CN100475685C - Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure - Google Patents
Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure Download PDFInfo
- Publication number
- CN100475685C CN100475685C CNB2005100284362A CN200510028436A CN100475685C CN 100475685 C CN100475685 C CN 100475685C CN B2005100284362 A CNB2005100284362 A CN B2005100284362A CN 200510028436 A CN200510028436 A CN 200510028436A CN 100475685 C CN100475685 C CN 100475685C
- Authority
- CN
- China
- Prior art keywords
- base material
- embattling
- based micro
- preparation
- shaped crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
A Method for preparation of surface Ni base macro nanometer acicular crystal array structure belongs to the fields of cross technology of electrochemistry, materials and macro nanometer technology. The invention places the catelectrode made of conductivity base material in the electroplating solution which contains crystallization modifier, and exert currents or voltage to make the electrocrystallization grows in a direction perpendicular to the surface in one-dimensional, after 5-3600 seconds, the needed Ni base macro nanometer acicular crystal array structure can form on the surface of the base material. The invention can form the needed Ni base macro nanometer acicular crystal array structure sizes from micrometer to nanometer on the surface of the base material, toy, the product can be used as component, and also can be used as material. So, the directional electrocrystallization means provided in the invention is provide with advantages of simple art work, low cost, no special requirement to the shap of the base material and the material quality, eligible for industrialization batch process.
Description
Technical field
What the present invention relates to is a kind of method of field of nanometer technology, specifically, is a kind of preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure.
Background technology
Micro-nano needle crystal array structure is meant a kind of structure that has the brilliant oldered array of vertical pin taper of micro-nano-scale at metal or nonmetallic surface.Real surface is long-pending big because this structure has, and high reaction activity under nanoscale and special needle-like array structure can produce many new functional characteristics, and its range of application is very wide.For example: (1) and other material compound tense, can obtain powerful bond strength, can be used for metal and metal, metal and pottery, various composites such as metal and resin.(2) should have remarkable heat dispersion, be expected to be used for the fin of microelectronic component.(3) should have excellent light diffuse scattering characteristic and good optical absorption characteristics, be expected to use it for optical material, laser camouflage material, light-Re transition material etc.(4) it as platinum, the carrier of chemical catalysts such as palladium can improve catalytic effect greatly.(5) pin awl crystalline substance is structured the formation as mould or reprint, on other material, can form the pin awl and structure the formation or back-off shape pin wimble structure.(6) because this structure has the crystallographic orientation characteristics, therefore can form special magnetic domain, be expected to produce giant magnetic effect.At present, mostly micro-nano card clothing battle array structure is to study from device angles, and general size is also mostly between micron and millimeter.About the preparation method mainly is template and LIGA (grenz ray deep layer photoetching electrotyping process technology) method.
Find by prior art documents, Liu Hongwen etc. are at " electrochemical deposition nanowires of gold structure and electrology characteristic thereof " (Acta PhySico-Chimica Sinica, 18 (4), 2002,359-363) mention template in the literary composition, specifically be to have porous oxide-film as template, plated metal crystal in the template nano-pore, a kind of method that template is dissolved away by chemical method more then.In addition, Chantal Khan Malek and VolkerSaile is in " Applications of LIGA technology to precision manufacturing ofhigh-aspect-ratio micro-components and-systems:areview " (application of LIGA technology in little member of high-aspect-ratio and the accurate manufacturing of micro-system), (Microelectronics Journal, microelectronics journal 35 (2004) 131-143) mentioning the LIGA method in, promptly is to adopt photoetching plate-making, electrotyping forming, go complex steps such as masterplate to carry out the micro-structural method for processing.It is big that these two kinds of methods all exist equipment investment, complex process, and efficient is low, the cost height, to the base material shape, size has shortcomings such as strict demand, and therefore, they only are applicable to the manufacturing of research purpose or micro element.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure is provided, make its technology simple, with low cost, to the ground shape, material does not have specific (special) requirements, is suitable for industrialized mass production.
The present invention is achieved by the following technical solutions, the present invention utilizes the electrochemical deposition principle, conductive substrate 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, after second, just can form desired Ni based micro-nano needle crystal array structure by 5-3600 at substrate surface.
Concrete steps of the present invention are as follows:
(1) base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment.
Described oil removing is meant the treatment process that the greasy dirt organic substance of substrate surface adhesion is removed.
Described rust cleaning is meant the treatment process that the oxide layer inorganic substances of substrate surface are removed.
Described activation is meant base material is soaked in having corrosive solution, by the slight corrosion of base material, increases surface-active, improves the treatment process of the bond strength of subsequent plating layer.
(2) will place electroplating solution through the base material that step (1) is handled well, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead;
(3) by electroplating power supply base material is implemented to electroplate, can adopt direct current also can adopt pulse or dipulse electric current during plating.Adopt direct current method condition enactment fairly simple, be convenient to production control.But the needle array structure is more single, and the control of its size, shape has certain degree of difficulty.Employing pulse or dipulse electric current obtain the array structure of different shape easily, but technological parameter is more, and be not easy to operate.
Described electroplating solution, specific requirement is as follows: the plated metal ion 0.1-2.5mol/L of nickel and alloy thereof, complexing agent 0.1-2mol/L, boric acid 0.5mol/L, agent 1-1000PPM, solution temperature 25-60 ℃, pH3.5-6.0 are adjusted in crystallization.
The plated metal ion of described nickel and alloy thereof is provided by the slaine that sulfate, chloride or amido xanthate constitute.
Described complexing agent is the organic complexing agent of fatty acid, yellow acid salt or amino-contained, hydroxy functional group.
Described complexing agent is by one or more constitute in citrate, malate, edetate, acetate, the ethylenediamine.
Complexing agent plays each metal ion species in the stabilizing solution here, the effects such as ratio of separating out of balance nickel and other metal ion.Boric acid mainly plays the buffer pH value.
Agent is adjusted in described crystallization, is made of Cu, Ag, Pd, Au, Zn, Sn, Ca and Y, La, Ce, Eu rare earth ion.The effect that agent is adjusted in crystallization is quantity, the furnishing crystalline growth direction of crystallization control active site and the speed that improves longitudinal growth.
The average height of described needle-like crystalline substance is the 0.05-10 micron, and the bottom average diameter is the 0.05-4 micron.
According to general electrocrystallization theory, metal is in electrochemical deposition process, and growing up of the formation of nucleus and crystal grain generally is to take place synchronously, and growing up of crystal grain is that multidimensional is carried out.On the other hand, from microcosmic angle, electrocrystallization at each constantly, each place be not uniform, it exists many instantaneous crystallization active sites, as the atomic density owing to the crystal face on each single grain all directions, the difference of spread pattern will cause the difference of prolonging crystals growth speed on each crystal face.Therefore, want to form micro/nano level pin awl crystal array structure, must be under the prerequisite of control active site quantity, the life-span of these active sites is prolonged as much as possible, enlarge simultaneously the difference of the above-mentioned speed of growth that causes because of the crystal face difference as much as possible, and the crystal face that the speed of growth is the fastest is adjusted to and is parallel to the metal surface, could obtain the needle crystal array structure of our desirable longitudinal growth like this.
The present invention utilizes above-mentioned electrochemical principle dexterously, promptly adjust agent by the crystallization that adds trace in the electroplate liquid, control the quantity of effective active site, and adjust the speed of growth and the direction of growth of each crystal face, make its crystallization by direction one dimension longitudinal growth, form above-mentioned Ni based micro-nano needle crystal array structure perpendicular to substrate surface.Directed electrocrystallization method provided by the invention is compared with existing methods such as template, LIGA methods, its biggest advantage is need be by any masterplate or mask, need not complex device, only need base material is placed the electrolyte solution that contains the Ni ion that possesses necessary condition as negative electrode, and additional electric current, the voltage that satisfies requirement of the present invention, through the electrocrystallization time of regulation, can make substrate surface form the Ni base needle crystal array structure of micro-nano-scale.Adopt this method, can both can be used as device, can be used as material again directly at the Ni base needle crystal array structure of required substrate surface formation from the micron to the nanoscale.Therefore, it is simple, with low cost that directed electrocrystallization method provided by the invention has technology, and to the ground shape, material does not have specific (special) requirements, is suitable for advantages such as industrialized mass production.
The specific embodiment
Embodiment 1
Concrete steps of the present invention are as follows:
(1) the copper coin base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment.
(2) will place following electroplating solution through the good base material of step (1) pre-treatment, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead.
The used electroplating solution of present embodiment consists of: nickelous sulfate 0.1mol/L, and citric acid tri-amonia 0.1mol/L, boric acid 0.5mol/L, agent copper chloride 1PPM, 25 ℃ of solution temperatures, pH3.5 are adjusted in crystallization.
(3) by electroplating power supply base material is implemented DC current, current density is 5A/dm
2, electroplating time is 20 seconds.
The result: this sample appearance is a furvous, and through 100,000 times of field emission electron microscopic observations, the needle-like crystalline substance of this body structure surface is of a size of: needle height 0.05-0.4 micron, base diameter is the 0.05-0.2 micron.
Embodiment 2
Concrete steps of the present invention are as follows:
(1) the copper coin base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment.
(2) will place following electroplating solution through the good base material of step (1) pre-treatment, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead.
The used electroplating solution of present embodiment consists of: nickel chloride 1.0mol/L, and ethylenediamine 1.0mol/L, boric acid 0.5mol/L, agent copper chloride 500PPM, 60 ℃ of solution temperatures, pH4.5 are adjusted in crystallization.
(3) by electroplating power supply base material is implemented the pulse square wave current, average current density is 0.5A/dm
2, electroplating time is 1200 seconds.
The result: this sample appearance is near black matrix, and through 100,000 times of field emission electron microscopic observations, the needle-like crystalline substance of this body structure surface is of a size of: needle height 0.1-0.8 micron, base diameter is the 0.05-0.3 micron.
Embodiment 3
Concrete steps of the present invention are as follows:
(1) the iron plate base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment.
(2) will place following electroplating solution through the good base material of step (1) pre-treatment, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead.
The used electroplating solution of present embodiment consists of: nickelous sulfate 1.5mol/L, and cobalt chloride 1.0mol/L, citric acid tri-amonia 2.0mol/L, boric acid 0.5mol/L, agent calcium chloride 1000PPM, 46 ℃ of solution temperatures, pH6.0 are adjusted in crystallization.
(3) by electroplating power supply base material is implemented the pulse square wave current, average current density is 1A/dm
2, electroplating time is 300 seconds.
The result: this sample appearance is dark-coloured, and through 100,000 times of field emission electron microscopic observations, the needle-like crystalline substance of this body structure surface is of a size of: needle height 3-5 micron, and base diameter is the 1-2 micron, Co content is 21 weight % in the alloy.
Embodiment 4
Concrete steps of the present invention are as follows:
(1) the copper coin base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment.
(2) will place following electroplating solution through the good base material of step (1) pre-treatment, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead.
The used electroplating solution of present embodiment consists of: nickel sulfamic acid 1.0mol/L, and Ammonium Acetate 1.0mol/L, boric acid 0.5mol/L, agent copper chloride 1000PPM, 60 ℃ of solution temperatures, pH6.0 are adjusted in crystallization.
(3) by electroplating power supply base material is implemented the pulse square wave current, average current density is 0.5A/dm
2, electroplating time is 1200 seconds.
The result: this sample appearance is near black matrix, and through 100,000 times of field emission electron microscopic observations, the needle-like crystalline substance of this body structure surface is of a size of: needle height 4-10 micron, base diameter is the 2-4 micron.
Claims (8)
1. the preparation method of a surface Ni based micro nanometer needle shaped crystal embattling structure, it is characterized in that, conductive substrate 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 of substrate surface, after second, just can form desired Ni based micro-nano needle crystal array structure by 5-3600 at substrate surface;
Described electroplating solution, specific requirement is as follows: the plated metal ion 0.1-2.5mol/L of nickel and alloy thereof, complexing agent 0.1-2mol/L, boric acid 0.5mol/L, agent 1-1000PPM, solution temperature 25-60 ℃, pH3.5-6.0 are adjusted in crystallization;
Agent is adjusted in described crystallization, by one of among Cu, Ag, Pd, Au, Zn, Sn or the Ca or by constituting one of in Y, La, Ce or the Eu rare earth ion.
2. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 1 is characterized in that, may further comprise the steps:
(1) base material that the surface need be formed micro-nano needle array structure carries out oil removing, rust cleaning and activation pre-treatment;
(2) will place electroplating solution through the base material that step (1) is handled well, and with base material as negative electrode, as anode, and make base material, nickel plate and electroplating power supply constitute the loop on nickel plate or insoluble pole plate by lead;
(3) by electroplating power supply base material is implemented to electroplate, can adopt direct current also can adopt pulse or dipulse electric current during plating.
3. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 2 is characterized in that, described oil removing is meant the greasy dirt organic substance removal that substrate surface is adhered to.
4. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 2 is characterized in that, described rust cleaning is meant the oxide layer inorganic substances of substrate surface are removed.
5. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 2 is characterized in that, described activation is meant base material is soaked in having corrosive solution.
6. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 1 is characterized in that, the plated metal ion of described nickel and alloy thereof is provided by the slaine that sulfate, chloride or amido xanthate constitute.
7. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 1 is characterized in that, described complexing agent is the organic complexing agent of fatty acid, yellow acid salt or amino-contained, hydroxy functional group.
8. the preparation method of surface Ni based micro nanometer needle shaped crystal embattling structure according to claim 1 is characterized in that, described complexing agent is by one or more constitute in citrate, malate, edetate, acetate, the ethylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100284362A CN100475685C (en) | 2005-08-04 | 2005-08-04 | Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100284362A CN100475685C (en) | 2005-08-04 | 2005-08-04 | Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730380A CN1730380A (en) | 2006-02-08 |
| CN100475685C true CN100475685C (en) | 2009-04-08 |
Family
ID=35962807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100284362A Expired - Fee Related CN100475685C (en) | 2005-08-04 | 2005-08-04 | Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100475685C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103147102B (en) * | 2013-02-20 | 2016-07-06 | 上海交通大学 | A kind of pin cone micro-nano twin-stage array structure materials and preparation method thereof |
| CN103603020B (en) * | 2013-10-17 | 2016-08-10 | 上海交通大学 | Electrochemical deposition prepares the method for copper-connection micro-nano needle wimble structure |
| CN103603017A (en) * | 2013-10-31 | 2014-02-26 | 东莞市科益纳米科技有限公司 | Environmental-friendly energy-saving nano electro nickel-plating technology |
| 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 |
-
2005
- 2005-08-04 CN CNB2005100284362A patent/CN100475685C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1730380A (en) | 2006-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Magnetic field-induced solvothermal synthesis of one-dimensional assemblies of Ni-Co alloy microstructures | |
| CN102400188B (en) | (111) texture nano-grade twin crystal Cu block material and preparation method thereof | |
| CN104419983B (en) | Single crystal copper, method of preparing the same, and substrate comprising the same | |
| CN100475685C (en) | Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure | |
| CN103147102B (en) | A kind of pin cone micro-nano twin-stage array structure materials and preparation method thereof | |
| FI126197B (en) | Method of extracting metal nanoparticles from solutions | |
| CN101323964B (en) | Synthetic method of load type floriform silver nanostructured material | |
| CN101698961B (en) | Preparation method of surface plasmonic crystal | |
| CN101498050B (en) | Preparation of nickel zinc alloy nano-wire array material | |
| CN101250719B (en) | Method for one-step synthesing and assembling cuprum nanometer particle | |
| CN101603176B (en) | Preparation method of surface metal base nano array ball distributing structure | |
| CN105908220A (en) | Method for manufacturing micro-nano-silver dendritic crystal through liquid-phase electrodeposition | |
| Mundotiya et al. | Morphology controlled synthesis of the nanostructured gold by electrodeposition techniques | |
| CN1676674A (en) | Method for preparing nickel-phosphor alloy base composite cladding containing nano particle | |
| CN101469453A (en) | Alloy nanotube and manufacturing method thereof | |
| CN109628968B (en) | TSV rapid filling method and device | |
| CN101792918A (en) | Preparation method of surface Co-based micro-nano needle crystal array structure | |
| CN105039943B (en) | A kind of plating solution and its plating process of Electroless Plating Ni-W-Zn-P alloy layers | |
| CN107385486A (en) | Method for pulse gold electroplating and gold plating layer formed by same | |
| CN103603020A (en) | Method for preparing micro-nano needle conical structure for copper interconnection by electrochemical deposition | |
| CN101041469A (en) | Preparation method for one-dimensional metallic oxide nano needle material | |
| CN102312257A (en) | Method for preparing nanocrystalline nickel-ferro-cobalt ternary alloy through pulse electrodeposition | |
| CN103603015A (en) | Electrochemistry preparation method for micro-nano conical needle structure for copper interconnection | |
| CN102936739B (en) | Preparation method for gold nanowire network through controllable electrodeposition | |
| GONG et al. | Preparation and characterization of La-Co alloy nanowire arrays by electrodeposition in AAO template under nonaqueous system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20060208 Assignee: Stats Chippac(shanghai)ltd Assignor: Shanghai Jiao Tong University Contract record no.: 2011310000073 Denomination of invention: Process for preparing surface Ni based micro nanometer needle shaped crystal embattling structure Granted publication date: 20090408 License type: Exclusive License Record date: 20110526 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090408 Termination date: 20160804 |