• 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:
    Electrochemical procedure to plate titanium studs and cell. The present invention relates to a method for plating titanium studs comprising pretreatment steps for the surface of the titanium stud prior to the platinum electrodeposition step and to an electrochemical cell in which to carry out said procedure. Therefore, the invention can be encompassed in the area of electrochemistry, particularly in electrodeposition processes. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2743828A1
    申请号:ES202030022
    申请日:2020-01-16
    公开日:2020-02-20
    发明作者:Domene Ramón Manuel Fernández；Antón José García；Tovar Rita Sánchez；García Dionisio García；Márquez Gemma Roselló；Tamarit María Encarnación Blasco；Portero María José Muñoz
    申请人:Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Electrochemical procedure for plating titanium and cell lugs
    [0003]
    [0004] The present invention relates to a method for plating titanium studs, which comprises stages of pretreatment of the titanium stud surface prior to the platinum electrodeposition stage and an electrochemical cell where to carry out said process.
    [0005]
    [0006] Therefore, the invention can be encompassed in the area of electrochemistry, particularly in electrodeposition processes.
    [0007]
    [0008] BACKGROUND OF THE INVENTION
    [0009]
    [0010] Platinum is a precious metal and one of the rarest elements in the earth's crust. It is a malleable material, ductile and with a very high resistance to corrosion, which is considered a noble metal. Platinum is normally used as a catalyst, for example, in catalytic converters, in fuel cells or in numerous electrolytic processes. It also has applications in the manufacture of pieces of equipment that work under severe temperature conditions and / or corrosive environments. It is also used in electronics due to its high conductivity.
    [0011]
    [0012] Despite its excellent properties, being a very scarce metal, the high costs associated with the manufacture of platinum parts or electrodes have greatly restricted its use on a large scale. The availability of platinum coated conductive materials, much more affordable from an economic point of view, can solve this problem. For example, in the field of electrocatalysis, compound electrodes formed by a conductive substrate on which a platinum layer is deposited are widely used in a multitude of processes. In other areas of electrochemistry, such as cathodic protection by printed current or in the electrolysis of concentrated solutions of alkali metal chlorides (chloro-alkaline industry), the commercial development of titanium-based and platinum-coated anodes has been a great Advance.
    [0013]
    [0014] Titanium is a metal with high corrosion resistance due to formation Spontaneously of a thin but compact oxide film on its surface (passive film), which insulates it from the electrolyte and protects it against corrosion. This property causes titanium to be used in many electrochemical processes, especially those in which anodes with high corrosion resistance are needed. However, the resistance of the passive film of titanium ceases to be stable and tends to break locally when high potential differences such as industrial electrochemical cells are used and consequently intense corrosion processes occur. To avoid the problems associated with the breakage of the passivation film, that is, to extend the life of the titanium electrode, said titanium anodes are usually coated with thin layers of platinum, especially in the areas of electrical contact, particularly in the areas of electrical contact. where the current is preferably supplied or moved. In this way, most of the current applied to the system passes through platinum. Thus, the low interfacial resistance between the platinum layer and the electrolyte causes the potential drop across the passive titanium film to remain within safe values and that the titanium / platinum composite anode remains intact.
    [0015]
    [0016] The first notable publication on platinum-coated titanium electrodes dates from 1958 (Cotton, JB, Platinum-faced Titanium for Electrochemical Anodes, Platinum Metals Review 2 (1958) 45-47), and since then numerous studies have been published (Preiser, HS, Cathodic Protection Applications Using Platinum Anodes, Platinum Metals Review 3 (1959) 38-43; Yoshimura, K., Aoki, K., Honda, S., Electrodeposition of platinum group metals on titanium, US Patent 3,373,092 ( 1968); Shreir, LL, Platinum Provides Protection for Steel Structures - An economic way to prevent corrosion, Platinum Metals Review 21 (1977) 110-121; Warne, MA, Hayfield, PCS, Electrolytic process employing electrodes having coatings which comprise platinum, US Patent 4,203,810 (1980); Itai, R., Kanai, H., Shinagawa, A., Yamazaki, T., Anode for electrolyzing sea water, JPS56146887A (1981); Gauger, JF, Hinden, JM, Katz, M. , Electrode coating with platinum-group metal catalyst and semi-conducting pol ymer, US Patent 4,402,996 (1983); Hayfield, PCS, Platinised Titanium Electrodes for Cathodic Protection, Platinum Metals Review 27 (1983) 2-8; Sakai, K., Yoshihara, R., Sakurai, H., Minamida, K., Long-life insoluble electrode and process for preparing the same, US Patent 4,477,316 (1984); Baumgartner, ME, Raub, Ch.J., The Electrodeposition of Platinum and Platinum Alloys, Platinum Metals Review 32 (1988) 188-197; Skinner, PE, Improvements in Platinum Plating - A new generation of electroplating baths, Platinum Metals Review 33 (1989) 102-105; Imanishi, K., Matsuzawa, H., Suzuki, I., Takenami, M., Tashiro, H., Electrode for electrolysis, JPH06200391A (1994); Iniesta, J., González-García, J., Fernández, J., Montiel, V., Aldaz, A., On the voltammetric behavior of a platinized titanium surface with respect to the specific hydrogen and anion adsorption and charge transfer process, Journal of Materials Chemistry 9 (1999) 3141-3145; Mudali, UK, Raju, VR, Dayal, RK, Preparation and characterization of platinum and platinum-iridium coated titanium electrodes, Journal of Nuclear Materials 277 (2000) 49-56 .; Rao, CRK, Trivedi, DC, Chemical and electrochemical depositions of platinum group metals and their applications, Coordination Chemistry Reviews 249 (2005) 613-631; Evans, SAG, Terry, JG, Plank, NOV, Walton, AJ, Keane, LM, Campbell, CJ, Ghazal, P., Beattie, JS, Su, TJ, Crain, J., Mount, AR; Electrodeposition of platinum metal on TiN thin films, Electrochemistry Communications 7 (2005) 125-129; Vladimirovich, AV, Borisovich, LA, Aleksandrovich, KS, Valentinovich, VV, Aleksandrovich, JA, Nikolaevich, KD, Salavatovna, CS, Jur'evich, SD, Aleksandrovna, SI, Platinumtitanium anodes forming method, RU2004108494A (2005) Pushpavanam, M., High speed platinum deposition from a sulphamate formulation, Journal of Applied Electrochemistry 36 (2006) 1069-1074; China Shipping Heavy Ind. Gro., Method for preprocessing metal oxide anode substrate, CN1880509A (2006); Arenas, LF, Ponce de León, C .; Boardman, RP, Walsh, FC, Electrodeposition of Platinum on Titanium Felt in a Rectangular Channel Flow Cell, Journal of the Electrochemical Society 164 (2017) D57-D66). In these studies several methods are proposed for the preparation of this type of platinum electrodes such as electrodeposition, thermal decomposition, chemical reduction of platinum compounds, etc. Preferably, electrodeposition is employed, since it is a relatively simple method, easy to control and scale and cheaper than other methods in which higher amounts of material are used.
    [0017]
    [0018] However, in all these studies the difficulties associated with the platinum electrodeposition process on titanium electrodes are mentioned. Thus, frequently, the adhesion of the electrodeposited layers of platinum is not good and they exfoliate to the point of exposing an important part of the underlying titanium surface. This problem appears especially for electrodeposited layers with thicknesses greater than 1 pm.
    [0019] Different pretreatments have been proposed in the literature to prepare the titanium surface and improve the adhesion of platinum deposits on said titanium surface. However, the procedures that give acceptable results usually involve complex and intensive chemical treatments in time and energy consumed, with dangerous reagents such as hydrofluoric acid, in high temperature conditions such as boiling or even working with molten salts for long periods.
    [0020]
    [0021] In other cases, in addition to chemical polishing, surface pretreatment involves the formation of additional platinum layers underlying the electrodeposited layer, manufactured, for example, by applying paints or resins, which are subsequently decomposed by subjecting the surface to laborious heat treatments.
    [0022]
    [0023] In the literature it is also relatively common to find electrodeposition procedures of Pt on Ti that comprise an additional stage subsequent to the electrodeposition of heat treatment at elevated temperatures (500 ° C or higher) in an inert atmosphere in order to increase its adhesion.
    [0024]
    [0025] DESCRIPTION OF THE INVENTION
    [0026]
    [0027] In the present invention, a process for forming adherent, resistant and homogeneous coatings of a noble metal such as platinum on titanium parts or substrates is described, using surface pretreatment steps that solve the complexity and safety problems of other methods. mentioned in the state of the art section. The main advantage of this procedure is that it extends the life of the electrode. In addition, the process as a whole is simple, without using stages whose consumption of resources, energy and time is high, and easily scalable, which provides a fundamental advantage over the state of the art. The substrates obtained by this procedure, as parts or electrodes, are likely to be used in electrochemical processes.
    [0028]
    [0029] Therefore, in a first aspect, the present invention relates to a process for coating titanium studs with platinum (Pt) (from here the process of the invention), characterized in that it comprises the following steps:
    [0030] a) deburred from the surface of the titanium stud,
    [0031] b) chemical cleaning of the surface of the titanium stud debuted in step (a),
    [0032] c) chemical polishing of the surface of the titanium stud obtained in step (b), d) electrochemical anodizing in the presence of oxalic acid, at a temperature between 20 ° C and 45 ° C, where the anode is the titanium stud obtained in step (c) and the cathode is platinum, and
    [0033] e) platinum electrodeposition on the titanium stud obtained in step (d).
    [0034]
    [0035] Said process is preferably carried out in the cell of the invention.
    [0036]
    [0037] In a preferred embodiment of the process of the present invention the chemical cleaning step (b) is carried out by impregnating the deburred surface of the titanium stud obtained in step (a) with a concentrated solution of NaOH at a temperature between 75 ° C and 80 ° C. Preferably the concentration of the NaOH solution ranges from 30 g / L to 60 g / L.
    [0038]
    [0039] In another preferred embodiment of the process of the present invention, in the chemical polishing step (c), the surface obtained in step (b) is immersed in a concentrated solution of HNO3 and NaF. Preferably the concentration of HNO3 is between 300 g / L and 500 g / L and where the concentration of NaF is between 40 g / L and 60 g / L.
    [0040]
    [0041] Step (d) of the process refers to electrochemical anodizing in the presence of oxalic acid, at a temperature between 20 ° C and 45 ° C, where the anode is the titanium obtained in step (c) and the cathode is platinum . Preferably the acid of step (d) is oxalic acid. Even more preferably the concentration of oxalic acid is between 80 g / L and 100 g / L.
    [0042]
    [0043] The term "electrochemical anodizing" is understood in the present invention as the electrolytic process used to increase the thickness of the natural oxide layer on the surface of the titanium obtained in step (c). It cannot be considered as a passive film due to its porous and not very compact character In fact, it is precisely this porous character that is to be obtained by the method of the invention, in order to obtain a surface suitable for the subsequent anchoring of the platinum.
    [0044] In another preferred embodiment of the process of the present invention the electrochemical anodizing of step (d) is carried out by applying a potential of between 60 V and 65 V for a period of time between 20 min and 40 min.
    [0045]
    [0046] The last stage of the process of the present invention relates to a platinum electrodeposition (step (e)). In a preferred embodiment of the process of the present invention step (e) of electrodeposition is carried out at a temperature between 20 ° C and 45 ° C by applying a current density of between 20 mA / cm2 and 40 mA / cm2 during a period of time between 10 min and 20 min.
    [0047]
    [0048] In another preferred embodiment of the process of the present invention, in the electrodeposition step (e), an electrolyte comprising H2PtCl6.6H2O and concentrated HCl is used.
    [0049]
    [0050] In another preferred embodiment of the process of the present invention the thickness of the platinum layer deposited in step (e) is between 2 pm and 4 pm.
    [0051]
    [0052] A second aspect of the present invention relates to the electrochemical cell (from here the cell of the invention) for plating titanium studs, preferably according to the procedure described above, which is characterized by comprising:
    [0053] • a top piece of Teflon with a cylindrical configuration that has a through inner circular hole,
    [0054] • a lower piece of Teflon with a cylindrical configuration adapted to place the upper part, said lower part comprises
    [0055] or a ring-shaped protrusion on an upper surface configured to house a cylindrical stud on which the electrodeposition is to be performed, where the stud has a T-type configuration, or and a through-opening interior,
    [0056] • a cylindrical pin, with a T-type configuration with a first upper part and a second lower part, where the first upper part in turn comprises a threaded upper hole configured to join with the head of the connecting piece and rest on the lower part and where the second part is configured to be housed in the through interior opening of the lower part, • a connection piece comprising a threaded head and a rod, where the head is configured to thread with the threaded top hole of the pin, • and a platinum electrode with a cylindrical configuration that is used as a counter electrode in the platinum electrodeposition on the pins, which comprises a central hole to be inserted through the connecting piece and staying in the inner circular hole of the top piece.
    [0057]
    [0058] Preferably, the upper part has an external diameter of between 51 mm and 300 mm, and its internal circular through hole has an internal diameter of between 35 mm and 210 mm.
    [0059]
    [0060] Preferably, the lower part has an outside diameter between 61 mm and 366 mm.
    [0061]
    [0062] Preferably, the protrusion of the lower part is in the form of a ring and its function is to accommodate the upper surface of the pin and, thus, to join the upper piece of Teflon.
    [0063]
    [0064] Preferably, the first upper part of the stud with a T-type configuration has a first diameter of between 32.5 mm and 195 mm. Said first part in turn comprises a threaded hole with a diameter of between 10 mm and 30 mm.
    [0065]
    [0066] Preferably, the second lower part of the stud is externally threaded with a second diameter between 16 mm and 103 mm.
    [0067]
    [0068] The rod of the connecting piece preferably has a length between 70 mm and 100 mm and a diameter between 4 mm and 12 mm.
    [0069]
    [0070] The threaded head of the connection piece preferably has a diameter between 10 mm and 30 mm and a height between 10 mm and 50 mm.
    [0071]
    [0072] As mentioned above, the circular platinum electrode comprises a central hole to be inserted through the connection piece and to be housed in the inner circular hole of the top piece. The platinum electrode does not connect to the connection piece, it is housed around this untouched connection piece, to avoid short circuits.
    [0073]
    [0074] Preferably, the outer diameter of the platinum circular electrode is between 35 mm and 210 mm. The central hole of the platinum electrode preferably has a diameter between 6 mm and 20 mm.
    [0075]
    [0076] Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0077]
    [0078] BRIEF DESCRIPTION OF THE FIGURES
    [0079]
    [0080] Figure 1 shows the cell of the invention in exploded perspective (disassembled or disassembled) and a detailed view of the stud (5).
    [0081]
    [0082] Figure 2 shows an image of the surface of the electrode, of the titanium stud, after carrying out the pretreatment and electrodeposition of platinum, obtained by means of scanning electron microscopy of field emission (FESEM).
    [0083]
    [0084] Figure 3 shows an image of the space between the platinum nodules, after carrying out their electrodeposition obtained by means of field emission scanning electron microscopy (FESEM).
    [0085]
    [0086] Figure 4 a and b shows an image of the surface of the electrode, of the titanium stud, after carrying out the platinum electrodeposition obtained by confocal microscopy and field emission scanning electron microscopy (FESEM), respectively. No pretreatment
    [0087]
    [0088] EXAMPLES
    [0089]
    [0090] Next, the invention will be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the invention.
    [0091]
    [0092] Figure 1 shows the cell of the invention in exploding perspective (disassembled or disassembled) where the following elements are observed:
    [0093] (1) Teflon top piece
    [0094] (2) inner circular hole through the upper part
    [0095] (3) Teflon bottom piece
    [0096] (4) extrusion of the lower Teflon piece
    [0097] (5) busty
    [0098] (6) through opening of the lower part
    [0099] (7) threaded top hole of the stud
    [0100] (8) connection piece
    [0101] (9) connecting piece rod
    [0102] (10) head of the connecting piece
    [0103] (11) platinum electrode
    [0104] (12) central hole of the platinum electrode
    [0105] and a detail view of the stud (5).
    [0106]
    [0107] In this embodiment, a cell with the following dimensions has been used:
    [0108] • The upper part (1) has an external diameter of 102 mm.
    [0109] • The inner circular hole (2) of the upper part (1) has an inner diameter of 70 mm.
    [0110] • The lower part (3) has an outside diameter of 122 mm.
    [0111] • The stud (5) has a T-type configuration, where the first upper part has a first diameter of 65 mm and a threaded hole (7) with a diameter of 14 mm and where the second lower part has a second diameter of 36 mm . • The rod (9) of the connecting piece (8) has a length of 71 mm and a diameter of 6 mm.
    [0112] • The threaded head (10) of the connecting piece (8) has a diameter of 16 mm and a height of 24 mm.
    [0113] • The outer diameter of the circular platinum electrode (11) is 68 mm.
    [0114] • The central hole of the platinum electrode (12) has a diameter of 16 mm.
    [0115]
    [0116] Example 1. Manufacture of titanium io electrodes coated with a platinum layer
    [0117]
    [0118] Before proceeding with platinum electrodeposition, the surface of the titanium electrode was adequately conditioned to ensure proper adhesion of the coating.
    [0119] First, said electrode was subjected to physical roughing with SiC sandpaper, in order to eliminate possible heterogeneities.
    [0120]
    [0121] Next, a step of cleaning the debased surface was carried out by impregnating it with a concentrated solution (30-60 g / L) of hot NaOH (75 ° C -80 ° C).
    [0122]
    [0123] Subsequently, chemical polishing was carried out by immersing the surface in a very concentrated solution of HNO3 (300-500 g / L) in the presence of fluoride anions at high concentrations (40-60 g / L) for several minutes.
    [0124]
    [0125] Finally, electrochemical anodizing was carried out under potentiostatic conditions, applying a cell potential of 60-65 V for a period of 20 40 minutes, using a platinum mesh as a cathode and using a solution of oxalic acid (80-100 g / L) at room temperature.
    [0126]
    [0127] The platinum electrodeposition process itself was carried out using the experimental assembly described in Figure 1. For this purpose, a Teflon cell formed by two coupled parts is used to allow the pin on which the electrodeposition is to be carried out inside. . The electrolyte composition was 10-30 g / L of H2PtCl6-6H2O in concentrated HCl medium (100-400 g / L). The electrodeposition was carried out at room temperature and in a galvanostatic manner, applying a current density of 20-40 mA cm-2 for several minutes (10-20 minutes).
    [0128]
    [0129] The electrodeposited platinum layers have thicknesses of 2-4 p, m, are fully adherent and are formed by small platinum nodules distributed homogeneously throughout the entire surface of the titanium electrode (Figure 2). In the space between these nodules and on them, the presence of small platinum crystals can be observed (Figure 3).
    [0130]
    [0131] Figures 4 (a) and (b) show, by way of comparison, microscopic images of the surface of a sample to which no pretreatment was applied, clearly observing that platinum coatings are very thin and that they simply exfoliate when removed from the solution and get in contact with the air.
    权利要求:
    Claims (11)
    [1]
    1. A procedure for coating titanium studs with platinum, characterized in that it comprises the following steps:
    a) deburred from the surface of the titanium stud,
    b) chemical cleaning of the surface of the titanium stud debuted in step (a),
    c) chemical polishing of the surface of the titanium stud obtained in step (b), d) electrochemical anodizing in the presence of oxalic acid, at a temperature between 20 ° C and 45 ° C, where the anode is the titanium stud obtained in step (c) and the cathode is platinum, and
    e) platinum electrodeposition on the titanium stud obtained in step (d).
    [2]
    2. The process according to claim 1, wherein the chemical cleaning step (b) is carried out by impregnating the deburred surface of the titanium stud obtained in step (a) with a concentrated solution of NaOH at a temperature between 75 ° C and 80 ° C.
    [3]
    3. The process of claim 2, wherein the concentration of the NaOH solution ranges from 30 g / L to 60 g / L.
    [4]
    4. The process according to any one of claims 1 to 3, wherein, in the chemical polishing step (c), the surface of the titanium stud obtained in step (b) is immersed in a concentrated solution of HNO3 and NaF.
    [5]
    5. The method according to claim 4, wherein the concentration of HNO3 is between 300 g / L and 500 g / L and where the concentration of NaF is between 40 g / L and 60 g / L.
    [6]
    6. The process according to any of claims 1 to 5, wherein the concentration of oxalic acid is between 80 g / L and 100 g / L.
    [7]
    7. The method according to any one of claims 1 to 6, wherein the electrochemical anodizing of step (d) is carried out by applying a potential of between 60 V and 65 V for a period of time between 20 min and 40 min.
    [8]
    8. The method according to any one of claims 1 to 7, wherein the electrodeposition step (e) is carried out at a temperature between 20 ° C and 45 ° C by applying a current density between 20 mA / cm2 and 40 mA / cm2 for a period of time between 10 min and 20 min.
    [9]
    9. The method according to any one of claims 1 to 8, wherein, in step (e) of electrodeposition an electrolyte comprising H2PtCl6.6H2O and concentrated HCl is used.
    [10]
    10. The method according to any of claims 1 to 9, wherein the thickness of the platinum layer deposited in step (e) is between 2 pm and 4 pm.
    [11]
    11. An electrochemical cell for plating titanium studs, characterized in that it comprises:
    • a top piece (1) of Teflon with a cylindrical configuration that has an internal circular hole (2) through,
    • a lower piece (3) of Teflon with a cylindrical configuration adapted to place the upper part (1), said lower part comprises
    or a ring-shaped protrusion (4) on an upper surface configured to accommodate a cylindrical stud (5) on which the electrodeposition is to be performed, where the stud with a T-type configuration, or and an inner opening (6 ) intern.
    • a cylindrical stud (5), with a T-type configuration with a first upper part and a second lower part, where the first upper part in turn comprises a threaded upper hole (7) configured to join with the head (10) of the connecting piece (8) and resting on the lower part (3) and where the second part is configured to be housed in the through interior opening of the lower part (6),
    • a connection piece (8) comprising a threaded head (10) and a rod (9), where the head (10) is configured to thread with the threaded top hole of the stud (7), and
    • a platinum electrode (11) comprising a central hole (12) to be inserted through the connection piece (8) and to be housed in the inner circular hole (2) of the upper part.
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    同族专利:
    公开号 | 公开日
    ES2743828B2|2020-06-25|
    WO2021144481A1|2021-07-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3096272A|1957-10-24|1963-07-02|Amalgamated Curacao Patents Co|Noble metal coated titanium electrode and method of making and using it|
    US3650861A|1965-07-01|1972-03-21|Imp Metal Ind Kynoch Ltd|Surface treatment of titanium|
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    PCT/ES2020/070791| WO2021144481A1|2020-01-16|2020-12-14|Electrochemical method for platinum-plating titanium lugs and cell|
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