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WO2006021507A1 - Surface a microstructure diminuant l'adherence et procede de fabrication associe - Google Patents

Surface a microstructure diminuant l'adherence et procede de fabrication associe Download PDF

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Publication number
WO2006021507A1
WO2006021507A1 PCT/EP2005/053902 EP2005053902W WO2006021507A1 WO 2006021507 A1 WO2006021507 A1 WO 2006021507A1 EP 2005053902 W EP2005053902 W EP 2005053902W WO 2006021507 A1 WO2006021507 A1 WO 2006021507A1
Authority
WO
WIPO (PCT)
Prior art keywords
microstructure
nanostructure
pulses
produced
pulse
Prior art date
Application number
PCT/EP2005/053902
Other languages
German (de)
English (en)
Inventor
Christian Hansen
Ursus KRÜGER
Manuela Schneider
Original Assignee
Siemens Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Priority to EP05787076A priority Critical patent/EP1781841A1/fr
Priority to BRPI0514625-9A priority patent/BRPI0514625A/pt
Priority to US11/660,814 priority patent/US20080217180A1/en
Priority to CN2005800367999A priority patent/CN101048537B/zh
Publication of WO2006021507A1 publication Critical patent/WO2006021507A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers

Definitions

  • the invention relates to a surface having a haftungsver ⁇ reducing microstructure and a method for producing such a surface elektroche ⁇ mix.
  • Adhesion-reducing surfaces of the type mentioned come z. B. as so-called lotus effect surfaces are used and are for example in DE 100 15 855 Al ⁇ written .
  • lotus effect surfaces are used and are for example in DE 100 15 855 Al ⁇ written .
  • such surfaces are characterized by a microstructure which can be obtained by a layer deposition from solutions, but also by an electrolytic deposition. This mimics an effect observed on the leaves of the lotus flower, according to which the microstructure produced, which for this purpose has elevations and depressions with a radius of 5 to 100 ⁇ m, reduces the adhesion of water and dirt particles. In this way, contamination of the corresponding surface can be counteracted.
  • z. B. lime deposits vermei ⁇ the.
  • the object of the invention is to specify a surface with an adhesion-reducing microstructure or a production method for this surface, wherein the effect of reducing the adhesion should be comparatively strongly pronounced.
  • a ge ⁇ solves in which the surface by electrochemical pulses Plating is prepared, wherein a microstructure on ⁇ overlapping nanostructure by reverse pulse plating is generated.
  • the superposition of the microstructure by a Na ⁇ carried nanostructure according to the invention characterized in that on the O- ber laketopologie with radii of curvature of heatnpro ⁇ fils is prepared in the micrometer range (microstructure) atrento ⁇ topology, whose radii of curvature preferably in the range of a few nanometers to 100 nanometers ( Nanostructure).
  • the formation of the nanostructure on the microstructure is achieved by reverse pulse plating with current pulses of a length in the millisecond range. Depending on the choice of process parameters such as pulse length and deposition density, the microstructure can be produced simultaneously or separately.
  • the nanostructure of the surface in combination with the microstructure advantageously improves the effect of reducing the adhesion of substances on the surface. As a result, the lotus effect of the surface is advantageously improved.
  • the pulse length in the method step for producing the nanostructure is less than 500 ms.
  • favorable deposition be set at the surface to be generated, so that the nanostructure generated in its dimensions ge sufficiently different from the microstructure produced.
  • the individual current pulses are advantageously in the range between 10 and 250 milliseconds in terms of their length. It has been found that the nanostructure of the surface is advantageously particularly pronounced in the case of the mentioned parameters.
  • the cathodic pulses have at least three times the length of the a nodonic pulses.
  • cathodic pulses within the meaning of He-making ⁇ those pulses are perceived, at which there is ei ⁇ ner deposition on the surface, while the view anodic pulses produce a resolution of the surface.
  • the needle-like basic elements of the nanostructure advantageously be generated with a high density on the microstructure, which favors to ER- targeting Lotus effect.
  • the reverse pulse plating the cathodic pulses are performed with a higher current density than the anodic see pulses.
  • the deposition rate of the cathodic pulses is increased in comparison to the removal rate of the anodic pulses, so that advantageously a layer ⁇ growth of the nanostructuring is generated.
  • NATURALLY The measures of a modification of the pulse duration and the variation of the current density can be combined with one another. In each case, an optimum is to be found by setting the mentioned parameters for the material to be deposited.
  • the pulse length is at least one second in an upstream process step for producing the microstructure.
  • the required time may advantageously Mikro ⁇ low electrochemically ⁇ chemical means are produced in the structure of the surface if it does not or not generation of sufficient severity in the process step for Er ⁇ arises the nanostructure.
  • the surface is additionally produced with a macrostructure which superimposes the microstructure.
  • the macrostructure can be electrochemically or by other means z. B. be made mechanically.
  • a topography of the surface of a macrostructure understood here logy whose geometric Abmes ⁇ solutions of the elementary structural components by at least ei ⁇ ne order of magnitude greater than that of the microstructure. For a wavy macrostructure, this would mean for the radius of the waves, for example, that this in corresponding
  • the macrostructure advantageously permits an additional increase in the adhesion-reducing properties of the surface.
  • the macrostructure of the surface can advantageously have additional functions, such. B. egg ⁇ ner improve the flow characteristics of the surface.
  • the surface according to the invention solves the previously mentioned problem by superimposing on the microstructure a nanostructure produced by pulse-plating. With this surface construction according to the invention, the already mentioned advantages, in particular an improvement of the adhesion-reducing properties of the surface, can be achieved.
  • this is superhydrophobic.
  • the superhydrophobic properties cause insbe ⁇ sondere poor wettability of the surface for what ⁇ ser, so forming individual droplets on the surface befindliches water, by virtue of a contact angle for O berflache of more than 140 ° easily roll off, while also possibly on the Contain surface with dirt ⁇ tear. Therefore, surfaces with superhydrophobic properties are particularly suitable for forming the surface as a lotus effect surface.
  • FIG. 1 shows the schematic structure of an embodiment of the surface according to the invention in a schematic section
  • Figure 2 shows the surface profile of a lotus effect surface as an embodiment of the Ober ⁇ surface according to the invention in section
  • FIG. 3 shows perspective views of the lotus effect surface according to FIG. 2.
  • FIG. 1 shows a body 11 with a surface whose adhesion properties are reduced.
  • the surface 12 can be described schematically by a superposition of a macrostructure 12 having a microstructure 13 and a nanostructure 14.
  • the microstructure produces a waviness of the surface.
  • the microstructure is interpreted by semi-spherical elevations on the wavy macrostructure 12.
  • the nanostructure 14 is represented in FIG. 1 by nubs which are located on the hemispherical elevations (microstructure) and in the parts of the macrostructure 12 which form the depressions of the microstructure 13 and which are located between the elevations.
  • ⁇ is a relatively large contact angle ⁇ , which is defined by an angle leg 16a, the paral ⁇ lel to the surface, and an angle leg 16b, which forms a tangent to the skin of the water droplet, through the edge of the contact surface of the water droplet 15 with the Surface (or more precisely the angle leg 16a) runs. Shown in FIG. 1 is a contact angle ⁇ of more than
  • Pulse length (reverse pulses): 240 ms at 10 A / dm 2 cathodic, 40 ms at 8 A / dm 2 anodic
  • Electrolyte contained 50 g / l Cu, 20 g / l free cyanide, 5 g / l KOH
  • the surface is electrochemically generated in the following with ⁇ means of an SPM (Scanning Probe Microscope - AFM or also called A- Tomic Force Microscope) has been studied.
  • SPM Sccanning Probe Microscope - AFM or also called A- Tomic Force Microscope
  • FIG. 2 A section of the generated surface is shown in section in FIG. 2 as a measurement result of the SPM, with the profile being excessively elevated.
  • a waveform 18 is entered in FIG. 2, which illustrates the macrostructure superimposed on the surface structure.
  • the microstructure 13 can be recognized as a sequence of needle-like elevations 19 and depressions 20.
  • the nanostructure 14 can be recognized, which results from a narrow sequence of elevations and depressions, which are no longer to be resolved in the scale shown in FIG. 2 and can therefore only be seen as a thickening of the profile line of the surface profile.
  • FIG. 3a shows a perspective view of the SPM receptacle of the copper surface.
  • a square area of 100x100 microns has been selected as a section, with the Microstructure 13 determining, needle-like elevations 19 are clearly visible.
  • the resulting image reminds the viewer of a "coniferous forest” with the interstices between the "conifers” (elevations 19) forming the depressions 20.
  • the surface according to FIG. 3 a too is shown elevated in order to illustrate the elevations 19 and the depressions 20 of the microstructure 13.
  • the microstructure 13 is furthermore superimposed on a nanostructure 14.
  • the ridges 19 and depressions 20 appear more like a waviness of the surface (but not ness of Figure 2 may be confused due to the different scale with the wavy ⁇ ).
  • This wavy ⁇ are superimposed ness further increases smallest recesses 19n and 20n which rakter imagine the nanostructure of the surface cha ⁇ .
  • These, too, are pronounced in their structure of the expression of a "coniferous forest" already explained with reference to FIG. 3a, the geometrical dimensions of which are smaller by approximately two orders of magnitude, that is to say can not be recognized at the scale selected in FIG.
  • the bracket always comprises only a section of the respective structure, which contains an elevation and a depression, so that the brackets allow one another in each case within a figure a comparison of the orders of magnitude of the structures in relation to one another.
  • the measured for a drop of water was sene contact angle 152 °.
  • the superhydrophobic properties of the copper layer shown, which act a lotus effect be ⁇ is achieved by a combination of at least the micro ⁇ structure 13 and the nanostructure 14, wherein the superposition of a macro-structure 12, the observed effects improved.
  • suitable process parameters such lotus effect surfaces can be produced for different layer materials (for example, silver coatings have also been successfully tested) and for liquids with different wetting behavior.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une surface à microstructure diminuant l'adhérence et un procédé de fabrication associé. Ces microstructures diminuant l'adhérence sont connues, par exemple, pour former des surfaces autonettoyantes appliquant l'effet lotus. Selon l'invention, la surface est fabriquée électrochimiquement par électrodéposition sous impulsion de courant inversée. On obtient ainsi la microstructure connue et, simultanément ou bien lors d'une opération subséquente, une nanostructure recouvrant ladite microstructure. Selon l'invention, la longueur de l'impulsion du courant utilisé lors de l'électrodéposition sous impulsion de courant inversée est sélectionnée dans l'ordre de grandeur des millisecondes, le rapport de longueur d'impulsion étant supérieur à 1:3 (anode:cathode). La microstructure ainsi obtenue, constituée par des élévations (19) et des creux (20), est ensuite recouverte des élévations (19n) et des creux (20n) de la nanostructure d'ordre de grandeur plus petit, ce qui permet d'améliorer notablement l'effet lotus de la surface.
PCT/EP2005/053902 2004-08-26 2005-08-08 Surface a microstructure diminuant l'adherence et procede de fabrication associe WO2006021507A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP05787076A EP1781841A1 (fr) 2004-08-26 2005-08-08 Surface a microstructure diminuant l'adherence et procede de fabrication associe
BRPI0514625-9A BRPI0514625A (pt) 2004-08-26 2005-08-08 superfìcie com uma microestrutura diminuidora de aderência e processo para sua produção
US11/660,814 US20080217180A1 (en) 2004-08-26 2005-08-08 Surface with an Anti-Adhesion Microstructure and Method for Producing Same
CN2005800367999A CN101048537B (zh) 2004-08-26 2005-08-08 具有一种减少粘附性的微结构的表面及其制备方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004041813.6 2004-08-26
DE102004041813A DE102004041813A1 (de) 2004-08-26 2004-08-26 Oberfläche mit einer haftungsvermindernden Mikrostruktur und Verfahren zu deren Herstellung

Publications (1)

Publication Number Publication Date
WO2006021507A1 true WO2006021507A1 (fr) 2006-03-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/053902 WO2006021507A1 (fr) 2004-08-26 2005-08-08 Surface a microstructure diminuant l'adherence et procede de fabrication associe

Country Status (6)

Country Link
US (1) US20080217180A1 (fr)
EP (1) EP1781841A1 (fr)
CN (1) CN101048537B (fr)
BR (1) BRPI0514625A (fr)
DE (1) DE102004041813A1 (fr)
WO (1) WO2006021507A1 (fr)

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DE102014113097A1 (de) 2014-09-11 2016-03-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Reduzieren der Schmutzhaftung an einem Substrat

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US9005420B2 (en) * 2007-12-20 2015-04-14 Integran Technologies Inc. Variable property electrodepositing of metallic structures
US20100112286A1 (en) * 2008-11-03 2010-05-06 Bahadur Vaibhav A Superhydrophobic surfaces
US8545994B2 (en) * 2009-06-02 2013-10-01 Integran Technologies Inc. Electrodeposited metallic materials comprising cobalt
US8987632B2 (en) * 2009-10-09 2015-03-24 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Modification of surface energy via direct laser ablative surface patterning
CA2797205C (fr) 2010-04-28 2019-04-16 Kimberly-Clark Worldwide, Inc. Dispositifs medicaux pour l'administration d'arnsi
WO2012046149A1 (fr) 2010-04-28 2012-04-12 Kimberly-Clark Worldwide, Inc. Procédé d'augmentation de la perméabilité d'une barrière épithéliale
EP2563450B1 (fr) 2010-04-28 2017-07-26 Kimberly-Clark Worldwide, Inc. Dispositif pour administrer un médicament contre l'arthrite rhumatoïde
US9526883B2 (en) 2010-04-28 2016-12-27 Kimberly-Clark Worldwide, Inc. Composite microneedle array including nanostructures thereon
US8486319B2 (en) 2010-05-24 2013-07-16 Integran Technologies Inc. Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same
US9303322B2 (en) * 2010-05-24 2016-04-05 Integran Technologies Inc. Metallic articles with hydrophobic surfaces
US9492952B2 (en) 2010-08-30 2016-11-15 Endo-Surgery, Inc. Super-hydrophilic structures
US20120143228A1 (en) 2010-08-30 2012-06-07 Agency For Science Technology And Research Adhesive structure with stiff protrusions on adhesive surface
WO2013061209A1 (fr) 2011-10-27 2013-05-02 Kimberly-Clark Worldwide, Inc. Dispositifs implantables pour administrer des agents bioactifs
KR102265775B1 (ko) 2011-10-27 2021-06-16 소렌토 쎄라퓨틱스, 인코포레이티드 고점도 생체활성 제제의 경피 전달 방법
US20170246439A9 (en) 2011-10-27 2017-08-31 Kimberly-Clark Worldwide, Inc. Increased Bioavailability of Transdermally Delivered Agents
JP6153945B2 (ja) 2011-12-29 2017-06-28 エシコン・インコーポレイテッドＥｔｈｉｃｏｎ， Ｉｎｃｏｒｐｏｒａｔｅｄ 表面上に組織貫入突起を有する接着構造体
US8926881B2 (en) 2012-04-06 2015-01-06 DePuy Synthes Products, LLC Super-hydrophobic hierarchical structures, method of forming them and medical devices incorporating them
US8969648B2 (en) 2012-04-06 2015-03-03 Ethicon, Inc. Blood clotting substrate and medical device
US9278374B2 (en) 2012-06-08 2016-03-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Modified surface having low adhesion properties to mitigate insect residue adhesion
DE102012112550A1 (de) 2012-12-18 2014-06-18 Lpkf Laser & Electronics Ag Verfahren zur Metallisierung eines Werkstücks sowie ein Schichtaufbau aus einem Werkstück und einer Metallschicht
CN104284685B (zh) * 2013-01-11 2017-06-27 Bvw控股公司 生物选择性表面纹理
DE102014006739B3 (de) 2014-05-12 2015-06-25 Albert-Ludwigs-Universität Freiburg Verfahren zur Beschichtung von Oberflächen mit Nanostrukturen, nach dem Verfahren her- gestelltes Bauteil und Verwendung des Bauteils
CN106591896A (zh) * 2016-12-06 2017-04-26 南京理工大学 一种制备具有植物叶片结构超疏水铜表面的方法

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Publication number Priority date Publication date Assignee Title
WO2001021294A2 (fr) * 1999-09-24 2001-03-29 Semitool, Inc. Evolution en fonction du trace du profil superficiel en metal de depot electrochimique
US20020038764A1 (en) * 1999-10-15 2002-04-04 Taylor E. Jennings Sequential electrodeposition of metals using modulated electric fields for manufacture of circuit boards having features of different sizes
DE10064520A1 (de) * 2000-12-22 2002-07-04 Daimler Chrysler Ag Verfahren zur Herstellung von selbstreinigenden Oberflächenstrukturen
US20030075450A1 (en) * 2001-10-15 2003-04-24 Taylor E. Jennings Electrodeposition of metals in high-aspect ratio cavities using modulated reverse electric fields
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Publication number Priority date Publication date Assignee Title
DE102014113097A1 (de) 2014-09-11 2016-03-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Reduzieren der Schmutzhaftung an einem Substrat
US10557196B2 (en) 2014-09-11 2020-02-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for reducing the adhesion of dirt to a substrate

Also Published As

Publication number Publication date
US20080217180A1 (en) 2008-09-11
EP1781841A1 (fr) 2007-05-09
CN101048537A (zh) 2007-10-03
BRPI0514625A (pt) 2008-06-17
CN101048537B (zh) 2010-06-16
DE102004041813A1 (de) 2006-03-02

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