• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to an electrolyte for electropolishing metal surfaces, wherein the electrolyte comprises methanesulfonic acid, and additionally at least one phosphonic acid is contained, as well as its use for post-processing made of metal powder by additive method parts, in particular of titanium and aluminum alloys.
    公开号:AT520365A1
    申请号:T50716/2017
    申请日:2017-08-29
    公开日:2019-03-15
    发明作者:
    申请人:Hirtenberger Eng Surfaces Gmbh；
    IPC主号:
    专利说明:

    The invention relates to an electrolyte for electropolishing metal surfaces, in particular parts produced from metal powder by means of an additive method, the electrolyte containing methanesulfonic acid.
    The additive manufacturing of metal parts (3D printing) is a relatively new technology that is used more and more frequently due to its flexibility in the design of components, which is considerably expanded compared to conventional manufacturing processes. The principle of this manufacturing process is to sinter or melt a layer of metal powder in a controlled manner using a laser or electron beam. At the end, the finished component is embedded in the metal powder.
    The surfaces of components manufactured in this way have ripples and roughnesses due to the process, which are due to the grain size of the metal powder used, the layer thickness used for the structure and the beam geometry of the energy beam used. This fact makes the practical use of parts manufactured in this way difficult in technology. A classic mechanical post-processing of 3D printed parts is usually either not economical or practically impossible due to the complex geometry of the component.
    Electropolishing processes according to the prior art are suitable for leveling roughness in the one-digit to the low double-digit micrometer range (the removal here is typically 10 pm to 40 pm), but they regularly fail due to the roughness that occurs in 3D printing, which extends into the tenth of a millimeter range ,
    DE 10 2006 053 586 B3 describes such an electropolishing process, in which an electrolyte of the type mentioned at the beginning is used.
    It is therefore an object of the invention to overcome the disadvantages of the known
    Eliminate electropolishing processes and in particular to provide an electrolyte that allows surface treatment of parts made from metal powder using an additive process.
    / 14
    According to the invention, this object is achieved by an electrolyte of the type mentioned at the outset in that at least one phosphonic acid is additionally present in the electrolyte.
    The electrolyte according to the invention is able to level out the large roughnesses that arise due to the process in 3D printing. Of course, the electrolyte according to the invention can also be used in the post-processing of conventionally produced metal components. It is particularly suitable for the post-processing of components made of titanium alloys, with a suitable variation of the composition is also the processing of
    Aluminum alloys possible.
    According to the invention, the at least one phosphonic acid is selected from a group that contains mono-, di- and / or polyphosphonic acids, preferably amino-tris (methylenephosphonic acid) or mixtures thereof.
    Investigations by the inventors have shown that, particularly in the case of components made of titanium alloys, excellent results are obtained in their remaining surface roughness if the at least one phosphonic acid is present in a concentration of 0.1% to 10% by weight.
    It is particularly advantageous, particularly when used for 3D printed parts, if at least one polyhydric alcohol, preferably with at least three, particularly preferably more than three, functional hydroxyl groups and / or at least one polyalcohol is additionally present in the electrolyte according to the invention, the alcohol preferably consisting of a group is selected which contains glycol, glycerin, polyvinyl alcohol, inositol or sorbitol or mixtures thereof. It has been shown that these alcohols, as complexing agents, wetting agents and viscosity modifiers, have a significant influence on the leveling effect. In particular, this effect increases with an increasing number of functional hydroxyl groups of the alcohol used. Mixtures of different alcohols can also be used.
    The at least one alcohol is usually contained in a concentration of up to 10% by weight in the electrolyte according to the invention.
    / 14
    Depending on the surface and material of the component to be treated, further additives are contained in the electrolyte according to the invention. Here, in particular, further additives are used which are selected from a group which contains mineral acids, in particular phosphoric acid and sulfuric acid, fluorides, in particular ammonium difluoride, and amines, in particular ethanolamines and isopropanolamines. The mineral acids are usually contained in the electrolyte in a concentration of up to 50% by weight, the fluorides in a concentration of up to 20% by weight and the amines in a concentration of up to 15% by weight.
    The electrolyte according to the invention is used in particular for the finishing of parts made from metal powder by means of an additive method, in particular from titanium and aluminum alloys.
    The invention is explained in more detail below on the basis of non-restrictive exemplary embodiments. The percentages are to be understood as percentages by weight, unless stated otherwise.
    In preparation for the electrochemical post-processing of 3D printed parts, mechanical cleaning is carried out in a first step, for example by blasting or shot peening, in order to remove loosely adhering metal powder or metal powder that has accumulated in cavities and undercuts and is not connected to the component.
    After this cleaning step, the component is mechanically fixed at a suitable point, electrically contacted, immersed in the electrolytes according to the invention and anodically loaded according to an electrochemical process that is matched to the material and the component geometry.
    The concentrations of the individual constituents of the electrolyte are adjusted in such a way that a predefined final roughness of the component surface is achieved.
    Depending on the requirements, the current used can be direct current, a unipolar pulse current or a bipolar reverse pulse current. The combination of different processes is also possible.
    / 14
    The bath temperature is between 20 ° C and 75 ° C and is also matched to the workpiece to be treated.
    An improvement in the results is achieved if movement of the electrolyte by pumping and / or stirring is provided in order to achieve an effective electrolyte circulation at those points where the greatest removal is to take place.
    Example 1: Aftertreatment of a 3D printed component made of Ti6Al4V
    A 3D printed component for technical applications made of the titanium alloy Ti6Al4V is removed from the 3D printer, mechanically pre-cleaned and electrically contacted. Then the component is in an electrolyte bath consisting of 98% methanesulfonic acid, 2% amino-tris (methylenephosphonic acid) and at a temperature of 50 ° C, at an average voltage of 20 V and an average current density of 12.5 A / dm 2 by means of Treated pulse current for 30 minutes. The component is then rinsed with deionized water and dried using compressed air.
    1 shows an SEM image of a surface area of the component before the method according to the invention described above is carried out. 2 shows this surface after the method according to the invention has been carried out. The Ra value is reduced from 15 pm before to 3 pm after the aftertreatment according to the invention.
    Example 2: Post-treatment of a 3D printed component made of AlMgSi10
    A 3D-printed component made of the highly silicon-containing alloy AlMgSi10 is after mechanical cleaning and electrical contacting in an electrolyte consisting of 4.4% methanesulfonic acid, 45.6% phosphoric acid, 32.7% sulfuric acid, 4.5% triethanolamine, 0, 4% amino-tris (methylenephosphonic acid) and 12.4% ammonium difluoride at a voltage of 18 V and a current density of 4 A / dm 2 smoothed for 40 minutes. The component is then rinsed with deionized water and dried using compressed air.
    / 14
    3 and FIG. 4 again show an SEM image of the surface of the component before or after the method according to the invention has been carried out, the Ra value determined decreasing from 1.4 pm to 0.3 pm.
    Example 3: Post-treatment of a 3D printed component made of Ti6Al4V
    A 3D printed component for technical applications made of the titanium alloy Ti6Al4V is removed from the 3D printer, mechanically pre-cleaned and electrically contacted. The component is then placed in an electrolyte bath consisting of 98% methanesulfonic acid, 1.5% amino-tris (methylenephosphonic acid) and 0.5% inositol at a temperature of 45 ° C, at an average voltage of 20 V and an average current density of 5 A / dm 2 treated with pulse current for 30 minutes. The component is then rinsed with deionized water and dried using compressed air.
    5 shows the surface of the component, which had an Ra value of 15 pm. After the component had been treated in the manner described above using the method according to the invention, the Ra value was only 3 pm. 6, the smoothing of the surface of the component treated according to the invention is evident.
    Example 4: Aftertreatment of a 3D printed component made of Ti6Al4V
    After mechanical cleaning and electrical contacting, a 3D-printed component for medical applications is placed in an electrolyte consisting of 90% methanesulfonic acid, 1.5% 1-hydroxyethane (1,1diphosphonic acid), 3% amino-tris (methylenephosphonic acid) and 5. 5% glycol at a voltage of 22 V and a current density of 10 A / dm 2 smoothed by direct current for 60 minutes. The component is then rinsed with deionized water and dried using compressed air.
    As shown in FIG. 7 in an SEM image of the surface, this component has a grid-like structure, the roughness of which is caused by powder residues from the 3D printing adhering to the surface. After the treatment by means of the method according to the invention, these particle residues are practically completely removed (FIG. 8).
    权利要求:
    Claims (8)
    [1]
    P A T E N T A N S P R Ü C H E
    1. Electrolyte for electropolishing metal surfaces, the electrolyte having methanesulfonic acid, characterized in that it additionally contains at least one phosphonic acid.
    [2]
    2. Electrolyte according to claim 1, characterized in that the phosphonic acid is selected from a group containing mono-, di- and / or polyphosphonic acids, preferably amino-tris (methylenephosphonic acid) or mixtures thereof.
    [3]
    3. Electrolyte according to claim 1 or 2, characterized in that the at least one phosphonic acid is contained in a concentration of 0.1 wt% to 10 wt%.
    [4]
    4. Electrolyte according to one of claims 1 to 3, characterized in that in addition at least one polyhydric alcohol, preferably with at least three functional hydroxy groups and / or at least one polyalcohol, which is preferably selected from a group consisting of glycol, glycerol, polyvinyl alcohol , Inositol or sorbitol or mixtures thereof.
    [5]
    5. Electrolyte according to claim 4, characterized in that the at least one alcohol is contained in a concentration of up to 10% by weight.
    [6]
    6. Electrolyte according to one of claims 1 to 5, characterized in that it contains further additives which are selected from a group consisting of mineral acids, in particular phosphoric acid and sulfuric acid in a concentration of up to 50% by weight, fluorides, in particular
    Ammonium difluoride in a concentration of up to 20% by weight, and amines, in particular ethanolamines and isopropanolamines, in a concentration of up to 15% by weight are contained.
    [7]
    7. Use of an electrolyte according to one of claims 1 to 6 for post-processing of parts produced by means of an additive method from metal powder, in particular from titanium and aluminum alloys.
    7/14
    [8]
    8. Use of an electrolyte according to claim 7, characterized in that the post-processing in the electrolyte is carried out by means of direct current, alternating current, pulsed current or pulse reverse current.
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    同族专利:
    公开号 | 公开日
    AT520365B1|2019-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE3302011C1|1983-01-21|1984-06-20|Kraftwerk Union AG, 4330 Mülheim|Process for electrolytically polishing the surfaces of finished parts made of zirconium and/or zirconium alloys|
    DE102006045221B3|2006-09-25|2008-04-03|Poligrat Gmbh|Electropolishing process for cobalt and cobalt alloys and electrolyte|
    DE102006047713B3|2006-10-09|2008-03-27|Poligrat Gmbh|Electrolyte for electro-polishing surfaces of metal and metal alloys used in the production of gas turbines contains methane sulfonic acid and ammonium difluoride|
    DE102006050317B3|2006-10-25|2008-06-19|Poligrat Gmbh|Electrolyte, useful for electro-polishing surfaces from iron-chromium alloy, comprises phosphoric acid electrolyte, methane sulfonic acid and a tertiary amine|
    DE102006053586B3|2006-11-14|2008-04-17|Poligrat Gmbh|Electropolishing the surface of metals comprises using an electrolye comprising methanesulfonic acid and an alkanediol or cycloalkanol|
    DE102007011632B3|2007-03-09|2008-06-26|Poligrat Gmbh|Method for electropolishing and/or electrochemical deburring of surfaces made from titanium or titanium-containing alloys comprises using an electrolyte made from methane sulfonic acid or one or more alkane diphosphonic acids|
    WO2015078930A1|2013-11-28|2015-06-04|Abbott Laboratories Vascular Enterprises Limited|Electrolyte composition and method for the electropolishing treatment of nickel-titanium alloys and/or other metal substrates including tungsten, niob and tantal alloys|WO2021148318A1|2020-01-23|2021-07-29|Mahle International Gmbh|Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition|
    法律状态:
    2021-06-15| PC| Change of the owner|Owner name: RENA TECHNOLOGIES AUSTRIA GMBH, AT Effective date: 20210416 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50716/2017A|AT520365B1|2017-08-29|2017-08-29|ELECTROLYTE FOR ELECTROPOLISHING METAL SURFACES|ATA50716/2017A| AT520365B1|2017-08-29|2017-08-29|ELECTROLYTE FOR ELECTROPOLISHING METAL SURFACES|
    EP17816393.7A| EP3551786B1|2016-12-09|2017-12-07|Electropolishing method and electrolyte for same|
    DK17816393.7T| DK3551786T3|2016-12-09|2017-12-07|ELECTROPOLATION PROCEDURE AND ELECTROLYTE THEREOF|
    US16/467,206| US20200080222A1|2016-12-09|2017-12-07|Electropolishing method and electrolyte for same|
    ES17816393T| ES2879297T3|2016-12-09|2017-12-07|Electropolishing and electrolyte method for the same|
    PCT/AT2017/060326| WO2018102845A1|2016-12-09|2017-12-07|Electropolishing method and electrolyte for same|
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