• 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:
    Use of dry electrolytes to polish Ti and other metal and alloy surfaces through ionic transport characterized in that the conductive liquid of the dry electrolyte comprises HCI. Preferably the concentration of HCI in relation to the solvent is between 1 and 38% and more preferably it is between 5 and 15%. Dry electrolyte characterized in that it comprises hydrochloric acid as a conductive liquid according to any of the preceding claims. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2734500A1
    申请号:ES201831093
    申请日:2018-11-12
    公开日:2019-12-10
    发明作者:Millet Pau Sarsanedas
    申请人:Drylyte SL；
    IPC主号:
    专利说明:

    [0001]
    [0002] USE OF A HCI IN DRY ELECTROLYTES TO POLISH YOU AND OTHER METAL AND ALLOY SURFACES THROUGH IONIC TRANSPORT
    [0003]
    [0004] Field of the Invention
    [0005] The field of the present invention is the industry sector focused on the smoothing, burnishing and polishing of metal surfaces, with applications in fields such as dentistry, medicine, laser sintering, automotive and aeronautics among much others.
    [0006]
    [0007] Object of the invention
    [0008] The object of the present invention relates to a method of smoothing and polishing surfaces of titanium and other metals characterized by the use of ionic transport using a dry electrolyte containing hydrochloric acid as an electrolyte and, also, to the mentioned dry electrolyte containing acid hydrochloric to perform this method. The use of said system has distinguished advantages and characteristics that represent a remarkable novelty compared to the prior art.
    [0009]
    [0010] Background of the invention
    [0011] Titanium and derived alloys are materials that have low weight and good corrosion resistance. Therefore, they play a key role in numerous applications such as components in the chemical industry, medical implants, automobiles and aeronautics, among many others. Today there is an increasing demand for polished titanium surfaces.
    [0012] In addition, there is an increasing market in selective laser sintering and selective laser fusion, usually called 3D metal printing. These are additive manufacturing techniques capable of producing complex shapes using various types of materials. The use of these processes with titanium and other metals results in very rough surfaces. This is a major disadvantage in many fields of application because rough surfaces increase friction and corrosion, facilitate colonization of bacteria and fungi and hide imperfections and stress fractures. Therefore, an efficient and cost-effective method is needed to polish complex shapes.
    [0013] Mechanical abrasion polishing techniques are not suitable for shapes complex. In addition, these methods tend to remove a large amount of metal, produce inclusions and contamination on the metal surface and round excessively sharp edges and vertices.
    [0014] Current electropolishing techniques cause a reduction of up to 50% of the initial roughness. This implies that parts with a high initial roughness must be pretreated with another polishing method to achieve acceptable results, which increases overall time and costs.
    [0015] The large area beam irradiation is capable of polishing titanium to generate surfaces with low roughness. However, it is a very complex technique to handle and has high associated costs.
    [0016] The same applicant is the owner of the ES2604830A1 patent which refers to a "method for smoothing and polishing metals through ionic transport by means of free solid bodies (...)". Said free solid bodies capable of carrying out the ionic transport consist of a set of porous particles that retain a certain amount of liquid and a conductive liquid electrolyte to be retained in the particles, preferably aqueous hydrogen fluoride between 1 and 10%. However, said electrolyte does not provide satisfactory results in many metals, such as titanium.
    [0017] The object of the present invention is a method for smoothing and polishing titanium and other metals using a dry electrolyte based on HCl through ionic transport.
    [0018]
    [0019] Summary of the invention
    [0020] The use of hydrochloric acid in dry electrolytes to polish metal surfaces through ionic transport is a novelty in the field of metal polishing that has advantages and features that are explained in the text below.
    [0021] A dry electrolyte comprises a set of porous particles with the ability to retain a certain amount of liquid and a certain amount of electrically conductive liquid retained in the particles.
    [0022] The present invention specifically relates to dry electrolytes comprising porous particles with the ability to retain a certain amount of liquid and a certain amount of electrically conductive liquid containing hydrochloric acid.
    [0023] The particles may be of any material, such as polymer or ceramic, provided they have the capacity to retain a certain amount of liquid and are chemically resistant to hydrochloric acid. Preferably, the particles are based on polymeric materials. Porous particles based on a sulfonated polymer (which means that the polymer has bonded active sulfonic acid groups) have been shown to provide good results. Preferably, the sulfonated polymer of the porous particles is based on a copolymer of styrene and divinylbenzene.
    [0024] The size and shape of the particles can be selected based on the roughness to be treated. Specifically, the porous particles may be ion exchange resin spheres, such as, for example, but not limited to, AMBERLITE 252RFH with an ion exchange capacity of 1.7 eq L-1, a density of 1.24 g ml -1, a diameter size between 0.6 and 0.8 mm and a water retention capacity between 52 and 58%.
    [0025] The main feature of the present invention is that the electrically conductive liquid contains HCl. The concentration of HCl in the dry electrolyte depends, among other parameters, on the metal or alloy to be polished, on the total surface and on the shape. Among all possible solvents, water is the preferred solvent. The electropolishing process can be carried out using a dry electrolyte containing an equivalent electrically conductive liquid (when the total amount of solvent in the resin is taken into account) to a solution of HCl in water in a range between 1 and 38%. A concentration higher than 38% would cause the emission of corrosive hydrogen chloride gas, which would make it necessary to work in a sealed pressurized system. Better results are obtained in a range of 3 to 20%, preferably 5 to 15%. Approximately 15% concentrations obtain a fast processing speed that adapts to large surface areas. Approximate lower concentrations at a yield of 5% are better for smaller surface areas and more complex shapes.
    [0026] A common problem in electropolishing systems is the formation of passivated layers on the metal surface that block the process. This problem is extreme in the case of titanium, which forms a homogeneous layer of TiO2, which is not conductive and is not easy to transport.
    [0027] Experimentally, it has been shown that, in a non-obvious way, hydrochloric acid favors the vehiculization of metal ions from the surface to the particles. Hydrochloric acid has several effects. It is a strong acid, which means that it provides protons or hydronium ions (H + H3O +) to the solution. These ions have the highest ionic mobility in the water, which increases the electrical conductivity, accelerating the process. On the other hand, it contributes Cl-chloride anions to the medium. In Presence of this anion, the oxidation of titanium generates not only titanium oxide, but also a fraction of titanium chloride.
    [0028] Ti0 2 H2O ^ TIO2 4 H + 4 e-Ti0 4 Cl- ^ TiCl4 4 e-It is not evident that the formation of titanium chloride destabilizes the passivation layer formed on the surface, thus making it prone to withdrawal. In addition, chloride anions have a relatively high metal complexation capacity, which favors the vehiculization of metal ions from the surface to the particle.
    [0029] The use of hydrochloric acid solution for electropolishing can be cumbersome due to the emanations of gaseous hydrogen chloride, which are dangerous to health and cause corrosion in electrical equipment. In addition, prolonged immersion of the metal part in hydrochloric acid can cause attacks on the surface and can have a detrimental effect on the leveling process.
    [0030] Therefore, the effect of hydrochloric acid when it is part of a dry electrolyte is interesting. Due to the fact that it is confined in particles, the effect of HCl would focus on the peaks of surface roughness, thus having a stronger effect where it is needed. In addition, the relative movement of the particles with respect to the metal part makes the metal particle contact time relatively short, which favors a localized action on the surface. Moreover, the fact that hydrochloric acid is confined within the particles reduces the emanation of gaseous hydrogen chloride.
    [0031] In summary, a dry electrolyte containing HCl can be used to polish metal surfaces, even when the metal forms stable passivation layers. For this reason, a dry electrolyte containing HCl in a wide range of metals can be used, however, it is especially suitable for those metals that form these passivation layers such as titanium.
    [0032] Therefore, the use of dry electrolytes containing hydrochloric acid allows electropolishing of surfaces of titanium and other metals in a fast and cost-effective manner.
    [0033] The dry electrolyte containing hydrochloric acid is also an object of the present invention.
    [0034]
    [0035] Example embodiments
    [0036] These are some example cases without limiting purposes.
    [0037] Example 1
    [0038] A dry electrolyte made of AMBERLITE 252RFH containing 7% HCl in water was used as a conductive liquid to polish a titanium surface. A piece of titanium with an area of 8 cm2 was moved inside the dry electrolyte in an orbital cycle and the dry electrolyte vessel was vibrated. An electric current of 18 V, 20 ps positive, 20 ps negative and 10 ps at 0 V was applied to the titanium piece using an iridium mesh on titanium as a counter electrode. After 10 min, the surface had acquired specular properties.
    [0039] Example 2
    [0040] A dry electrolyte, AMBERLITE 252RFH containing 14% HCl in water was used as a conductive liquid, for polishing. A 55 cm2 piece of titanium was moved into the dry electrolyte in an orbital cycle and the dry electrolyte vessel was vibrated. An electric current of 40 V, 20 ps positive, 20 ps negative and 10 ps at 0 V was applied to the titanium piece using an iridium mesh on titanium as a counter electrode. After 30 min, the surface had acquired specular properties.
    权利要求:
    Claims (4)
    [1]
    1. Use of dry electrolytes to polish Ti and other metal and alloy surfaces through ionic transport characterized by
    The conductive liquid of the dry electrolyte comprises HCl.
    [2]
    2. Use of dry electrolytes for polishing Ti and other metal and alloy surfaces through ionic transport according to claim 1 characterized in that the concentration of HCl in relation to the solvent is between 1 and 38%.
    [3]
    3. Use of dry electrolytes to polish Ti and other metal and alloy surfaces through ionic transport according to claim 2 characterized in that the concentration of HCl in relation to the solvent is between 5 and 15%.
    [4]
    4. Dry electrolyte characterized in that it comprises hydrochloric acid as a conductive liquid according to any of the preceding claims.
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3882379A4|2022-01-12|
    ES2734500B2|2020-06-03|
    US20210262112A1|2021-08-26|
    WO2020099699A1|2020-05-22|
    CN113195799A|2021-07-30|
    EP3882379A1|2021-09-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3087874A|1961-02-13|1963-04-30|Don H Greisl|Electropolishing of titanium base alloys|
    WO2001061080A1|2000-02-14|2001-08-23|Advanced Cardiovascular Systems, Inc.|Electro-polishing fixture and electrolyte solution for polishing nitinol stents and method of using same|
    ES2604830A1|2016-04-28|2017-03-09|Drylyte, S.L.|Process for smoothing and polishing metals by ionic transport through free solid bodies, and solid bodies to carry out said process. |
    GB1513532A|1977-08-11|1978-06-07|Kodak Ltd|Method of electrolytically graining aluminium|
    AU3038789A|1988-01-21|1989-08-11|Electro-Nucleonics Inc.|Dry ion-selective electrodes for the determination of ionic species in aqueous media|
    JP2003113500A|2001-10-03|2003-04-18|Toshiba Corp|Electrolytic polishing method|
    CN101171371A|2005-04-29|2008-04-30|纳幕尔杜邦公司|Membrane-mediated electropolishing with topographically patterned membranes|
    法律状态:
    2019-12-10| BA2A| Patent application published|Ref document number: 2734500 Country of ref document: ES Kind code of ref document: A1 Effective date: 20191210 |
    2020-06-03| FG2A| Definitive protection|Ref document number: 2734500 Country of ref document: ES Kind code of ref document: B2 Effective date: 20200603 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201831093A|ES2734500B2|2018-11-12|2018-11-12|Use of an HCl in dry electrolytes to polish Ti and other metal and alloy surfaces through ion transport|ES201831093A| ES2734500B2|2018-11-12|2018-11-12|Use of an HCl in dry electrolytes to polish Ti and other metal and alloy surfaces through ion transport|
    CN201980083852.2A| CN113195799A|2018-11-12|2019-11-06|Polishing titanium and other metal and alloy surfaces by ion transport using HCL in dry electrolyte|
    PCT/ES2019/070751| WO2020099699A1|2018-11-12|2019-11-06|Use of hcl in dry electrolytes to polish ti and other metal and alloy surfaces by ion transport|
    EP19884027.4A| EP3882379A4|2018-11-12|2019-11-06|Use of hcl in dry electrolytes to polish ti and other metal and alloy surfaces by ion transport|
    US17/318,532| US20210262112A1|2018-11-12|2021-05-12|Use of hcl in dry electrolytes to polish ti and other metal and alloy surfaces by ion transport|
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