WO2018196241A1 - 一种电泳辅助微纳颗粒熔融自组装表面改性设备 - Google Patents

一种电泳辅助微纳颗粒熔融自组装表面改性设备 Download PDF

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WO2018196241A1
WO2018196241A1 PCT/CN2017/099463 CN2017099463W WO2018196241A1 WO 2018196241 A1 WO2018196241 A1 WO 2018196241A1 CN 2017099463 W CN2017099463 W CN 2017099463W WO 2018196241 A1 WO2018196241 A1 WO 2018196241A1
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electrophoresis
nanoparticle
processed
micro
surface modification
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PCT/CN2017/099463
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English (en)
French (fr)
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何俊峰
郭钟宁
邓宇
刘莉
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广东工业大学
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Priority to US16/153,773 priority Critical patent/US20190040542A1/en
Publication of WO2018196241A1 publication Critical patent/WO2018196241A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • the invention relates to the field of surface modification, in particular to an electrophoresis-assisted micro-nano particle melting self-assembly surface modification device.
  • metal is widely used in various fields of product processing.
  • metallic materials also have their inherent defects.
  • Metallic materials usually fail from the surface, and the most common forms of failure are wear, corrosion, and fracture.
  • the surface characteristics of metal materials mainly depend on the processing technology, so the processed products are prone to performance defects or deficiencies due to their process characteristics and processing quality. In order to improve the surface properties of metal materials such as strength, hardness, rigidity, wear resistance, corrosion resistance, etc., it needs to be post-treated to meet the requirements of use and performance.
  • the preparation of superhydrophobic surfaces mostly uses electrochemical etching or chemical etching to construct the rough structure required for superhydrophobic surfaces.
  • the electrochemical etching method prepares a regular rough surface by anodization, and then uses a low surface energy substance to modify to prepare a superhydrophobic surface.
  • the method is applicable to a wide range of materials and has good controllability, but the conditions are relatively harsh, and the electrolyte used is mostly corrosive acid. Or a mixture of alkalis, the consumption of the electrolyte is large, and the waste liquid recovery process is troublesome, which is not conducive to industrial production.
  • Chemical corrosion method firstly uses nitric acid, hydrochloric acid, hydrofluoric acid, etc.
  • the chemical etching method is simple and easy, but the materials used as the etching liquid are highly corrosive, and the waste liquid processing is troublesome, which limits the development of the chemical etching method.
  • nanoparticles are generally surface modified to be widely used in various fields: magnetic fluid, color imaging, magnetic recording materials, and biomedicine. Due to the surface hydrophobicity of the nanoparticles and the large surface-to-body ratio, it is easy to agglomerate in the organism, adsorbing plasma proteins, and is easily removed by the reticuloendothelial system (RES). Therefore, the surface modification of the nanoparticles is required to increase the pro Water-based, extending the cycle half-life.
  • RES reticuloendothelial system
  • Nanoparticles are currently one of the most active directions in the field of biomedical nanomaterials. Nanoparticles prepared by different methods have various biomedical applications after being modified by different polymers or molecular surfaces.
  • the existing metal surface modification methods generally include a thermal sintering method and a nickel salt thermal decomposition method.
  • the thermal sintering method immerses the carbon material in a liquid phase containing a modifying substance, and then melts the modified substance with a carbon surface by a medium-high temperature heat treatment. Binding to thereby adjust the hydrophilicity of the carbon surface.
  • This method is mainly to enhance the hydrophobicity by treatment with polytetrafluoroethylene, and to enhance the hydrophilicity by treatment with amines.
  • the molten material can protect the surface structure of the material, so the method has little effect on the surface structure of the carbon material.
  • the thermal sintering method introduces elements and groups in the modifying substance on the carbon surface.
  • the amino functional group is introduced into the carbon surface during the amination treatment and is mainly present in the form of an amide group. The introduction of an amino group on the surface of the carbon fiber can form a hydrogen bond with the epoxy group of water and epoxy resin, and the wettability is greatly improved.
  • PTFE is attached to the carbon surface to introduce a fluorocarbon group. Due to the increased PTFE content, the hydrophilic-hydrophobic balance can be better achieved. Thermal sintering to regulate hydrophilicity The advantage is that the steps are simple and the time is short.
  • the nickel salt thermal decomposition method firstly adsorbs NI2+ on the surface of the substrate, and then obtains a nickel catalytic center by thermally decomposing the nickel salt.
  • the activated glass solution of nickel sulfate and sodium hypophosphite was used to activate the hollow glass microspheres under ultrasound-assisted conditions for 2 min, and then thermally oxidized and reduced at 175 °C for 50 min to successfully achieve palladium-free electroless nickel-phosphorus plating of hollow glass microspheres. alloy.
  • the ceramic microbeads were immersed in the activation solution for 30 min, and then thermally oxidized and reduced at 175 ° C for 50 min to realize palladium-free electroless nickel-phosphorus alloy plating on the surface of the ceramic microbeads.
  • the disadvantage of the thermal sintering method is that high temperature treatment is required, the cost is high, and the adhesion of the modified substance may be uneven during the impregnation process, which may easily lead to uneven hydrophilic and hydrophobic properties on the surface of the treated carbon material.
  • the disadvantage of using nickel salt thermal decomposition method is that it is not suitable for base materials with lower melting point, and is only suitable for heat-resistant materials such as ceramics, glass, and silicon carbonate.
  • the chemical reagents used at the same time are low surface energy modifiers, which are polluted and dangerous to operate. Direct grinding pretreatment and heat treatment reduce the surface roughness of the metal.
  • the object of the present invention is to provide an electrophoresis-assisted micro-nanoparticle melting self-assembly surface modification device capable of enhancing the bonding force between a metal surface and a nanoparticle.
  • an electrophoresis-assisted micro-nanoparticle melting self-assembly surface modification device comprising:
  • a particle solution mixing cycle vessel mounted to the workbench and used to mix the nanoparticle solution
  • a processing tank installed on the workbench and used for placing a metal workpiece to be processed
  • An infusion device for transporting a nanoparticle solution to a surface of a metal workpiece to be processed
  • an electrophoresis auxiliary device installed on the worktable and respectively connected to connect the electrophoresis auxiliary cathode and the metal workpiece to be processed, and form an electrophoresis auxiliary electric field for nanoparticle deposition between the metal workpiece to be processed and the electrophoresis auxiliary cathode;
  • a vacuum heating device mounted on the table and used to heat a metal workpiece to be processed to melt a portion of the nanoparticles on the surface thereof;
  • the integrated control cabinet is internally provided with a controller that communicatively connects and controls the particle solution mixing cycle container, the infusion device, and the vacuum heating device.
  • the particle solution mixing cycle container is internally provided with an ultrasonic vibration device for vibrating the nanoparticles, a magnetic stirring device for stirring the nanoparticle solution, a suspension suction device for guiding the nanoparticle solution, and a filter circulation nanometer.
  • a solution circulation device for the granular solution is internally provided with an ultrasonic vibration device for vibrating the nanoparticles, a magnetic stirring device for stirring the nanoparticle solution, a suspension suction device for guiding the nanoparticle solution, and a filter circulation nanometer.
  • a solution circulation device for the granular solution for the granular solution.
  • the workbench is mounted with a micro-three-dimensional motion platform communicatively coupled to the controller
  • the processing slot is mounted on the micro-three-dimensional motion platform, and synchronously moves with the micro-three-dimensional motion platform to make a metal workpiece to be processed Align the infusion set.
  • the upper side of the processing tank bottom plate is fixedly mounted with a workpiece holder for holding a metal workpiece to be processed.
  • the working table is provided with a main shaft
  • the infusion device comprises a suction tube and a suction tube clamp
  • an opening of one end of the suction tube communicates with the particle solution mixing circulation container
  • the suction tube clamp clamps the attraction
  • the opening at the other end of the suction tube is aligned with the metal workpiece to be processed
  • the suction tube clamp is mounted to the spindle and movable along the spindle.
  • a cathode clamp is mounted on the main shaft, and the cathode clamp clamps the electrophoresis auxiliary cathode, one output end of the electrophoresis auxiliary device is connected to the cathode clamp, and the other output end is connected to the workpiece clamp.
  • the integrated control cabinet is externally provided with a keyboard and a display screen communicatively connected to the controller.
  • the table is mounted with a video detecting device for detecting the state of the surface of the metal workpiece to be processed.
  • the video detecting device includes a bracket mounted to the table and a charge coupled image sensor mounted to the bracket.
  • the invention provides an electrophoresis-assisted micro-nano particle melting self-assembly surface modification device, which comprises a worktable, a processing tank, an infusion device, an electrophoresis auxiliary device, a vacuum heating device and an integrated control cabinet.
  • the particle solution mixing circulation container is installed on the workbench and used for mixing the nanoparticle solution;
  • the processing tank is installed on the workbench and used for placing the metal workpiece to be processed;
  • the infusion device is used for conveying the nanoparticle solution to the surface of the metal workpiece to be processed;
  • the electrophoresis auxiliary device is installed And connecting the electrophoresis auxiliary cathode and the metal workpiece to be processed respectively to the worktable, and forming an electrophoresis auxiliary electric field for nanoparticle deposition between the metal workpiece to be processed and the electrophoresis auxiliary cathode;
  • the vacuum heating device is installed on The workbench is used to heat a metal workpiece to be processed to melt a part of the nanoparticles on the surface thereof;
  • a controller is disposed inside the integrated control cabinet, and the controller communicatively connects and controls the particle solution mixing circulation container, the infusion device, and the vacuum heating device.
  • the nanoparticle solution is thoroughly mixed in the particle solution mixing circulation container, and then the nanoparticle solution is transported to the surface of the metal to be processed, so that the mixed nanoparticles are deposited once or in stages on the metal surface to obtain an ordered particle arrangement, and then passed through a vacuum heating device.
  • the characteristics of the metal surface are then obtained by pro-hydrophobic micro-texture.
  • the Brownian motion of the particles is offset by the action of gravity, and is in a relatively balanced state in the suspension, which cannot be deposited or the deposition rate is slow and the efficiency is low, so the electrophoresis auxiliary device is utilized.
  • the electrophoresis-assisted electric field is formed, and a certain electric field is applied thereto by the electrophoresis effect of the microparticles.
  • the electrophoretic deposition has the advantages of convenient control, no special requirements on the particle type and the surface state of the particles, it can be in any plane, curved surface, convex table, concave Irregular metal surfaces such as grooves perform migration and adsorption of mixed micro/nano particles, or fractional migration and adsorption of different kinds of particles. It can greatly improve the deposition efficiency of extremely fine particles in the solution, and the deposition rate and deposition thickness can be adjusted by adjusting the electric field strength.
  • FIG. 1 is a schematic structural view of a specific embodiment of an electrophoresis-assisted micro-nanoparticle melting self-assembly surface modification device according to the present invention.
  • the core of the invention is to provide an electrophoresis-assisted micro-nano particle melting self-assembly surface modification device, which can enhance the bonding force between the metal surface and the nano particle.
  • FIG. 1 is a schematic structural view of a specific embodiment of an electrophoresis-assisted micro-nanoparticle melting self-assembly surface modification device according to the present invention.
  • a specific embodiment of the present invention provides an electrophoresis-assisted micro-nanoparticle melting self-assembly surface modification apparatus, including a work table 1, a particle solution mixing circulation container 2, a processing tank 7, an infusion device, an electrophoresis auxiliary device 12, and a vacuum heating device 10.
  • the particle solution mixing circulation container 2 is mounted on the table 1 and used to mix the nanoparticle solution.
  • the particle solution mixing cycle container 2 is internally provided with an ultrasonic vibration device for vibrating the nanoparticles, a magnetic stirring device for stirring the nanoparticle solution, a suspension suction device for guiding the nanoparticle solution, and a filter for circulating the nanoparticle.
  • Solution circulation device for the solution. A thorough mixing of the same particles or different particles can be achieved.
  • the particle size is on the order of nanometers, so that the nano-sized particles are fully fused in solution by ultrasonic vibration and magnetic stirring, and nanometer-sized different kinds of metal particles or different kinds of non-metal particles or different kinds of metal and non-metal particles are thoroughly mixed in the solution. .
  • the processing tank 7 is mounted on the table 1 and is used to place the metal workpiece 6 to be processed.
  • the worktable 1 is mounted with a micro three-dimensional motion platform 9 of a communication connection controller
  • the processing slot 7 is mounted on the micro three-dimensional motion platform 9 and moves in synchronization with the micro three-dimensional motion platform 9 to align the metal workpiece 6 to be processed with the infusion device.
  • the micro three-dimensional motion platform 9 can make the machining slot 7 perform an directional movement accurately, ensure the relative position of the machining groove 7 and the main shaft 4, and accurately place the pre-processing suspension on the metal workpiece 6 to be processed.
  • the workpiece holder 8 for holding the metal workpiece 6 to be processed is fixedly mounted on the upper side of the bottom plate of the machining groove 7.
  • the infusion device is used to transport the nanoparticle solution to the surface of the metal workpiece 6 to be processed.
  • the worktable 1 is provided with a main shaft 4, and the infusion device comprises a suction tube and a suction tube clamp 5, and the suction tube 1
  • the opening of the end is connected to the particle solution mixing circulation container 2, and the suction pipe clamp 5 clamps the other end of the suction pipe so that the opening of the other end of the suction pipe is aligned with the metal workpiece 6 to be processed, and the suction pipe clamp 5 is mounted on the main shaft 4 and can be along the main shaft 4. mobile.
  • the main shaft 4 is conveniently combined with the particle solution mixing circulation container 2, and the nanoparticle solution is sucked from the particle solution mixing circulation container 2 to the surface of the metal workpiece 6 to be processed through the suction tube clamp 5 connected to the main shaft 4, once. It is also possible to place the mixed solution on the surface of the metal workpiece 6 to be processed a plurality of times.
  • the electrophoresis auxiliary device 12 is mounted on the table 1 and electrically connected to the electrophoresis auxiliary cathode and the metal workpiece 6 to be processed, respectively, and forms an electrophoresis auxiliary electric field for nanoparticle deposition between the metal workpiece 6 to be processed and the electrophoresis auxiliary cathode.
  • a cathode clamp 5 is mounted on the main shaft 4, and the cathode clamp 5 holds the electrophoresis auxiliary cathode.
  • One output end of the electrophoresis auxiliary device 12 is connected to the cathode clamp 5 as a cathode, and the other output end is connected to the workpiece clamp 8.
  • the AC or DC power source is used to form an auxiliary electric field between the metal workpiece 6 to be processed and the cathode, and the auxiliary particles are deposited in an orderly manner, and the deposition efficiency is improved.
  • Different cathodes can be switched on-line, and electrophoresis auxiliary electric fields are formed with different workpieces to realize electrophoresis-assisted deposition.
  • electrophoretic deposition has the advantages of convenient control, no special requirements on the particle type and the surface state of the particles, it can be used in any plane, curved surface, convex table, groove and other irregular metals.
  • the surface is mixed with micro-nanoparticles for migration and adsorption, or fractionated to migrate and adsorb different types of particles. It can greatly improve the deposition efficiency of extremely fine particles in the solution, and the deposition rate and deposition thickness can be adjusted by adjusting the electric field strength.
  • the two-dimensional ordering of colloidal particles at the solid-liquid interface has the general property of maintaining colloidal stability at the interface.
  • the applied DC voltage or square wave pulse has a significant influence on the deposition structure of the particles, and the assembly process is modulated by applying a DC voltage or a square wave pulse to improve the order control of the two-dimensional deposition structure.
  • the colloidal particle suspension can form a variety of ordered curved surfaces or planar structures at the interface under the condition of an alternating/DC electric field perpendicular to the interface.
  • the vacuum heating device 10 is mounted to the table 1 and is used to heat the metal workpiece 6 to be processed to melt a portion of the nanoparticles on its surface.
  • the mixed suspension is placed on the metal workpiece 6 to be processed through the suction tube, and different kinds of particles are deposited once or in stages on the surface of the metal workpiece 6 to be processed. Arranged into ordered particles, and then placed in the vacuum heating device 10, heated to the melting temperature of the lower melting point of the sacrificial particles. Due to the different melting temperatures of the different particles, only certain kinds of particles will be melted under the control of specific temperature. Melted state.
  • the molten particles are wrapped or adhered to another modified particle, and the particle and the metal workpiece are "welded" together, thereby effectively improving the bonding force, forming a micro-nano nested structure and the effect of the particle self-bonding to achieve
  • the surface of the metal workpiece is modified by surface micro-nano particles to enhance the surface-hydrophobic modification and enhance the bonding force between the particles and the metal workpiece.
  • the integrated control cabinet 11 is internally provided with a controller that communicatively connects and controls the particle solution mixing circulation container 2, the infusion device and the vacuum heating device 10, and controls the operation of each device through the controller.
  • the integrated control cabinet 11 is externally provided with a keyboard and a display screen of the communication connection controller. It is also within the scope of the present invention to implement various functions of the device by providing different devices.
  • a video detecting device 3 for detecting the state of the surface nano-particles of the metal workpiece 6 to be processed may be mounted on the worktable 1, Real-time detection of the surface deposition of the processed metal workpiece 6 and the distribution of the particles in the molten state can be performed in real time.
  • the video detecting device 3 includes a bracket mounted on the workbench 1 and a charge coupled image sensor mounted on the bracket to improve the accuracy of detection, and can also be detected by other types of video detecting devices, all of which are protected by the present invention.

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Abstract

一种电泳辅助微纳颗粒熔融自组装表面改性设备，包括工作台(1)、颗粒溶液混合循环容器(2)、加工槽(7)、输液装置、电泳辅助装置(12)、真空加热装置(10)和集成控制柜(11)。使熔点较低的牺牲颗粒处于熔融状态，熔融的颗粒包裹或者粘连到另一种改性颗粒和金属工件(6)表面，增加金属工件(6)与微纳颗粒的结合力，利用改性颗粒本身的特点，进而使金属表面得到亲疏水微织构。电泳辅助装置可极大的提高溶液中极细颗粒的沉积效率，通过调节电场强度可以调节沉积速率和沉积厚度。

Description

一种电泳辅助微纳颗粒熔融自组装表面改性设备
本申请要求于2017年4月25日提交中国专利局、申请号为201710277890.4、发明名称为“一种电泳辅助微纳颗粒熔融自组装表面改性设备”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及表面改性领域，特别是涉及一种电泳辅助微纳颗粒熔融自组装表面改性设备。
背景技术
当今社会，材料的应用涉及到生活、生产的各个方面，不同材料各有其特点和应用范围。而金属作为目前最常用的材料，被广泛应用于产品加工的各个领域。然而金属材料也有其固有的缺陷，金属材料的失效通常源于表面，最常见的失效形式为磨损、腐蚀、断裂。金属材料的表面特性主要取决于其加工工艺，所以加工成型的产品由于其工艺特点与加工质量等原因，容易出现性能缺陷或者不足。为了提高金属材料的强度、硬度、刚性、耐磨性、耐腐蚀等表面性能，需要对其进行后处理，以满足使用及性能要求。
现代科技的高速发展，对金属材料表面性能要求的日益提高，对表面处理技术及工艺有了新的发展和扩充，对金属工件表面进行亲疏水等仿生结构的表面改性是较为热门的表面技术。随着疏水表面“荷叶效应”的发现，超疏水材料广泛用于自清洁、防冻、防雾、防腐、防阻、微流体芯片、无损液体输送等方面，展示了超疏水材料的广阔运用前景。
目前，超疏水表面的制备大多采用电化学腐蚀法或化学腐蚀法，构建超疏水表面所需粗糙结构。电化学腐蚀法通过阳极氧化制备规则的粗糙表面，然后使用低表面能物质改性制备超疏水表面。该方法适用的材料范围广，可控性好，但条件相对苛刻，所使用的电解液大多是腐蚀性较强的酸 或碱的混合液，电解液的消耗量较大，废液回收处理麻烦，不利于工业化的生产。化学腐蚀法常先采用硝酸、盐酸、氢氟酸等通过化学腐蚀来形成表面粗糙结构，然后再用热处理来构建表面的纳米结构，最后用低表面能物质改性制备超疏水表面。化学腐蚀法简单易行，但用作腐蚀液的物质都具有强的腐蚀性，废液处理麻烦，限制了化学腐蚀法的发展。
纳米尺寸的金属与功能分子的自组装在未来纳米电子器件中具有广阔的应用前景,对其基本理论和实际应用的研究正成为一个新兴的研究领域。目前纳米颗粒一般都要经过表面改性，使其广泛应用于各个领域：磁流体、彩色成像、磁记录材料以及生物医学。由于纳米颗粒的表面疏水性及较大的体表比，它在生物体内容易团聚,吸附血浆蛋白，容易被网状内皮系统(RES)清除，所以需要对纳米颗粒进行表面改性，增大亲水性,延长循环半衰期。可用于表面改性的物质很多，一般为有机物，也有无机物和蛋白质或抗体等。纳米颗粒目前是生物医用纳米材料领域异常活跃的方向之一。不同方法制备的纳米颗粒经不同聚合物或分子表面改性后具有多方面的生物医学应用。
现有的金属表面改性方法一般包括热烧结法和镍盐热分解法，热烧结法将碳材料浸渍在含改性物质的液相中，再通过中高温热处理使改性物质熔融与碳表面结合，从而调节碳表面亲疏水性。这种方法主要是通过聚四氟乙烯处理来增强疏水性，通过胺类物质处理来增强亲水性。
热处理时，熔融物质能够保护材料表面结构，所以该方法对碳材料表面结构的影响不大。通过原子力显微镜(AFM)表征指出多乙烯多胺熔融后能够保护碳纤维表面，形貌变化弱于仅热处理过的碳纤维。在化学组成方面，热烧结法在碳表面引入了改性物质中的元素和基团。在亲水改性方面，氨基官能团在氨化处理过程中被引入碳表面，并主要以酰氨基形式存在。碳纤维表面引入氨基后可以与水和环氧树脂的环氧基团形成氢键，浸润性得到很大改善。在疏水改性方面，PTFE附着碳表面后引入碳氟基团。由于PTFE含量增加，能更好地实现亲疏水平衡。热烧结法调控亲疏水性 的优点是步骤简便、时间短。
镍盐热分解法是先将NI2+吸附在基体表面，再通过热分解镍盐获取镍催化中心。人们用硫酸镍、次磷酸钠配置的活化液在超声辅助的条件下对空心玻璃微珠活化2min，再在175摄氏下热氧化还原50min，成功实现空心玻璃微珠的无钯活化化学镀镍磷合金。随后又采用该活化液浸泡陶瓷微珠30min，同样在175摄氏度下热氧化还原50min，实现在陶瓷微珠表面的无钯活化化学镀镍磷合金。
热烧结法的缺点是需要高温处理，成本较高，并且在浸渍过程中改性物质附着可能不均，容易导致处理碳材料表面亲疏水性质不均匀。采用镍盐热分解法的缺点是不适用于熔点较低的基体材料，只适用于陶瓷、玻璃、碳酸硅等耐热物质。同时使用的化学试剂为低表面能改性剂，有污染，操作有危险，直接打磨预处理和热处理使金属表面粗糙度降低。
如何提供一种能够增强金属表面与纳米颗粒结合力的金属表面改性设备是本领域技术人员目前需要解决的技术问题。
发明内容
本发明的目的是提供一种电泳辅助微纳颗粒熔融自组装表面改性设备，能够增强金属表面与纳米颗粒结合力。
为解决上述技术问题，本发明提供一种电泳辅助微纳颗粒熔融自组装表面改性设备，包括：
工作台；
颗粒溶液混合循环容器，安装于所述工作台并用于混合纳米颗粒溶液；
加工槽，安装于所述工作台并用于放置待加工金属工件；
输液装置，用于向待加工金属工件表面输送纳米颗粒溶液；
电泳辅助装置，安装于所述工作台并分别导通连接电泳辅助阴极和待加工金属工件，且在待加工金属工件和所述电泳辅助阴极之间形成用于纳米颗粒沉积的电泳辅助电场；
真空加热装置，安装于所述工作台，并用于加热待加工金属工件以熔融其表面的部分纳米颗粒；
集成控制柜，内部设置有控制器，所述控制器通信连接并控制所述颗粒溶液混合循环容器、所述输液装置和所述真空加热装置。
优选地，所述颗粒溶液混合循环容器内部设置有用于振动纳米颗粒的超声振动装置、用于搅拌纳米颗粒溶液的磁力搅拌装置、用于引导纳米颗粒溶液的悬浮液吸引装置和用于过滤循环纳米颗粒溶液的溶液循环装置。
优选地，所述工作台上安装有通信连接所述控制器的微三维运动平台，所述加工槽安装于所述微三维运动平台，并与所述微三维运动平台同步运动使待加工金属工件对准所述输液装置。
优选地，所述加工槽底板上侧固定安装有用于夹持待加工金属工件的工件夹具。
优选地，所述工作台上设置有主轴，所述输液装置包括吸引管和吸引管夹具，所述吸引管一端的开口连通所述颗粒溶液混合循环容器，所述吸引管夹具夹持所述吸引管的另一端，使所述吸引管另一端的开口对准待加工金属工件，所述吸引管夹具安装于所述主轴并能够沿所述主轴移动。
优选地，所述主轴上安装有阴极夹具，所述阴极夹具夹持所述电泳辅助阴极，所述电泳辅助装置的一个输出端连接所述阴极夹具，另一个输出端连接所述工件夹具。
优选地，所述集成控制柜外部设置有通信连接所述控制器的键盘和显示屏。
优选地，所述工作台上安装有用于检测待加工金属工件表面纳米颗粒状态的视频检测装置。
优选地，所述视频检测装置包括安装于所述工作台的支架和安装于所述支架的电荷耦合图像传感器。
本发明提供一种电泳辅助微纳颗粒熔融自组装表面改性设备，包括工作台、加工槽、输液装置、电泳辅助装置、真空加热装置和集成控制柜。 颗粒溶液混合循环容器安装于工作台并用于混合纳米颗粒溶液；加工槽安装于工作台并用于放置待加工金属工件；输液装置用于向待加工金属工件表面输送纳米颗粒溶液；电泳辅助装置，安装于所述工作台并分别导通连接电泳辅助阴极和待加工金属工件，且在待加工金属工件和所述电泳辅助阴极之间形成用于纳米颗粒沉积的电泳辅助电场；真空加热装置，安装于工作台，并用于加热待加工金属工件以熔融其表面的部分纳米颗粒；集成控制柜内部设置有控制器，控制器通信连接并控制颗粒溶液混合循环容器、输液装置和真空加热装置。
纳米颗粒溶液在颗粒溶液混合循环容器充分混合，然后将纳米颗粒溶液输送至待加工金属表面，使混合纳米颗粒在金属表面一次或者分次沉积，而得到有序的微粒排列，然后通过真空加热装置改变工件表面温度，使熔点较低的牺牲颗粒处于熔融状态，熔融的颗粒包裹或者粘连到另一种改性颗粒和金属工件表面，增加金属工件与微纳颗粒的结合力，利用改性颗粒本身的特点，进而使金属表面得到亲疏水微织构。同时对于尺寸很小的极细颗粒，颗粒的布朗运动与所受重力作用相抵消，在悬浊液中处于相对平衡的状态，不能沉积或者沉积速率很慢，效率较低，所以利用电泳辅助装置形成电泳辅助电场，通过微粒的电泳效应对其施加一定的电场作用，由于电泳沉积具有控制方便，对颗粒种类及颗粒表面状态无特殊要求等优点，所以可以在任意平面、曲面、凸台、凹槽等不规则金属表面进行混合微纳颗粒迁移和吸附，或者分次迁移和吸附不同种类颗粒。可极大的提高溶液中极细颗粒的沉积效率，通过调节电场强度可以调节沉积速率和沉积厚度。
附图说明
图1为本发明所提供的电泳辅助微纳颗粒熔融自组装表面改性设备的一种具体实施方式的结构示意图。
具体实施方式
本发明的核心是提供一种电泳辅助微纳颗粒熔融自组装表面改性设备，能够增强金属表面与纳米颗粒结合力。
为了使本技术领域的人员更好地理解本发明方案，下面结合附图和具体实施方式对本发明作进一步的详细说明。
请参考图1，图1为本发明所提供的电泳辅助微纳颗粒熔融自组装表面改性设备的一种具体实施方式的结构示意图。
本发明具体实施方式提供一种电泳辅助微纳颗粒熔融自组装表面改性设备，包括工作台1、颗粒溶液混合循环容器2、加工槽7、输液装置、电泳辅助装置12和真空加热装置10。
其中，颗粒溶液混合循环容器2安装于工作台1并用于混合纳米颗粒溶液。具体地，颗粒溶液混合循环容器2内部设置有用于振动纳米颗粒的超声振动装置、用于搅拌纳米颗粒溶液的磁力搅拌装置、用于引导纳米颗粒溶液的悬浮液吸引装置和用于过滤循环纳米颗粒溶液的溶液循环装置。可以实现相同颗粒或不同颗粒的充分混合。
颗粒尺度在纳米级，使纳米级的颗粒在溶液中通过超声振动和磁力搅拌充分融合，将纳米级的不同种类金属颗粒或者不同种类非金属颗粒或者不同种类金属与非金属颗粒充分混合在溶液中。
加工槽7安装于工作台1并用于放置待加工金属工件6。具体地，工作台1上安装有通信连接控制器的微三维运动平台9，加工槽7安装于微三维运动平台9，并与微三维运动平台9同步运动使待加工金属工件6对准输液装置。微三维运动平台9可以使加工槽7进行准确定向运动，保证加工槽7与主轴4的相对位置，并使加工前悬浊液准确置于待加工金属工件6上。为了保证加工过程中的稳定性，加工槽7底板上侧固定安装有用于夹持待加工金属工件6的工件夹具8。
输液装置用于向待加工金属工件6表面输送纳米颗粒溶液。具体地，工作台1上设置有主轴4，输液装置包括吸引管和吸引管夹具5，吸引管一 端的开口连通颗粒溶液混合循环容器2，吸引管夹具5夹持吸引管的另一端，使吸引管另一端的开口对准待加工金属工件6，吸引管夹具5安装于主轴4并能够沿主轴4移动。主轴4便于与颗粒溶液混合循环容器2组合，使纳米颗粒溶液通过与主轴4连接的吸引管夹具5把混合好的悬浮液从颗粒溶液混合循环容器2吸引至待加工金属工件6表面，可以一次也可以多次把混合好的溶液置于待加工金属工件6表面。
电泳辅助装置12安装于工作台1并分别导通连接电泳辅助阴极和待加工金属工件6，且在待加工金属工件6和电泳辅助阴极之间形成用于纳米颗粒沉积的电泳辅助电场。具体地，主轴4上安装有阴极夹具5，阴极夹具5夹持电泳辅助阴极，电泳辅助装置12的一个输出端连接阴极夹具5，作为阴极，另一个输出端连接工件夹具8。并在加工时通以交流或者直流电源，使待加工金属工件6与阴极间形成辅助电场，辅助颗粒有序沉积，并提高沉积效率。并可在线切换不同阴极，与不同工件组成电泳辅助电场，实现电泳辅助沉积。
通过微粒的电泳效应对其施加一定的电场作用，由于电泳沉积具有控制方便，对颗粒种类及颗粒表面状态无特殊要求等优点，所以可以在任意平面、曲面、凸台、凹槽等不规则金属表面进行混合微纳颗粒迁移和吸附，或者分次迁移和吸附不同种类颗粒。可极大的提高溶液中极细颗粒的沉积效率，通过调节电场强度可以调节沉积速率和沉积厚度。
在电场作用下，固液界面上胶体粒子的二维有序化具有在界面上保持胶体稳定性的普遍性质。外加直流电压或者方波脉冲对粒子的沉积结构具有明显影响，并通过外加直流电压或者方波脉冲调制组装过程，提高了二维沉积结构有序性的控制。在外加垂直于界面的交/直流电场的条件下，胶体粒子悬浮液可以在界面上形成多种有序曲面或平面结构。
真空加热装置10安装于工作台1，并用于加热待加工金属工件6以熔融其表面的部分纳米颗粒。把混合好的悬浊液通过吸引管置于待加工金属工件6上，在待加工金属工件6表面上一次或者分次沉积不同种类颗粒得 到有序的微粒排列，然后把工件置于真空加热装置10中，加热到熔点较低的牺牲颗粒融化温度，由于不同颗粒的融化温度不同，在特定温度控制下只有特定种类的颗粒会熔化成熔融状态。熔融的颗粒包裹或者粘连到另一种改性颗粒上，并把该种颗粒和金属工件“焊”在一起，有效提高结合力，形成微纳嵌套结构和颗粒熔融自结合的效果，以达到利用微纳颗粒对金属工件表面进行表面亲疏水改性并增强颗粒与金属工件间结合力的效果。
集成控制柜11，内部设置有控制器，控制器通信连接并控制颗粒溶液混合循环容器2、输液装置和真空加热装置10，通过控制器控制各装置的工作。具体地，集成控制柜11外部设置有通信连接控制器的键盘和显示屏。也可通过设置不同装置实现设备的各种功能，均在本发明的保护范围之内。
在上述各具体实施方式提供的电泳辅助微纳颗粒熔融自组装表面改性设备的基础上，还可以在工作台1上安装用于检测待加工金属工件6表面纳米颗粒状态的视频检测装置3，可以实时对待加工金属工件6表面沉积情况和熔融状态下的颗粒分布情况进行实时检测。具体地，视频检测装置3包括安装于工作台1的支架和安装于支架的电荷耦合图像传感器，以提高检测的准确性，也可采用其他类型的视频检测装置进行检测，均在本发明的保护范围之内。
以上对本发明所提供的电泳辅助微纳颗粒熔融自组装表面改性设备进行了详细介绍。本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (9)

  1. 一种电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，包括：
    工作台(1)；
    颗粒溶液混合循环容器(2)，安装于所述工作台(1)并用于混合纳米颗粒溶液；
    加工槽(7)，安装于所述工作台(1)并用于放置待加工金属工件(6)；
    输液装置，用于向待加工金属工件(6)表面输送纳米颗粒溶液；
    电泳辅助装置(12)，安装于所述工作台(1)并分别导通连接电泳辅助阴极和待加工金属工件(6)，且在待加工金属工件(6)和所述电泳辅助阴极之间形成用于纳米颗粒沉积的电泳辅助电场；
    真空加热装置(10)，安装于所述工作台(1)，并用于加热待加工金属工件(6)以熔融其表面的部分纳米颗粒；
    集成控制柜(11)，内部设置有控制器，所述控制器通信连接并控制所述颗粒溶液混合循环容器(2)、所述输液装置和所述真空加热装置(10)。
  2. 根据权利要求1所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述颗粒溶液混合循环容器(2)内部设置有用于振动纳米颗粒的超声振动装置、用于搅拌纳米颗粒溶液的磁力搅拌装置、用于引导纳米颗粒溶液的悬浮液吸引装置和用于过滤循环纳米颗粒溶液的溶液循环装置。
  3. 根据权利要求1所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述工作台(1)上安装有通信连接所述控制器的微三维运动平台(9)，所述加工槽(7)安装于所述微三维运动平台(9)，并与所述微三维运动平台(9)同步运动使待加工金属工件(6)对准所述输液装置。
  4. 根据权利要求3所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述加工槽(7)底板上侧固定安装有用于夹持待加工金 属工件(6)的工件夹具(8)。
  5. 根据权利要求4所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述工作台(1)上设置有主轴(4)，所述输液装置包括吸引管和吸引管夹具，所述吸引管一端的开口连通所述颗粒溶液混合循环容器(2)，所述吸引管夹具夹持所述吸引管的另一端，使所述吸引管另一端的开口对准待加工金属工件(6)，所述吸引管夹具安装于所述主轴(4)并能够沿所述主轴(4)移动。
  6. 工件权利要求5所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述主轴(4)上安装有阴极夹具(5)，所述阴极夹具(5)夹持所述电泳辅助阴极，所述电泳辅助装置(12)的一个输出端连接所述阴极夹具(5)，另一个输出端连接所述工件夹具(8)。
  7. 根据权利要求1所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述集成控制柜(11)外部设置有通信连接所述控制器的键盘和显示屏。
  8. 根据权利要求1至7任意一项所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述工作台(1)上安装有用于检测待加工金属工件(6)表面纳米颗粒状态的视频检测装置(3)。
  9. 根据权利要求8所述的电泳辅助微纳颗粒熔融自组装表面改性设备，其特征在于，所述视频检测装置(3)包括安装于所述工作台(1)的支架和安装于所述支架的电荷耦合图像传感器。
PCT/CN2017/099463 2017-04-25 2017-08-29 一种电泳辅助微纳颗粒熔融自组装表面改性设备 WO2018196241A1 (zh)

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