4.5 are adjusted in crystallization.
(3) adjust current density 1A/min, electroplate 20min.
(4) will place chemical plating solution through the good metal base of (3) step process, solution composition is: six hydration nickel sulfate 0.7mol/L, sodium dihydrogen phosphite 0.7mol/L, trisodium citrate 0.7mol/L, sodium acetate 0.7mol/L, 90 ℃ of solution temperatures, pH9, time 2min.
Result: observe nanometer plating pin height 0.05-0.4 micron, base diameter 0.05-0.2 micron, nanometer ball diameter 0.05-0.2 micron through SEM.
Embodiment 5
(1) oil removing, rust cleaning and cleanup acid treatment are carried out in the copper sheet surface of needs being carried out hydrophobic treatment.
(2) will place electroplating solution through the good metal base of (1) step process, metal base is as negative electrode, and the nickel plate is as anode, by lead both and power supply, electroplate liquid constituted the loop.Electroplate liquid consists of: nickelous chloride 1.9mol/L, and citric acid tri-amonia 1.5mol/L, boric acid 0.5mol/L, agent cupric chloride 800ppm, 50 ℃ of solution temperatures, pH5 are adjusted in crystallization.
(3) adjust current density 1A/min, electroplate 20min.
(4) will place chemical plating solution through the good metal base of (3) step process, solution composition is: six hydration nickel sulfate 1.9mol/L, sodium dihydrogen phosphite 1.9mol/L, trisodium citrate 1.9mol/L, sodium acetate 1.9mol/L, 70 ℃ of solution temperatures, pH10.0, time 2min.
Result: observe nanometer plating pin height 0.05-0.4 micron, base diameter 0.05-0.2 micron, nanometer ball diameter 0.05-0.2 micron through SEM.
Claims (4)
1. the preparation method of a surface metal base nano array ball distributing structure is characterized in that, may further comprise the steps:
The first step, choose suitable metal base, metal base is carried out successively surface degreasing is handled, surface derusting is handled and cleanup acid treatment;
Second step, metal base is put into plating tank as negative electrode, nickel tinsel or insoluble pole plate be as anode, and with lead anode, negative electrode, electroplating power supply and electroplate liquid series connection are constituted the loop, by electroplating power supply metal base implemented to electroplate then;
The 3rd step, the metal base after will electroplating are put into the coating bath 2min that another contains chemical plating fluid, carry out making surface metal base nano array ball distributing structure after the electroless plating;
Described metal base is a copper sheet;
The component of described electroplate liquid and concentration are: nickelous chloride 0.1-2.5mol/L, triammonium citrate 0.1-2mol/L, boric acid 0.5mol/L and cupric chloride 1-1000ppm;
The component of described chemical plating fluid and concentration are: six hydration nickel sulfate 0.1-2.5mol/L, sodium dihydrogen phosphite 0.1-2.5mol/L, trisodium citrate 0.1-2.5mol/L and sodium acetate 0.1-2.5mol/L.
2. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described surface degreasing is handled and is meant: the adherent greasy dirt organic substance of metallic substrate surface is removed.
3. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described surface derusting is handled and is meant: the zone of oxidation inorganic substance of metallic substrate surface are removed.
4. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described cleanup acid treatment is meant metal base is soaked in having corrosive solution.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792918A (en) * | 2010-04-09 | 2010-08-04 | 上海交通大学 | Preparation method of surface Co-based micro-nano needle crystal array structure |
| CN103406248B (en) * | 2013-08-26 | 2016-01-06 | 武汉理工大学 | The preparation method of copper substrate superhydrophobic surface structure |
| CN104308369B (en) * | 2014-10-28 | 2016-08-24 | 吉林大学 | The preparation method of the super-hydrophobic bionic surface of iris at the bottom of a kind of cuprio |
| CN104616727B (en) * | 2015-01-26 | 2016-09-14 | 河南大学 | A kind of nano-cable transparent conductive film with silver as inner core and preparation method thereof |
| CN105670370B (en) * | 2016-01-04 | 2017-11-03 | 北京环境特性研究所 | A kind of wool top molded breadth frequency stealth material |
| CN108075142B (en) * | 2016-11-17 | 2020-03-10 | 中国科学院大连化学物理研究所 | Preparation method of nano-array catalyst layer for anion exchange membrane fuel cell |
| 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 |
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