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    • 专利摘要:
    Method for the production of superhydrophilic and superhydrophobic surfaces. The present invention describes a method for the production of superhydrophilic and superhydrophobic surfaces based on the modification of the wettability of the original surface by means of the action of a laser beam. The surfaces generated by said method are also object of this invention. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2597861A2
    申请号:ES201531076
    申请日:2015-07-21
    公开日:2017-01-23
    发明作者:Pablo POU ÁLVAREZ；Jesús Del Val García；Fernando Lusquiños Rodríguez；Antonio Riveiro Rodríguez；Rafael Comesaña Piñeiro；Mohamed Boutinguiza Larosi；Félix Quintero Martínez；Juan María Pou Saracho
    申请人:Universidade de Vigo；
    IPC主号:
    专利说明:

     2D DESCRIPTION METHOD FOR THE PRODUCTION OF SURFACE AND HYDROPHYPHIC SURFACES 5 TECHNICAL FIELD This invention is framed within the techniques of surface processing of materials to modify their properties with respect to wettability. The technique described in the present invention allows to obtain superhydrophilic and superhydrophilic surfaces. THE INVENTION Wettability is the fundamental property that defines the tendency of a liquid to extend or contract when it comes into contact with the surface of a solid.This phenomenon constantly comes into play in everyday life whenever any liquid contacts a solid body or, for example, when the skin repeatedly comes into contact with any solid surface.In addition, wettability fundamentally affects applications in all kinds of sectors, from biomedical to naval, through microelectronics, automotive or textile, among others. Phenomena such as metal corrosion, adhesion and proliferation of cells, dispersion of detergents, lubricants and all kinds of coatings or even heat transmission and signal transfer depend on the degree of wettability of a liquid with the solid surface with which It comes into contact. Those surfaces that have a minimum wettability in contact with the corresponding liquid, usually water, are called superhydrophobic surfaces.25 On the contrary, they are called superhydrophilic surfaces, those surfaces that have a maximum wettability in contact with the corresponding liquid, normally water.In relation to superhydrophobic surfaces, the main attraction that drives its development is its self-cleaning capacity. Due to the high value of the contact angle and the great ease of sliding, the drops of water are able to capture and drag the dirt that rests on said surface as they slide on it. This ability promotes the development of all types of outdoor surfaces, as well as by3Example in photovoltaic solar energy panels, where dirt is a deterioration of efficiency. The poor adhesion of water to these types of surfaces prevents the formation of ice, which is detrimental in the transmission of signals in radars and antennas, and even dangerous in the wings and fuselage of airplanes. This type of surfaces also prevents the formation of fog and corrosion in the case of metals, since the contact time with the liquid is greatly reduced. Given that they have a reduced contact with water, superhydrophobic surfaces are interesting in Dynamic fluid applications, such as pipes, boat hulls and fluid handling devices on a micrometric scale. In addition, in the biomedical field, repulsion towards water prevents adhesion of tissues and microorganisms. This may be advantageous to avoid colonization of microbacteria in exposed parts of implants or to reduce tearing of tissues by unwanted adhesion in surgical instruments. In relation to superhydrophilic surfaces, its self-cleaning capacity is also remarkable, while favoring the introduction of a layer of water between the contaminant and the surface. In this aspect they have the disadvantage compared to the superhydrophobic ones that the removal of dirt is much slower. However, in the case where the contaminants are hydrophobic, such as oils or fats, the spherical drops formed on a superhydrophobic surface are not able to drag them, which is achieved with a superhydrophilic surface.25 On the other hand this type of surface , while favoring the extension of a film of liquid, prevents condensation of drops in the form of mist. It is also found that good adhesion to water favors the growth of osteoblasts and the consequent improvement in implant integration.30 Lastly, superhydrophilic surfaces can help optimize heat transmission in water pipes and tubes. It is found that when the liquid reaches temperatures close to boiling, the nucleation of vapor bubbles around the heat conductive surface begins, reaching a maximum in the heat transmission. However, if the nucleation is excessive, a vapor layer forms on the surface that acts as an insulator, causing the transmission of4call decrease noticeably. If a surface manages to maintain a layer of adhered liquid it can delay the formation of the vapor layer and therefore optimize the process.One of the techniques used to obtain superhydrophobic and superhydrophilic surfaces, is the modification of the chemical composition of the surface by means of the application of a coating. Thus, coatings with covalent bonds and silane derivatives have been used, with low surface energy to achieve superhydrophobic surfaces. As regards superhydrophilic surfaces, they are usually obtained by means of chlorosilane-based alcohol-based coatings.10 The use of coatings is inconvenient due to the additional cost of the material to be applied to the workpiece, the relatively low durability of these coatings and the modification of the chemical composition of the material to be treated.The other technique used is the modification of the surface texture. This usually uses techniques based on EDM, lithography or stamping. 15The scope of these techniques is limited, either because of their high cost, or because the required surface modifications are not easily attainable given the microscopic nature of the required surface. On the other hand, the high surface speed of processing required to provide microscopic motifs to large areas discards micromachining methods by chip removal or any other contact method. 20To solve these difficulties, in recent years the use of laser ablation using ultra-short pulse lasers has been raised, that is, with a duration of picoseconds or femtoseconds to modify the wettability of certain surfaces, with the addition, in some cases, of a coating after the laser treatment.25 Well, the method object of the present invention uses a laser with longer pulses, in the range of microseconds or nanoseconds as a tool for the elaboration of both superhydrophilic and superhydrophobic surfaces, on Several different materials. The results are obtained with relatively high processing speeds and in a single step, without the need for coatings to chemically alter the surface beyond the effects of the treatment itself. All this improves the economic viability of this type of treatments at industrial level with respect to the currently existing methods.35DESCRIPTION OF THE INVENTION The present invention provides a method for modifying the surface wettability of different materials, characterized in that it comprises a stage of application on the surface to be treated of a laser beam, such that the texture and / or modification is modified. the chemical composition of said surface at micrometric and nanometric level 5 minimizing or maximizing the interfacial tension of the air / liquid (water base) / material set.The method object of the present invention comprises an application stage on the surface to be treated of a laser beam whose wavelength is within the range of 10532nm to 1064 nm. The average power within the range 1 W to 20 W, and the pulse width within it is at least 1ns.15 When it comes to obtaining a superhydrophilic surface, laser treatment encourages the liquid / solid interfacial tension is minimal. When it comes to obtaining a superhydrophobic surface ca, the laser treatment encourages the gas / solid interfacial tension to be minimal.20 Optionally, the application on the surface to be treated of a laser beam can be carried out following a predefined geometric pattern formed by lines in one or two directions on the surface to be treated .25 Optionally, the application on the surface to be treated of a laser beam according to a predefined geometric pattern formed by lines is applied by moving the laser beam, keeping the surface to be treated fixed, or moving the surface to be treated, keeping the laser beam fixed, where the movable element does so by describing a linear or rotary movement.30Optionally, the application on the surface to be treated of a laser beam comprises a sub-stage for redirecting the laser beam on the surface to be treated.Optionally, the application on the surface to be treated a laser beam comprises a focusing beam of the laser beam on Re the surface to be treated.6Optionally, the application on the surface to be treated of a laser beam is carried out in the presence of an inert gas atmosphere such as argon.Optionally, the application on the surface to be treated of a laser beam is carried out in the presence of an atmosphere of oxidizing gas such as air2.5 The method of the present invention allows to generate surfaces with controlled wettability without generating environmental pollution or toxic waste and can be integrated into a production chain, for different part geometries, from flat, cylindrical surfaces with various diameters to regulated surfaces or warped. 10 The method of the present invention does not require the application of a coating, a subsequent mechanical or chemical treatment. The method of the present invention offers greater durability of the treated surfaces, a greater uniformity of the wetting properties throughout the surface area and a greater repeatability of said properties for different treated surfaces according to the same processing parameters. DESCRIPTION OF THE DRAWINGS 20 To complement the description that is being made and in order to help a better understanding of the features of the invention, are attached as an integral part of said description the following figures. Figure 1 shows the surface of a sheet of AISI 304 stainless steel with prior to the application of the method of the present invention. This micrograph has been obtained by means of a scanning electron microscope. Note the grain edges. Figure 1b shows the wettability of the untreated surface that has a contact angle of 88º. 30 Figure 2 shows the surface of an AISI 304 stainless steel sheet after the application of the method of the present invention to give it a superhydrophilic character. This micrograph has been obtained by means of a scanning electron microscope. Processing conditions: wavelength = 532 nm; speed = 25 mm / s; frequency = 20,000 Hz; Overlap = 75%; Energy per pulse = 0.3 mJ; Atmosphere: air.357In this case, a superhydrophilic surface is obtained as shown in Figure 2b (contact angle of 0 °) .In Figure 3 the surface of an AISI 304 stainless steel sheet is shown after the application of the method of the present invention for Give it a superhydrophilic character. This micrograph has been obtained by means of a scanning electron microscope. Processing conditions: wavelength = 1064 nm; speed = 50 mm / s; frequency = 10000 Hz; Overlap = 90%; Energy per pulse = 0.37 mJ; Atmosphere: air. In this case, a superhydrophilic surface is obtained as shown in Figure 3b (contact angle of 4 °) .10 Figure 4 shows the surface of an AISI 304 stainless steel sheet after the application of the method of the present invention for Give it a superhydrophobic character. This micrograph has been obtained by means of a scanning electron microscope. Processing conditions: wavelength = 532 nm; speed = 25 15mm / s; frequency = 20,000 Hz; Overlap = 75%; Energy per pulse = 0.3 mJ; Atmosphere: argon In this case a superhydrophobic surface is obtained as shown in Figure 4b (152 ° contact angle). Figure 5a shows the surface of an AA2024-T3 aluminum alloy sheet 20 after the application of the method of the present invention to give it a superhydrophilic character. This micrograph has been obtained by means of a scanning electron microscope. Processing conditions: wavelength = 1064 nm; speed = 20 mm / s; frequency = 20,000 Hz; Overlap = 0%; Energy per pulse = 0.53 mJ; Atmosphere: air. In this case, a superhydrophilic surface is obtained as shown in Figure 5b 25 (contact angle of 0 °). Figure 6a shows the surface of an AA2024-T3 aluminum alloy plate after the application of the method of present invention to give it a superhydrophobic character. This micrograph has been obtained by means of a scanning electron microscope. Processing conditions: wavelength = 1064 nm; speed = 20 mm / s; frequency = 20,000 Hz; Overlap = 0%; Energy per pulse = 0.53 mJ; Atmosphere: argon In this case a superhydrophobic surface is obtained as shown in Figure 6b (160 ° contact angle) .35PREFERRED REALIZATION OF THE INVENTION The present invention relates to a method of surface treatment that allows modifying the wettability thereof.The method object of the present invention comprises an application stage on the surface to be treated of a laser beam whose length of Wave is within the range of 532 nm to 1064 nm, the average power within the range 1W to 20 W, and the pulse width is at least 1 ns, so that the obtainable surface modifies the interfacial tension of the air / liquid set (water based) / material.This laser beam can perform a continuous sweep over the surface following a certain geometric pattern or be expanded and radiate the entire surface to be treated in a single exposure.When it comes to obtaining a superhydrophilic surface, the treatment by laser it encourages the liquid / solid interfacial tension to be minimal.15 When it comes to obtaining a superhydrophobic surface , the laser treatment encourages the gas / solid interfacial voltage to be minimal.The stage of application on the surface to be treated with a laser beam comprises a sub-stage in which at least one of the following parameters is adjusted: average power of the laser beam , laser beam size at the focus, pulse width, wavelength, type of interaction (fusion / vaporization), overlap between consecutive sweeps of the laser beam on the surface and type of atmosphere. These parameters are easily controllable and tunable depending on the type of material to be treated, its effects being visible when determining the wettability of the surface obtained.25 Below are examples of application of different types of lasers, with different powers, operating frequencies and speed of scanning on different materials. EXAMPLE 130: A laser of Nd: YVO4 (532 nm) of 7 W of average power was used, operating with a frequency of 20,000 Hz, 75% overlap, pulse duration of 14 ns, energy per pulse of 0.3 mJ, with a value of M2 <1.2, with a scanning speed of 25mm / s and in an air atmosphere, on the surface (material AISI304). A surface like the one shown in figure 2a is generated. As shown in Figure 2b, the surface is superhydrophilic (angle of 359th contact) In this case, the liquid / solid interfacial tension is minimized thanks to a modification of the surface texture and the generation of metal oxides. EXAMPLE 2 A 13 W average Nd: YVO4 (1064 nm) laser was used, operating at 10000 5Hz, overlap of 90%, pulse duration of 20 ns, energy per pulse of 0.37 mJ, with a value of M2 <1.2, with scanning speed of 50 mm / s and in air atmosphere, over the surface (material AISI304) .A surface is generated as shown in figure 3a. As shown in Figure 3b, the surface is superhydrophilic (contact angle 4º) .In this case, the liquid / solid interfacial tension is minimized thanks to a modification of the surface texture and the generation of metal oxides. EXAMPLE 3 It was used a laser of Nd: YVO4 (532 nm) of 7 W of average power, operating with a frequency of 20,000 Hz, overlap of 75%, pulse duration of 14 ns, energy per pulse of 15 mJ, with a value of M2 <1.2, with a scanning speed of 25 mm / s and in an argon atmosphere, on the surface (material AISI 304). A surface like the one shown in Figure 4a is generated. As shown in Figure 4b, the surface is superhydrophobic (contact angle152º). In this case, the interfacial / solid voltage is minimized thanks to a modification of the surface texture.20 EXAMPLE 4 A 13 W Nd: YVO4 (1064 nm) laser of average power was used, operating at 20,000 Hz, 0% overlap , pulse duration of 20 ns, energy per pulse of 0.53 mJ, with a value of M2 <1.2, with a scanning speed of 20 mm / s and in an air atmosphere, on surface 25 (material AA2024-T3 ). A surface like the one shown in Figure 5a is generated. As shown in Figure 5b, the surface is superhydrophilic (contact angle 0 °). In this case, the liquid / solid interfacial tension is minimized thanks to a modification of the surface texture and the generation of metal oxides.30 EXAMPLE 5 A 13 W Nd: YVO4 (1064 nm) laser of average power was used, operating at 20,000 Hz, 0% overlap, pulse duration of 20 ns, energy per pulse of 0.53 mJ, with a value of M2 <1.2, with a scanning speed of 20 mm / s and in an argon atmosphere, over the surface (material AA2024-T3). A surface like the one shown in Figure 6a is generated. 35 As shown in Figure 6b, the surface is superhydrophobic (contact angle10160º). In this case, the gas / solid interfacial tension is minimized by a modification of the surface texture. As used herein, the term "approximately" means a slight variation of the specified value, preferably within 10 percent of the specified value. However, the term "approximately" may mean a greater tolerance of variation depending for example on the experimental technique used. One skilled in the art understands such variations of a specified value and is within the context of the present invention. In addition, to provide a more concise description, some of the quantitative expressions provided herein do not qualify with the term "approximately." It is understood that, whether the term "approximately" is explicitly used or otherwise, it is intended that all amounts provided herein refer to the actual value given, and are also intended to refer to the approximation to that value given that it would be reasonably deduced based on the usual experience in the art, including equivalents and approximations due to the experimental and / or measurement conditions for such a given value. Once the nature of the present invention is sufficiently described, as well as how to bring it to the In practice, it only remains to be added that as a whole and its component parts, it is possible to introduce changes in form, materials and disposition as long as said alterations do not substantially vary said invention. 
    权利要求:
    Claims (1)
    [1]
    11 CLAIMS 1. Method for modifying the wettability of surfaces of different materials, characterized in that it comprises a step of applying a laser beam on the surface to be treated whose wavelength is within the range of 532 nm to 51064 nm, in such a way that modifies the texture and / or chemical composition of said surface at the micrometric and nanometric level minimizing or maximizing the interfacial tension of the air / liquid (water-based) / material assembly. 2. A method according to claim 1 in which the beam The laser can carry out a continuous scan over the surface following a determined geometric pattern, or be expanded and irradiate the entire surface to be treated in a single exposure. 3. A method according to claims 1 and 2 in which the average power of the laser beam is within the range 1 W to 20 W. 154. A method according to claims 1 to 3 in which the pulse width is at least 1 ns. 5. A method according to the preceding claims that makes it possible to obtain a superhydrophilic surface by promoting the minimum liquid / solid interfacial tension. 6. A method according to claims 1 to 4 that allows to obtain a superhydrophobic surface by promoting the The gas / solid interfacial tension is at a minimum. 7. A method according to the preceding claims in which the irradiation of the laser beam on the surface to be treated is carried out in the presence of an atmosphere of inert gas such as argon. 308 A method according to claims 1 to 6 in which the irradiation of the laser beam on the surface to be treated is carried out in the presence of an atmosphere of highly reactive gas such as air. 359. A method according to the preceding claims in which the application on the12 surface to be treated of a laser beam can be carried out following a predefined geometric pattern formed by lines in one or two directions on the surface to be treated. 10. A method according to the preceding claims which the application on the surface to be treated of a beam Laser according to a predefined geometric pattern formed by lines is applied by moving the laser beam, keeping the surface to be treated fixed, or by moving the surface to be treated, keeping the laser beam fixed, where the movable element does so by describing a linear or rotary movement .1011.Surface obtainable by the method of any of the preceding claims. 12.Surface according to any of the preceding claims, characterized by being superhydrophobic, with a contact angle value greater than or equal to 150 °. 1513.Surface according to any of the claims 1 to 11 characterized by being superhydrophilic, with a value of the contact angle less ro equal to 5 ° 14.Use of the surface generated according to claims 11 to 13 as a self-cleaning surface. 15.Use of the surface generated according to claims 11 and 12 as a water repellent surface, avoiding the formation of ice, detrimental to transmission of signals in radars and antennas and even dangerous in the wings and fuselage of airplanes. 25 16. Use of the generated surface according to claims 11 and 12 to avoid the formation of fog and corrosion in the case of metals. 17. Use of the generated surface according to claims 11 and 13 to help optimize heat transmission in water conduction tubes and plates. 18.Use of the surface generated according to claims 11 and 13 to avoid condensation of drops in the form of mist. 3519.Use of the surface generated according to claims 11 and 13 to promote the13 osteoblast growth and the consequent improvement in implant integration.
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    同族专利:
    公开号 | 公开日
    ES2597861A8|2017-02-27|
    ES2597861B1|2017-12-20|
    ES2597861R1|2017-02-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2019015143A1|2017-07-17|2019-01-24|英诺激光科技股份有限公司|Method for performing corrosion resistance processing on surface of metal by using laser, and application thereof|JPH04353529A|1991-05-30|1992-12-08|Teijin Ltd|Method for modifying surface of polyester|
    JP3209875B2|1995-03-23|2001-09-17|株式会社日立製作所|Substrate manufacturing method and substrate|
    GB9806352D0|1998-03-25|1998-05-20|British Nuclear Fuels Plc|A method of improving wettability and enamelling|
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