• 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 metal surfaces through ion transport, characterized in that the conductive liquid of the dry electrolyte comprises at least one sulfonic acid. Preferably, the porous particles of the dry electrolyte comprise sulfonated polymer and more preferably polystyrene-divinylbenzene. Preferably, the conductive liquid of the dry electrolyte comprises methanesulfonic acid. Preferably, the concentration of sulfonic acid in relation to the solvent is between 1 and 70%. Optionally, the conductive liquid of the dry electrolyte comprises a complexing agent and/or a chelating agent. Dry electrolyte characterized in that it comprises sulfonic acid as a conductive liquid according to any of the preceding claims. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2734415A1
    申请号:ES201930148
    申请日:2019-02-21
    公开日:2019-12-05
    发明作者:Gimpera Marc Sarsanedas；Hernández Marc Soto
    申请人:Drylyte SL；
    IPC主号:
    专利说明:

    [0001]
    [0002] USE OF SULPHONIC ACIDS IN DRY ELECTROLYTES TO POLISH METAL SURFACES THROUGH ION TRANSPORTATION
    [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, for example, the dental, medical, automobile and aeronautical industry, among many others.
    [0006]
    [0007] Object of the invention
    [0008] The object of this invention relates to the method of smoothing and polishing metal surfaces characterized by the use of ionic transport using free solid bodies containing sulfonic acids as electrolytes, and also free solid bodies containing sulfonic acids to perform this method. The use of said free solid bodies containing sulfonic acids has distinct advantages and characteristics that represent a remarkable novelty compared to the prior art.
    [0009]
    [0010] Background of the invention
    [0011] There are established systems for the polishing of metals characterized by the use of particles that are not attached to any support, that is, free solid bodies, which produce mechanical abrasion by friction due to a relative movement between the particles and the surface to be treated. These particles have to be harder than the material to be treated.
    [0012] Systems based on mechanical abrasion suffer from a lack of uniformity because the effect of abrasion is related to the pressure between the surface and the particles. This means that the protruding metal parts suffer more abrasion than the occluded parts. This generally results in excessive rounding of vertices and edges of the pieces to be treated. This is a major obstacle in the use of mechanical abrasion systems on metals that require precision or sharp edges.
    [0013] In addition, systems based on mechanical abrasion produce deformations, at a level that depends on the size of the particles, on the surface of metal In this process, metal surfaces are contaminated with inclusions from the particle. These modifications of the metal surface composition often result in a decrease, for example, in chemical resistance, tensile strength or durability.
    [0014] There are also established systems for metal polishing characterized by the use of an electric current on the metal submerged in a liquid electrolyte. These electropolishing systems resulted in metal surfaces free of external inclusions.
    [0015] However, electropolishing systems have a smoothing effect on the roughness of the order of magnitude of micrometers. Commercial conventional electropolishing systems often claim a roughness reduction of 50 to 60% over initial roughness. In many applications, this level of smoothing is not enough.
    [0016] In addition, electropolishing systems, due to their intrinsic operation, tend to reveal the underlying crystalline structure of the metal, or the metal salt or metal oxide formed. This results in stepped surfaces, holes and other defects corresponding to the metal structure. In this way, electropolishing systems extend into metals and alloys that, due to their chemical properties, can intrinsically overcome these limitations, for example, aluminum. However, they cannot be used in many other metals and alloys without these inconveniences.
    [0017] Some of the problems of metal grinding systems based on mechanical abrasion and electropolishing systems were solved by using free solid bodies to polish metal surfaces through ion transport. The same applicant owns the ES2604830A1 patent which refers to a "method for smoothing and polishing metals through the transport of ions by means of free solid bodies (...)". Said free solid bodies can carry out an ion transport composed of a set of porous particles that retain a certain amount of liquid, and a conductive liquid electrolyte that is retained in the particles, preferably aqueous HF between 1 and 10%. However, said electrolyte does not provide satisfactory results in many metals, such as iron and iron alloys.
    [0018] The objective of this invention is to develop an improved dry electrolyte for use in the method of smoothing and polishing metals through the transport of ions by means of free solid bodies.
    [0019] Summary of the invention
    [0020] The use of sulphonic acids in free solid bodies or particles to polish metal surfaces through ion transport is a novelty in the field of metal polishing that has advantages and features that are explained in the following text.
    [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.
    [0022] This 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 that contains at least one sulfonic acid.
    [0023] In this invention, the electrically conductive liquid comprises at least one sulfonic acid. Sulfonic acids are compounds with a general formula RSO3H, in which R can be any organic, alkyl or aromatic substituent, another functional group or a halogen atom. This is the general structure of a sulfonic acid.
    [0024]
    [0025]
    [0026]
    [0027] Preferably, the sulfonic acids used are those with a high solubility in water or other chosen solvent. In addition, preferably, those sulfonic acids that form soluble salts with the corresponding metals. For example, but not limited to, sulfonic acids such as methanesulfonic acid CH3SO3H, trifluorosulfonic acid CF3SO3H, fluorosulfonic acid FSO3H, chlorosulfonic acid ClSO3H, para-toluenesulfonic acid 4 -CH3C6H4SO3H and all sulfamic acid NH2SO3H, can be used They are represented below.
    [0028]
    [0029]
    [0030]
    [0031] Sulfonic acids can be used pure if they are liquid at the working temperature or in solution. The optimal concentration of sulfonic acid must be determined empirically since it depends on the sulfonic acid chosen, the solvent and also on the parameters of the piece to be treated, such as the type of metal, the total surface and the shape. In solution, preferred solvent options are water or a polar solvent due to conductivity and solubility reasons. Preferably, water is the solvent of choice. Sulfonic acid concentrations in the conductive liquid between 1 and 70% have proven to be active in this process. Preferably, concentrations between 2 and 40%. These concentrations refer to the final concentration of the electrically conductive liquid in the dry electrolyte, regardless of how dry electrolytes are prepared.
    [0032] Sulfonic acids are strong acids, and their handling in liquids or solutions, in terms of their use in classical electropolishing, has led to many handling risks. In a liquid state or in solution, these sulfonic acids can produce an unwanted attack on the metal surfaces. Therefore, after using sulfonic acids in the classical electropolishing, a subsequent neutralization step is often required.
    [0033] However, when they are limited to porous particles, handling becomes easier and the risks of unwanted attacks on the surface are avoided. In addition, due to the fact of being confined in particles, the effect 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 particle-metal contact time relatively short, which favors a localized action on the surface.
    [0034] Sulfonic acids with an organic moiety, such as, for example, without limitation purposes, methanesulfonic acid, trifluorosulfonic acid and paratoluenesulfonic acid, are much less polar than inorganic acids. Therefore, the localized reduced polarity of these sulfonic acids facilitates their movement through the apolar resin. Especially, the smaller sulfonic acid containing an organic moiety, methanesulfonic acid, would benefit from this effect as long as it does not suffer steric hindrances.
    [0035] In addition, other chemical compounds can be added to the conductive liquid, such as complexing agents. These agents can capture the formed metal ions and increase the ability to remove metal oxides and salts from the surface.
    [0036] Complexing agents with more than one functional group are known as chelating agents. The effects of capture and transfer of metal ions would be even greater by the use of chelating agents, such as citric acid, EDTA or phosphonates. Such agents would have a high affinity for metal ions formed on the surface and would help transport those ions to the particles.
    [0037] In a preferred embodiment the chelating complexing agent is a polyether.
    [0038] Polyether is defined as a compound that includes more than one ether group (C-O-C) in its structure, without prejudice that it can in turn include other functional groups such as esters, acids, amino, amide, etc.
    [0039]
    [0040] It has been found that the addition of polyethers to the formulation of the liquid contained in the particles increases the rate of transfer of ionic metals and therefore increases the speed of the polishing process.
    [0041]
    [0042] In an even more preferred embodiment the polyether is a linear alkyl polyether. Specifically, the group of polyethers includes crown ethers and alkyl polyethers. Alkyl polyethers can have different shapes, such as linear, star, branched or comb. For the electropolishing process we have discovered linear alkyl polyethers produce better results in the process, since they are more active in forming metal complexes.
    [0043]
    [0044] Within the category of linear alkyl polyether chelating complexing agents, polyethylene glycol or PEG stands out, also called poly (oxy-1,2-ethynediyl), poly (ethylene oxide), polyoxyethylene, polyethylene oxide and trade names such as Carbowax or Macrogol;
    [0045]
    [0046] Within the category of linear alkyl polyether chelating complexing agents, polypropylene glycol or PPG also stands out.
    [0047]
    [0048] PEG and PPG are represented below, where R can be any radical or functional group, preferably H or CH3. The number "n" of repetitions of the repetition unit is an important factor. Metal complexes with polyethers mostly adopt a tetrahedric or octahedral conformation, that is, the metal ion is surrounded by four or six oxygen atoms respectively, so the optimal number of repetitions is around n = 6, since it covers both possibilities . .
    [0049]
    [0050]
    [0051] In the case of PEG, molecular weights of 200 to 500 Da are preferred. Specifically PEG 300 is the most preferred.
    [0052]
    [0053] The addition of these PEG and PPG polymers to the electrically conductive liquids used in the preparation of dry electrolytes containing sulfonic acids produce electropolishing processes at high speeds and with speculative final finishes. This effect, not at all obvious, is due to a series of accumulated factors: they are soluble in the phase in which they find sulfonic acids, they have the capacity to complex with the extracted metal ions, they act as phase transfer agents between the liquid retained in the particles and the gel phase of the particles themselves, are stable to the voltages and current intensities to which the process is subjected, and, in addition, are biologically safe.
    [0054]
    [0055] The certain amount of electrically conductive liquid to impregnate the porous particles has to be high enough to allow a measurable electrical conductivity through the dry electrolyte. In addition, this amount must be below the saturation point of the porous particle, so that there is no observable free liquid, thus being a "dry" electrolyte. Preferably, the amount of conductive liquid is close but below the saturation point of the porous particle. This amount should be determined empirically since it depends on the sulphonic acid used, the type of resin, the temperature, the solvent and the concentration. As an example, AMBERLITE 252RFH with a water retention capacity between 52 and 58% of the optimal amount of a conductive liquid consisting of 32% methanesulfonic acid in water is between 35 and 50% with respect to Absolutely dry weight of the resin.
    [0056]
    [0057] The porous particle material used is preferably based on a sulfonated polymer, which means that it has RSO3H or RSO3-linked active sulfonic acid groups. Preferably, the sulfonated porous particle polymer is based on a copolymer of styrene and divinylbenzene. Specifically, the porous particles can be ion exchange resins, such as, but for no limiting purpose, AMBERLITE 252RFH with an ion exchange capacity of 1.7 eq / l, a density of 1.24 g / ml, a diameter of between 0.6 and 0.8 mm, and a water retention capacity of between 52 and 58%.
    [0058] The cooperative effect between the sulfonic acid groups bound to the polymer and the sulfonic acids in the conductive liquid is interesting. It has been discovered, in a non-obvious way, that the fact that these groups have the same chemical structure, although in a different state, helps the circulation of metal ions from the conductive liquid to the polymer matrix. The direct chemical environment of metal ions in solution (complexed by sulphonates in solution) and in the polymer (complexed by sulfonates bound to the polymer) is similar. Therefore, the difference in energy levels between these states must be very low, which presumably implies a transition state with low energy, which becomes a faster liquid-solid transfer rate. This has two positive effects for the process, on the one hand, it makes the process faster and, on the other, it improves the overall ability of the resin to act as a metal ion receptor, which extends the life of the dry electrolyte.
    [0059] However, the sum of these different non-obvious effects when using sulfonic acids in dry electrolytes to polish metal surfaces through ion transport allows higher speed processes to obtain specular results while increasing the life of the dry electrolyte.
    [0060] The dry electrolyte containing sulfonic acid is also an object of this invention.
    [0061]
    [0062] Exemplary Embodiments
    [0063] Below are some exemplary cases without any limiting purpose.
    [0064]
    [0065] Example 1
    [0066] A dry electrolyte was prepared by mixing and homogenizing 1.5 kg of AMBERLITE 252RFH ion exchange resin with 550 ml of a 4% methanesulfonic acid solution in water. This dry electrolyte was used to polish a piece of iron alloy with the following composition expressed in% C (0.17-0.23) Si (0.40) Mn (0.65-0.95) V (0.025) S (0.050) Cr (0.35-0.70) Ni (0.40-0.70) Mo (0.15-0.55) Cu (0.35) Al (0.050) with a surface area of 5 cm2. The counter electrode was a network of iridium on titanium. The current used was a positive wave of an electric current from 50 Hz to 20 V, which provided an intensity of 0.1 A. The piece had an up / down movement at approximately 4 Hz and the container of Dry electrolyte was subjected to vibration. After 5 minutes of this procedure, the metal surface had acquired specular properties.
    [0067]
    [0068] Example 2
    [0069] A dry electrolyte was prepared by mixing and homogenizing 5.3 kg of AMBERLITE 252RFH ion exchange resin with 1950 ml of a 32% methanesulfonic acid solution in water. This dry electrolyte was used to polish a piece of iron alloy with the same composition as before with a surface area of 36 cm2. The counter electrode was a network of iridium on titanium. The current used was a positive wave of an electric current of 50 Hz to 30 V. The piece had an up / down movement at approximately 4 Hz and the dry electrolyte vessel was subjected to vibration. After 10 minutes of this procedure, the metal surface had acquired specular properties.
    [0070]
    [0071] Example 3
    [0072]
    [0073] A solution with 550 mL of 70% methanesulfonic acid, 160 mL PEG and 3000 mL of deionized water was prepared. This solution is mixed and homogenized with 6.7 kg of AMBERLITE 252RFH ion exchange resin to produce a dry electrolyte. This dry electrolyte was used to polish a piece of 36 cm2 carbon steel. The counter electrode used was an iridium network on titanium. The current used was a positive wave of an electric current of 50 Hz at 30 V. The piece had an up / down movement ca. 4 Hz and the dry electrolyte vessel was subjected to vibration. After 5 minutes of this procedure, the metal surface had acquired specular properties.
    [0074]
    [0075] With these instructions, it is assumed that one skilled in the art could reproduce these results without any additional problems.
    权利要求:
    Claims (13)
    [1]
    1. Use of dry electrolytes to polish metal surfaces through ion transport, characterized in that the conductive liquid of the dry electrolyte comprises at least one sulfonic acid.
    [2]
    2. Use of dry electrolytes to polish metal surfaces through ion transport as indicated in claim 1, characterized in that the porous particles of the dry electrolyte comprise sulfonated polymer.
    [3]
    3. Use of dry electrolytes to polish metal surfaces through ion transport as indicated in claim 2, characterized in that the porous particles of the dry electrolyte comprise polystyrene-divinylbenzene ion exchange resins.
    [4]
    4. Use of dry electrolytes to polish metal surfaces through ion transport according to any preceding claim, characterized in that the conductive liquid of the dry electrolyte comprises methanesulfonic acid.
    [5]
    5. Use of dry electrolytes to polish metal surfaces through ion transport according to claims 1 and 4, characterized in that the concentration of sulfonic acid in relation to the solvent is between 1 and 70%.
    [6]
    6. Use of dry electrolytes to polish metal surfaces through ion transport according to any of the preceding claims, characterized in that the conductive liquid of the dry electrolyte comprises a complexing agent.
    [7]
    7. Use of dry electrolytes to polish metal surfaces through ion transport according to claim 6 characterized in that the complexing agent comprises a polyether
    [8]
    8. Use of dry electrolytes to polish metal surfaces through ion transport according to claim 7 characterized in that the polyether is linear alkyl.
    [9]
    9. Use of dry electrolytes to polish metal surfaces through ion transport according to claim 8 characterized in that the polyether is polyethylene glycol.
    [10]
    10. Use of dry electrolytes to polish metal surfaces through ion transport according to claim 9 characterized in that the polyethylene glycol has a molecular weight between 200 and 500 Da.
    [11]
    11. Use of dry electrolytes to polish metal surfaces through ion transport according to claim 8 characterized in that the polyether is polypropylene glycol.
    [12]
    12. Use of dry electrolytes to polish metal surfaces through ion transport according to any of the preceding claims, characterized in that the conductive liquid of the dry electrolyte comprises a chelating agent.
    [13]
    13. - Dry electrolyte characterized in that it comprises sulfonic acid as a conductive liquid according to any of the preceding claims.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20030178320A1|2001-03-14|2003-09-25|Applied Materials, Inc.|Method and composition for polishing a substrate|
    WO2007121999A2|2006-04-26|2007-11-01|Supramol.Lecular Systems, S.L.|Electrolytic solution for the electrochemical polishing of metal articles|
    US20080099345A1|2006-10-09|2008-05-01|Poligrat Gmbh|Electropolishing process for niobium and tantalum|
    US20080188162A1|2007-02-06|2008-08-07|Itsuki Kobata|Electrochemical mechanical polishing apparatus conditioning method, and conditioning solution|
    US20080217186A1|2007-03-09|2008-09-11|Poligrat Gmbh|Electropolishing process for titanium|
    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. |
    JP2017214615A|2016-05-31|2017-12-07|株式会社カネカ|Electrolytic polishing liquid and method for producing electrolytically polished metal compact|ES2756948A1|2020-02-04|2020-04-27|Drylyte S L|SOLID ELECTROLYTE FOR DRY METAL POLISHING WITH ACTIVITY MODERATOR |ES2721170B2|2018-01-26|2019-12-11|Drylyte S L|USE OF SO4H2 AS ELECTROLYTE FOR PROCESSES OF SMOOTHING AND POLISHING OF METALS BY ION TRANSPORTATION THROUGH FREE SOLID BODIES.|ES2846299A1|2021-05-18|2021-07-28|Drylyte S L|DEVICE AND METHOD FOR ELECTROPOLISHING BY CONDUCTING SURFACE |
    法律状态:
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    优先权:
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