EP3083076A1 - Procédés d'hydrophobisation ou d'oléophobisation d'un matériau et élément hydrophobisé ou oléophobisé - Google Patents

Procédés d'hydrophobisation ou d'oléophobisation d'un matériau et élément hydrophobisé ou oléophobisé

Info

Publication number
EP3083076A1
EP3083076A1 EP15707284.4A EP15707284A EP3083076A1 EP 3083076 A1 EP3083076 A1 EP 3083076A1 EP 15707284 A EP15707284 A EP 15707284A EP 3083076 A1 EP3083076 A1 EP 3083076A1
Authority
EP
European Patent Office
Prior art keywords
gas
hydrophobing
component
hydrophobizing
oleophobierungsmittel
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.)
Granted
Application number
EP15707284.4A
Other languages
German (de)
English (en)
Other versions
EP3083076B1 (fr
Inventor
Reiner Nico Behrendt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Volkswagen AG
Original Assignee
Volkswagen AG
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 Volkswagen AG filed Critical Volkswagen AG
Publication of EP3083076A1 publication Critical patent/EP3083076A1/fr
Application granted granted Critical
Publication of EP3083076B1 publication Critical patent/EP3083076B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/025—Processes for applying liquids or other fluent materials performed by spraying using gas close to its critical state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/90—Form of the coating product, e.g. solution, water dispersion, powders or the like at least one component of the composition being in supercritical state or close to supercritical state

Definitions

  • the invention relates to a method for hydrophobing and / or oleophobization of a material and a component of an electric machine comprising or consisting of an oleophobated material.
  • Components are often made, at least in some areas, with polymers coated materials. These polymers are used, for example, as potting compounds for electrical machines, printed circuit boards or electrical assemblies, but also for bonding and, for example in the form of protective coatings, as a coating. Many material groups of the components involved often show signs of corrosion or swelling on contact with oily and / or aqueous solutions. An example of this is the so-called copper corrosion, which often starts when electrical and / or electronic components come into contact with media necessary for the functioning. In the field of bonding, however, in particular problems occur when moisture penetrates between the contact areas of polymer and component and there leads to corrosion, decomposition and swelling, which in turn can lead to destruction of the adhesive bond and the component. Particularly relevant are such problems in the field of electrical machines.
  • Drive motors for motor vehicles, starters, generators or starter generators convert electrical energy into mechanical energy (motors) or mechanical energy into electrical energy (generators).
  • This electromechanical transformation is based on electromagnetic induction.
  • Such electrical machines include a fixed stator (stator), the stator of a common type (laminated core) with
  • a movable component which is formed in the most common type as a rotor (rotor), which is rotatably mounted in or around the annular stator and has a plurality of permanent magnets.
  • a current flow in the stator winding is generated (generator) or due to the through Magnetic field generated by the stator causes the mechanical movement / rotation of the rotor (motor).
  • Reverse construction types in which the rotor comprises a winding and the stator comprises magnets are also known.
  • Parts of the winding and the switching ring having stator and / or rotor are embedded for the purpose of their electrical insulation and their mechanical protection and protection against chemical influences in a potting compound.
  • the casting compound is used in particular for embedding the switching ring (also referred to as a switching ring or contact bridge), which electrically interconnects the individual windings.
  • potting compounds are based on a silicone rubber.
  • these silicone elastomers often contain an addition of high filler fractions, for example in the form of quartz particles.
  • high filler fractions for example in the form of quartz particles.
  • Such materials meet most of the technical requirements for potting compounds, in particular they have a very low electrical conductivity, high temperature and thermal shock resistance, high thermal conductivity, high oxidation stability, good substrate adhesion and ease of curing and high processing tolerance.
  • the problem is the high affinity of the silicones for hydrocarbons. So they show the tendency to include engine and transmission oils and swell. The swelling affects the mechanical properties. For example, the strength and hardness of the material decreases, the temperature resistance decreases, and detachment and possibly embrittlement of the potting compound can be the result.
  • the design-related contact with gear oils in contact is thus the reduction or
  • the Magnetverklebung should basically the same technical
  • Adhesive effect for the magnets or laminated cores have.
  • the silicone resin system used should also not be impaired by the penetration of moisture or oils and the adhesive strength should be reduced.
  • DE 31 33 734 C2 describes an electrical insulation for a winding head of a stator or rotor of an electrical machine, which simultaneously protects against moisture.
  • the coating contains a silicone rubber as a base material which contains rod-shaped copolymers based on styrene-butyl acrylate instead of a mineral filler.
  • Gasphasenfluor ist applied which is a complex combination of plasma treatment, air supply, grafting of fluorocarbon monomers and then another
  • Plasma treatment in CF 4 atmosphere requires (US 201 1045200A1).
  • US 5,416,373 describes a winding of a stator or rotor of an electrical machine, in which the winding is coated with an electrically insulating film or with a Glimmmerband. In the exposed winding head area, a fluorine-containing coating is additionally applied in order to protect the winding against moisture.
  • the object of the invention is to provide a process for the hydrophobization and / or oleophobization of components which solves or at least alleviates the problems of the prior art.
  • the durability and durability of the hydrophobization and / or oleophobization should be significantly increased.
  • a first aspect of the invention relates to a process for the hydrophobization and / or oleophobization of a material comprising
  • the process sequence may, if necessary, be the same or different
  • Hydrophobing and / or Oleophobianssmittel be repeated.
  • Spraying or dipping on the materials to be isolated only a protective layer in the nanometer range can be applied. If the surface is damaged or has these foreign phases, for example due to filler particles, oil can penetrate into these places, damage the material and further damage the insulation layer
  • the inventive method achieves a depth impregnation of the treated material.
  • This can be achieved by using a compressed gas as a carrier for a hydrophobing and / or oleophobizing agent.
  • the loaded gas penetrates deep into the materials to be isolated together with the hydrophobing and / or Oleophobi für für assupra.
  • the hydrophobizing and / or Oleophobi für assupra a subsequent removal of the gas. Accordingly, both a depth impregnation of a few nanometers and a surface impregnation of a material can be achieved by the method according to the invention.
  • the loading of the compressed gas generally takes place under pressure and can be carried out in a pressure chamber, for example an autoclave. Under loading in the present invention, a process is understood in which it by sorption to a pressure chamber, for example an autoclave.
  • a hydrophobizing and / or oleophobizing agent is to be understood as meaning an agent which has the oleophobic, ie the oil-repellent character of a substance, in particular its content
  • the oleophobicity can be measured, for example, by (in particular static) measurement of the contact angle of a drop of oil on a flat surface of the material, with the contact angle correspondingly increasing with increasing oleophobicity.
  • For water repellents and Hydrophobicity is analogous, whereby the water-repellent character is measured using a drop of water.
  • hydrophobizing and / or oleophobizing agents also and preferably include those which also have a hydrophobicizing effect via their oleophobic properties.
  • the hydrophobing and / or Oleophobieren a material according to the invention by contacting the material with the loaded gas. These materials are part of a component.
  • Components are to be understood as materials which are processed in production processes and enter or represent the end products. This includes both semi-finished products, such as individual components, semi-finished products, such as stators and rotors in a manufacturing stage, but also finished products, such as e-machines. Furthermore, both components of metals and non-metals as well as organic and inorganic
  • the contacting of the material with the loaded gas can also in a
  • Pressure chamber happen which is conveniently adjacent to the pressure chamber in which the compressed gas was loaded with the hydrophobing and / or Oleophobi für sstoff.
  • the opening of a lock would then cause the laden gas in the chamber in which the component is located to spread and fill. It is preferred that there is no decompression of the gas, but the gas is still compressed, so that the compressed gas saturates the surface and the near-surface region of the material.
  • the gas can be separated from the material and removed from the chamber. This results in a separation between gas and hydrophobing and / or Oleophobitechnischsstoff.
  • the hydrophobing and / or Oleophobitechnischsstoff remains on and / or in the material.
  • the gas can be returned to the process and reused.
  • the material may be subject to subsequent treatments, e.g. a temperature step for reacting the reactive hydrophobing and / or Oleophobi mecanicsstoffs with the material to be subjected.
  • the component is one or more parts of an electric machine.
  • Electrical machines in particular rotors, stators, coils, their slot insulation, crimp connections, high-voltage and coil connections and shift rings are frequently exposed to engine and / or transmission oils. They persist, however often of materials such as copper, tin and other metals, which tend under the influence of such oils to corrosion and thus destruction.
  • these components are to be protected by a hydrophobing and / or oleophobization whose durability is in a meaningful relationship to the useful life, such as running time of the electric machine or the parts of an electric machine.
  • components For the purpose of electrical insulation and / or encapsulation, components, at least in some areas, have a surface comprising a polymer. In a preferred embodiment of the invention, it is in the hydrophobic and / or oleophobierendem
  • Polymers are chemical compounds, in particular hydrocarbon compounds, from chains or branched molecules, which in turn consist of identical or similar units, the so-called repeating units.
  • silicones are particularly preferred for the isolation of components. These may advantageously be suitable both for sealing and for bonding.
  • the frequent use of silicone, such as potting compound in electric machines, stems in particular from the combination of high elasticity with low electrical conductivity, high thermal shock resistance, high thermal conductivity and high oxidation stability at the same time good underground adhesion ago.
  • Such properties are found especially in silicones and epoxy resins, especially toughened epoxy resins.
  • polymers in particular silicones, advantageously show a high permeability to the compressed gas.
  • the loaded compressed gas ensures that the loaded gas when contacting the component not only wets the surface of the polymer, but rather penetrates the polymer.
  • the loaded compressed gas also penetrates into the near-surface region of the polymeric material.
  • the compressed gas is present as a supercritical fluid.
  • a substance is then present as a supercritical fluid when pressure and temperature are above the critical point of the substance.
  • the substance is then in a state in which the differences between liquid and gaseous cease to exist.
  • Supercritical fluids therefore have significantly different properties than gases or liquids. For the most part, the diffusibility is similar to that of the gas, with the dissolving power closer to that of the liquid.
  • Solvent properties in turn depend strongly on the density, which can be influenced in a relatively wide range. Higher density increases the solubility of most Substances. Supercritical fluids are extremely agile substances thanks to their high diffusibility.
  • the compressed gas used in the process according to the invention is compressed in such a way that it is present as a supercritical fluid, it not only has a high degree of diffusibility, which makes it capable of producing the material
  • the gas is carbon dioxide.
  • Carbon dioxide is a gaseous non-toxic substance at room temperature.
  • the weak polarity, especially in the supercritical state, makes it an ideal solvent for most water repellents and oil repellents.
  • the critical point of carbon dioxide is 31 ° C and 73.8 bar. Therefore, carbon dioxide is in
  • oxygen in particular critical oxygen.
  • critical oxygen the location of the critical point (50.4 bar and -1 18.4 ° C) makes handling in production more difficult.
  • solution behavior in the case of oxygen is limited to non-polar solvents and thus does not cover the entire range of the preferred hydrophobizing and / or oleophobizing agents in materials science.
  • the hydrophobizing and / or oleophobizing agent comprises fluorocarbon compounds.
  • Fluorocarbon compounds are partially or perfluorinated hydrocarbon compounds.
  • the fluorocarbon compound is a fluoroalkylsiloxane. These are trifunctional organic compounds, more specifically by fluoroalkyl groups and optionally
  • Aminoalkyl groups functionalized oligosiloxanes are functionalized oligosiloxanes.
  • the particular advantage over other fluorocarbon compounds is that in addition to the hydrophobic and oleophobic ones Characteristics of the compound to form Si-O bonds and subsequent cross-linking to chemical reactions with the surface of the material, in particular a polymer, may occur, whereby a particularly good connection between surface and hydrophobizing or Oleophobistoffsstoff forms.
  • tridecafluorooctyltrietoxysiloxane as fluoroalkylsiloxane has proven particularly advantageous. This compound is particularly well suited for production, as it shows on the one hand very good adhesion, hydrophobing and Oleophobi réelleseigenschaften and also is non-toxic and therefore processable with little effort.
  • the fluorocarbon compounds have polar and / or ionic functional groups. These increase the oleophobic character of the fluorocarbon compounds.
  • the fluorocarbon compound is then preferably a fluorosurfactant, in particular an ionic fluorosurfactant.
  • fluorosurfactants comprise short to medium-length partially or perfluorinated carbon chains which have a hydrophobic character.
  • fluorosurfactants have a polar, in particular an ionic, group in preferably terminal position, which gives the compound the desired oleophobic character.
  • Preferred chain lengths of the hydrophobic partially or perfluorinated carbon chain are in the range of 2 to 40 carbon atoms, in particular from 4 to 30
  • Carbon atoms preferably from 5 to 15 carbon atoms.
  • Oleophobieren so the contacting of the material with the compressed gas over a period of one minute to 10 hours instead. Within this period, a balance of the concentration of the gas within the material and outside of the material is established and thus to an equilibrium concentration of the gas
  • Hydrophobizing or Oleophobianssmittels inside and outside the material This equilibrium concentration of hydrophobizing or Oleophobiansssch simultaneously represents the maximum concentration of the hydrophobing or
  • the saturation curve typically shows a hyperbolic pattern.
  • the concentration of hydrophobing and / or Oleophobistoffsstoff on the surface and within the material is proportional to the concentration of the hydrophobizing or Oleophobistoffsstoffs within the carrier, ie the gas or the supercritical fluid.
  • the concentration of the hydrophobizing or Oleophobitechnischsstoffs within the carrier in turn depends on the solvent power of the carrier.
  • the solvent properties of the carrier in turn, in particular in the supercritical state, are proportional to the density of the carrier. Since the carrier should preferably be present at least almost saturated with hydrophobizing or Oleophobi mecanicsstoff, the hydrophobicizing or oleophobizing preferably takes place under a pressure of at least 55 bar and / or at a temperature of at least 25 ° C.
  • the removal of the gas is triggered by pressure reduction.
  • a pressure reduction to ambient pressure in particular, the largest possible pressure gradient is realized. Preference is thus given to a sudden
  • the gaseous present preferably of
  • Hydrophobizing or oleophobizing liberated carrier can by suitable apparatus in the first chamber, in the formerly the loading of the carrier with
  • a further aspect of the present invention relates to a component of an electric machine comprising a material or consisting of a material, wherein a hydrophobing and / or oleophobizing agent in a near-surface region of the material to a depth of at least 1 mm, in particular at least 2mm, preferably at least 2, 5 mm, in which material is detectable.
  • the hydro- and / or oleophobizing agent in the said depths preferably has a mass fraction of at least 1 wt .-% based on the total mass of material and hydro- or Oleophobitechnischsmittel.
  • the component according to the invention is hydro-functional and / or oleophobic, for example by the method described above.
  • Figure 1 is a schematic representation of the method according to the invention.
  • FIG. 1 shows the invention
  • the chamber 30 should be a pressure chamber adapted to the necessary pressure and temperature conditions to produce a supercritical gas.
  • the hydrophobing and / or Oleophobianssstoff 21 preferably comprises a
  • Fluorocarbon compound which in the present example has polar and / or ionic groups.
  • fluorocarbon compound is a fluoroalkyl siloxane as from Evonik under the trademarks Dynasylan ® F8261, Dynasylan ® F8263, Dynasylan ® F8815, Dynasylan ® Sivo and Dynasylan ® Sivo CLEAR and Dynasylan ® Sivo Clear EC is sold.
  • an ionic fluorine surfactant is sold.
  • This preferably contains an acrylate-based binder and / or wetting agent.
  • a suitable product is available under the trade designation Capstone ® FS-63 (Fa. DuPont).
  • Capstone ® FS-81 FS Capstone 22, Capstone FS 61 FS 63 Capstone, Capstone FS 81 FS Capstone 3100 or Zonyl ® FSP can (all from DuPont) may be used.
  • oleophobic material 15 includes.
  • the component 10 may also after the
  • the component 10 is, for example, a stator of a
  • Component 10 has a material 15 on its surface.
  • the material 15 may be a layer of a polymer, here a potting compound. It is irrelevant whether the layer is applied over the entire surface or only in a certain area of the surface.
  • the material 15 is in particular a silicone, preferably a methylpolysiloxane rubber, for example a vinylmethylpolysiloxane rubber (VMQ) or a phenylvinylmethylpolysiloxane rubber (PVMQ).
  • a silicone preferably a methylpolysiloxane rubber, for example a vinylmethylpolysiloxane rubber (VMQ) or a phenylvinylmethylpolysiloxane rubber (PVMQ).
  • VMQ vinylmethylpolysiloxane rubber
  • PVMQ phenylvinylmethylpolysiloxane rubber
  • the loaded gas 20 is evenly distributed in the chamber 35 due to normal physical processes and the given degrees of freedom. It also deposits on it the surface of the component 10, in particular on the material / polymer 15 from ( Figure 1 c). Due to the high degree of diffusibility of compressed gases, the laden gas 20 penetrates into the region of the material 15 near the surface. Also favored is the inclusion of penetration of the laden gas 20 through the conditions prevailing in the interior of the chamber 35 conditions, such as pressure and temperature. Both parameters are increased in relation to the normal conditions (25 ° C and 1 bar). Again, since both parameters are directly related to the diffusivity of the loaded gas 20 and thus to the depth of penetration, the conditions within the chamber 35 favor laden gas 20 as high as possible in the material 15. In addition to the highest possible penetration depth, it is advantageous that the loaded gas 20 as evenly as possible on the surface of the
  • Material 15 is concentrated. These parameters are preferably influenced by the exposure time, ie the common residence time of loaded gas 20 and material 15 in the chamber 35 under elevated pressure. Ideal exposure times are between one minute and 10 hours, but preferably between 1 and 7 hours. Within this time, a saturation of the material 15 with loaded gas 20 occurs.
  • the compressed gas 20 is separated from the material 15 ( Figure 1 d). This may preferably be done by pressure reduction, wherein the compressed gas 20 is expanded and passes into a gaseous state. It loses his
  • Oleophobicating agent 21 is no longer present dissolved in the gas 22. While the gas 22 escapes from the material 15 and is conducted out of the chamber 35 via a way, not shown, the more inert hydrophobing and / or oleophobizing agent 21 remains in and on the material 15. Excess water repellent and / or oil repellent 21, ie such which has not penetrated into the material 15 or not
  • Oleophobing agents 21 are not contaminated in the process according to the invention, so that they are introduced again into the first chamber 30, optionally concentrated and

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne des procédés d'hydrophobisation ou d'oléophobisation d'un matériau. Selon l'invention, le procédé comprend les étapes consistant à : - charger un gaz comprimé (22) avec un agent d'hydrophobisation et/ou d'oléophobisation (21), - mettre le matériau (15) en contact avec le gaz (20) comprimé et chargé, et - éliminer le gaz (20) du matériau (15). L'invention concerne en outre un élément d'une machine électrique, comprenant un tel matériau ou constitué de celui-ci. Selon l'invention, un agent d'hydrophobisation et/ou d'oléophobisation peut être détecté dans une région, proche de la surface, du matériau jusqu'à une profondeur d'au moins 1 mm dans le matériau.
EP15707284.4A 2013-12-17 2015-01-06 Procédés d'hydrophobisation ou d'oléophobisation d'un matériau et élément hydrophobisé ou oléophobisé Active EP3083076B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013226215.9A DE102013226215A1 (de) 2013-12-17 2013-12-17 Verfahren zur Hydrophobierung und/oder Oleophobierung eines Werkstoffs sowie hydrophobiertes und/oder oleophobiertes Bauteil
PCT/EP2015/050093 WO2015161933A1 (fr) 2013-12-17 2015-01-06 Procédés d'hydrophobisation ou d'oléophobisation d'un matériau et élément hydrophobisé ou oléophobisé

Publications (2)

Publication Number Publication Date
EP3083076A1 true EP3083076A1 (fr) 2016-10-26
EP3083076B1 EP3083076B1 (fr) 2020-03-11

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EP15707284.4A Active EP3083076B1 (fr) 2013-12-17 2015-01-06 Procédés d'hydrophobisation ou d'oléophobisation d'un matériau et élément hydrophobisé ou oléophobisé

Country Status (4)

Country Link
EP (1) EP3083076B1 (fr)
CN (1) CN105992654A (fr)
DE (1) DE102013226215A1 (fr)
WO (1) WO2015161933A1 (fr)

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DE102013226215A1 (de) * 2013-12-17 2015-06-18 Volkswagen Aktiengesellschaft Verfahren zur Hydrophobierung und/oder Oleophobierung eines Werkstoffs sowie hydrophobiertes und/oder oleophobiertes Bauteil
EP3315214B1 (fr) 2016-10-25 2020-07-15 The Swatch Group Research and Development Ltd Procédé d'épilamage d'un élement d'une pièce d'horlogerie ou de bijouterie
CN109293974A (zh) * 2018-09-29 2019-02-01 张青美 一种高效吸油橡胶材料的制备方法
DE102019121653A1 (de) * 2019-08-12 2021-02-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. 3D-Druckverfahren von Multimaterialmischungen zur Erzeugung von Objekten, 3D-Druck-Fertigungsanlage für die Erzeugung von Objekten mit Multimaterialmischungen mittels Laserstrahlschmelzen, Objekt
CN112593431B (zh) * 2020-11-17 2023-06-13 浙江弘伦纸业有限公司 一种高透气疏水型吸尘袋纸及其生产工艺
CN115079556A (zh) * 2022-07-11 2022-09-20 湖南伟博智能科技有限公司 一种触摸精准的具有防潮功能的智能型电话手表

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DE102013226215A1 (de) * 2013-12-17 2015-06-18 Volkswagen Aktiengesellschaft Verfahren zur Hydrophobierung und/oder Oleophobierung eines Werkstoffs sowie hydrophobiertes und/oder oleophobiertes Bauteil

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Also Published As

Publication number Publication date
WO2015161933A1 (fr) 2015-10-29
EP3083076B1 (fr) 2020-03-11
CN105992654A (zh) 2016-10-05
DE102013226215A1 (de) 2015-06-18

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