EP4332278A1 - Verfahren zur elektrochemischen oberflächenbehandlung von biomedizinischen produkten aus titan oder ti-basierten legierungen - Google Patents

Verfahren zur elektrochemischen oberflächenbehandlung von biomedizinischen produkten aus titan oder ti-basierten legierungen Download PDF

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EP4332278A1
EP4332278A1 EP22193733.7A EP22193733A EP4332278A1 EP 4332278 A1 EP4332278 A1 EP 4332278A1 EP 22193733 A EP22193733 A EP 22193733A EP 4332278 A1 EP4332278 A1 EP 4332278A1
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Prior art keywords
treatment
electrochemical
biomedical product
reline
glyceline
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EP22193733.7A
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English (en)
French (fr)
Inventor
Anna Kityk
Miroslav HNATKO
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Centrum Pre Vyuzitie Pokrocilych Materialov Slovenskej Akademie Vied Verejna Vyskumna Institucia
Ustav Anorganickej Chemie Slovenskej Akademie Vied Verejna Vyskumna Institucia
Original Assignee
Centrum Pre Vyuzitie Pokrocilych Materialov Slovenskej Akademie Vied Verejna Vyskumna Institucia
Ustav Anorganickej Chemie Slovenskej Akademie Vied Verejna Vyskumna Institucia
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Priority to EP22193733.7A priority Critical patent/EP4332278A1/de
Priority to PCT/SK2023/050024 priority patent/WO2024049360A2/en
Publication of EP4332278A1 publication Critical patent/EP4332278A1/de
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/08—Etching of refractory metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/26—Polishing of heavy metals of refractory metals

Definitions

  • the invention relates to the technical field of electrochemical surface treatment of biomedical products based on Ti and Ti-alloys.
  • Ti and Ti-alloys remain the most common materials for the manufacture of prostheses and implants.
  • titanium and its alloys cannot meet all clinical requirements without a special pretreatment of their surfaces. Therefore, preliminary surface treatment (modification) of biomedical Ti-based alloys is often performed in order to improve the biological, chemical, and physical-mechanical properties.
  • preliminary surface treatment (modification) of biomedical Ti-based alloys is often performed in order to improve the biological, chemical, and physical-mechanical properties.
  • the common types of these surface modifications are associated with mechanical, laser, chemical and electrochemical surface treatments and also with combinations of these techniques.
  • Electrochemical surface treatment method is generally considered as one of the most efficient, convenient and adaptable technique for improvement of the physical-mechanical surface properties of titanium and titanium-based alloys [1].
  • the process of electrochemical surface treatment of titanium alloys is carried out in electrolytes based on concentrated acids (e.g., H 2 SO 4 , HF, H 3 PO 4 , HNO 3 , HClO 4 , etc.) and alcohols mixtures.
  • concentrated acids e.g., H 2 SO 4 , HF, H 3 PO 4 , HNO 3 , HClO 4 , etc.
  • alcohols mixtures e.g., ethanol, etc.
  • These electrolytes are environmentally hazardous, toxic and sometimes explosive. It is obvious that the use of highly concentrated acidic electrolytes is not only environmentally unsafe, but also dangerous for humans. In this regard, the search for environmentally friendly and safety alternatives to the classical acidic electrolytes for electrochemical surface treatment of Ti and Ti-alloys is important and relevant [2].
  • Ethaline has been proposed as an alternative to the most-common acidic electrolytes for the electropolishing of titanium alloys [3].
  • Ethaline has several disadvantages, such as poor reproduction of the electropolishing results, which in some cases leads to the subpar quality of the processed surfaces, and insufficient effectivity of the process.
  • the aim of this invention is to provide electrolytes for electrochemical surface treatment of titanium alloys prostheses and implants that are environmentally friendly, highly efficient and gives a reliably repeatable results, that are also cheap, easy to prepare, easily biodegradable.
  • This invention relates to the surface modification of biomedical Ti and Ti-alloys in deep eutectic solvent Reline or Glyceline at room temperatures without additional heating or cooling.
  • Reline is a eutectic mixture of choline chloride (vitamin B 4) and urea in molar ratio of components 1:2, respectively.
  • Glyceline is a eutectic mixture of choline chloride (vitamin B 4) and glycerol in molar ratio of components 1:2, respectively.
  • the formation of viscous near-electrode surface layer plays key role due to the crucial place of diffusion control in etching and polishing processes. It has been found out that a thickness and density of the near-electrode viscous layer suitable for high processing efficiency can be achieved for deep eutectic solvents with higher viscosity (density). The more viscous the electrolyte, the faster the formation of a near-electrode layer of suitable thickness and density is achieved. Moreover, the higher the viscosity and density of the electrolyte the more stable surface layer is formed.
  • the mixtures such as Reline or Glyceline that have relatively high density and also high viscosity at the room temperature are eminently suitable to be used as electrolytes for the electrochemical surface treatment according to this invention.
  • the density of Reline is 1.24 g cm -3 and viscosity is 750 cP (at 25 °C)
  • the density of Glyceline is 1.19 g cm -3
  • viscosity is 259 cP (at 25 °C) (for comparison, the same parameters for Ethaline is 1.12 g cm -3 and 37 cP, respectively).
  • the second important factor which can increase the efficiency of electropolishing or electrochemical etching, is a change in the mechanism of electrochemical processes (a decrease in the activation energy due to a change in the nature of intermediate particles, a decrease in the number of stages in the overall electrochemical reaction, etc.).
  • the deep eutectic solvents Reline and Glyceline which contains urea and glycerol, except ethylene glycol that component of Ethaline, will provide formation of the intermediate complexes with different nature (urea and glycerol Ti - containing complexes, except ethylene glycol Ti - containing complexes in Ethaline).
  • the method for electrochemical surface treatment of biomedical products made of titanium or Ti-based alloys according to the present invention comprises the steps:
  • Subsequent cleaning from electrolyte residuals after proposed electrochemical treatment can be performed in water ultrasonic bath during 5 to 15 min. and air drying until the water has completely evaporated.
  • Proposed electrochemical method of surface treatment of biomedical Ti and Ti-alloys in Reline or Glyceline is a highly efficient and eco-friendly technic for the surface properties enhancement.
  • This kind of treatment allows improving the surface chemistry, morphology, topography and such surface properties as wettability, corrosion resistance and bio-compatibility, which is very important for Ti and Ti-alloys for biomedical application.
  • Reline has melting point 12 °C, so at room temperatures it is a colorless transparent liquid with numerous attractive characteristics, such as cheapness, safety, non-toxicity, non-volatility, thermal stability, non-flammability, sustainability, and biodegradability. Melting point of Glyceline is -44 °C, thus, at all temperatures higher than -44°C this eutectic mixture is liquid.
  • Reline and Glyceline possess noticeable benefits in comparison with ordinary acidic electrolytes, such as high effectivity, eco-friendliness, low coast, resource-saving, low corrosivity towards steel equipment and human health safeness. Moreover, Reline and Glyceline have significant advantages as electrolytes for the electrochemical treatment in comparison with Ethaline, such as higher density and viscosity, higher biodegradability and lower price. Additionally, Reline is characterized by significantly lower hygroscopicity in comparison with Ethaline.
  • the key factor for the biodegradability of deep eutectic solvents is the neutrality of each hydrogen bond donor and acceptor, which produces a natural DESs mixture and can be easily metabolized by bacteria and fungi.
  • Biodegradability of Glyceline reaches 100 % in 28 days, Reline reaches 97.1 % in 28 days. In comparison, biodegradability of Ethaline is 81.9 % in 28 days. Thus, from ecological point of view, the industrial use of Reline or Glyceline is preferable.
  • Glyceline and Reline are cheaper in comparison with Ethaline.
  • Table 1 Comparative characteristic of physicochemical and bio properties of deep eutectic solvents Glyceline, Reline and Ethaline. Eutectic mixture Density ( ⁇ ), g cm -3 Viscosity ( ⁇ ), cP Biodegradability, % in 28 days Glyceline 1.19 259 95.9-100 Reline 1.24 750 97.1 Ethaline 1.12 37 81.9
  • the mechanism of electrochemical treatment of Ti and Ti-based alloys in Ethaline related with electrooxidation of Ti and formation one-dimensional Ti-glycolate complexes.
  • the mechanism of electrochemical treatment of pure titanium and Ti-alloys in Glyceline and Reline is different from that, which observed for Ethaline.
  • Electrooxidation of Ti in glycerol enriched media probably takes place with formation of Ti-glycerolate complexes like intermediate state for Ti 2+ , Ti 3+ stabilization before complete oxidation to the Ti 4+ .
  • the possibility of existence of Ti - glycerolate complexes in glycerol containing media is discussed previously in [4, 5].
  • the proposed electrochemical treatment of bio-medical Ti and Ti-alloys in Reline or Glyceline can be realized in two different modes: potentiostatic (constant potential) and galvanostatic (constant current).
  • Galvanostatic treatment is recommended for biomedical protheses and implants with well-known surface area and potentiostatic one for biomedical products with very complex shape, for which accurate measurement of the surface area is difficult or impossible.
  • the procedure of galvanostatic surface treatment realizes in two electrode system, where working electrode is Ti or Ti-alloy prosthesis or implant and counter electrode is Pt-grid or graphite with surface area comparable to the workpiece.
  • Reline or Glyceline is used as an electrolyte for surface treatment.
  • the volume of Reline/Glyceline can be variated depending on size of titanium bio-medical product.
  • the optimal time of treatment (5-60 min.) can be variated depending on initial state of Ti or Ti-alloy product (initial roughness, contamination, etc.).
  • prosthesis or implant must be located in electrochemical cell (bath) coaxially relative to the counter electrode, in this case the distance between all points of the workpiece and the counter electrode is approximately the same and current distribution uniform.
  • Electrochemical surface treatment must be carried out at temperature interval 15-40 °C. At temperatures below 15 °C it is possible local crystallization processes, which will change the electrolyte composition; at temperatures higher than 40 °C the conditions of the dissolution process will be changed from mass transfer controlled, which will lead to a significant deterioration in the processing result.
  • potentiostatic surface treatment treatment under constant potential, voltage
  • working electrode is Ti or Ti-alloy prosthesis or implant
  • counter electrode is Pt-grid or graphite with surface area comparable to the workpiece
  • reference electrode is Ag - wire, the electrode relative to which the potential in electrochemical cell is measured and controlled.
  • potentiostatic treatment can be used the same like for galvanostatic treatment volume of electrolyte, temperatures and time of treatment depending on desired result of surface morphology.
  • the potential (E [V]) during the treatment procedure controls by potentiostat.
  • etching potentials 1-5 V; for electropolishing is 6-30 V.
  • potentiostatic mode prosthesis or implant must be located in electrochemical cell (bath) coaxially relative to the counter electrode the same like for potentiostatic treatment.
  • the volume of electrolyte (Reline or Glyceline) is arbitrary depending on size and shape of the workpiece.
  • Table 3 Summarized parameters of electrochemical processing of Ti and Ti-based alloys in Reline and Glyceline. t/°C ⁇ /min.
  • 3D printed implants made of Ti-6AI-4V alloy - electrochemical treatment in Reline.
  • Reline was prepared by mixing of choline chloride (ChCI) and urea at a molar ratio of components 1:2 (ChCl : urea). The mixing was carried out at 250 rpm and 70 °C for 2 hours until a homogenous transparent colorless liquid was formed. After cooling electrolyte was ready for electrochemical using.
  • ChCI choline chloride
  • urea a molar ratio of components 1:2
  • Ti-6AI-4V alloy implants were degreased and cleaned before electrochemical processing. Ti-alloy details were immersed in ultrasonic water bath with 1 weight % of caustic soda for 5 min. at 40 °C. Afterwards the residues of the cleaning composition were thoroughly rinsed off with water. After drying in hot air flow Ti-6AI-4V alloy implants were ready for electrochemical treatment.
  • Electrochemical treatment procedure - galvanostatic mode
  • Galvanostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Reline was carried out in a two-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland). Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode. Electrochemical surface treatment was done in galvanostatic mode at two current densities (5 mA cm -2 and 25 mA cm -2 ). The surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 . Thus, processing currents were 0.04 A and 0.12 A, respectively.
  • the suitable volume of Reline for treatment of implants with mentioned surface area is 120 ml. The temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany). The duration of electrochemical treatment was 20 min. for each implant.
  • RMS surface roughness parameter
  • Electrochemical treatment procedure - potentiostatic mode
  • Potentiostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Reline was carried out in a three-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland).
  • Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode and Ag-wire was used as a pseudo-reference electrode.
  • Electrochemical surface treatment was done in potentiostatic mode at two chosen potentials (4 V and 15 V).
  • the surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 .
  • the suitable volume of Reline for treatment of implants with mentioned surface area is 120 ml.
  • the temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany).
  • the duration of electrochemical treatment was 20 min. for each implant.
  • RMS parameter the roughness of the implant surfaces was measured.
  • RMS is calculated as the Root Mean Square of a surfaces measured microscopic peaks and valleys.
  • the RMS values for potentiostatic treatment in Reline were 1410 nm and 175 nm for potentials of treatment 5 V and 30 V, respectively.
  • RMS parameter is 497 nm.
  • 3D printed implant made of Ti-6AI-4V alloy - electrochemical treatment in Glyceline.
  • Glyceline was prepared by mixing of choline chloride (ChCI) and glycerol at a molar ratio of components 1:2 (ChCI : glycerol). The mixing was carried out at 400 rpm and 70 °C for 1 hour until a homogenous transparent colorless liquid was formed. After cooling electrolyte was ready for electrochemical treatment of Ti-alloy implants.
  • ChCI choline chloride
  • glycerol glycerol
  • Ti-6AI-4V alloy implants were degreased and cleaned before electrochemical processing. Ti-alloy details were immersed in ultrasonic water bath with 1 weight % of caustic soda for 5 min. at 40 °C. Afterwards the residues of the cleaning composition were thoroughly rinsed off with water. After drying in hot air flow Ti-6AI-4V alloy implants were ready for electrochemical treatment.
  • Electrochemical treatment procedure - galvanostatic mode
  • Galvanostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Glyceline was carried out in a two-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland). Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode. Electrochemical surface treatment was done in galvanostatic mode at two current densities (5 mA cm -2 and 25 mA cm -2 ). The surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 . Thus, processing currents were 0.04 A and 0.12 A, respectively.
  • the suitable volume of Glyceline for treatment of implants with mentioned surface area is 120 ml. The temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany). The duration of electrochemical treatment was 20 min. for each implant.
  • RMS parameter The result of electrochemical treatment in Glyceline under galvanostatic conditions was evaluated by measuring the surface roughness (RMS parameter).
  • RMS is calculated as the Root Mean Square of a surfaces measured microscopic peaks and valleys.
  • the RMS values for galvanostatic surface treatment in Glyceline were 1245 nm and 226 nm for current densities of treatment 5 mA cm -2 and 25 mA cm -2 , respectively.
  • RMS parameter is 497 nm.
  • Electrochemical treatment procedure - potentiostatic mode
  • Potentiostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Glyceline was carried out in a three-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland). Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode and Ag-wire was used as a pseudo-reference electrode. Electrochemical surface treatment was done in potentiostatic mode at two chosen potentials (4 V and 15 V). The surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 . The suitable volume of Glyceline for treatment of implants with mentioned surface area is 120 ml. The temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany). The duration of electrochemical treatment was 20 min. for each implant.
  • RMS parameter The result of electrochemical treatment in Glyceline under potentiostatic conditions was evaluated by measuring the surface roughness (RMS parameter).
  • RMS is calculated as the Root Mean Square of a surfaces measured microscopic peaks and valleys.
  • the RMS values for potentiostatic surface treatment in Glyceline were 1280 nm and 220 nm for potentials of treatment 5 V and 30 V, respectively.
  • RMS parameter is 497 nm.
  • 3D printed implant made of Ti-6AI-4V alloy - electrochemical treatment in Ethaline.
  • Ethaline was prepared by mixing of choline chloride (ChCI) and ethylene glycol at a molar ratio of components 1:2 (ChCI : Ethgl). The mixing was carried out at 300 rpm and 70 °C for 1 hour until a homogenous transparent colorless liquid was formed. After cooling electrolyte was ready for electrochemical treatment of Ti-alloy implants.
  • ChCI choline chloride
  • Ethgl ethylene glycol
  • Ti-6AI-4V alloy implants were degreased and cleaned before electrochemical processing. Ti-alloy details were immersed in ultrasonic water bath with 1 weight % of caustic soda for 5 min. at 40 °C. Afterwards the residues of the cleaning composition were thoroughly rinsed off with water. After drying in hot air flow Ti-6AI-4V alloy implants were ready for electrochemical treatment.
  • Electrochemical treatment procedure - galvanostatic mode
  • Galvanostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Ethaline was carried out in a two-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland). Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode. Electrochemical surface treatment was done in galvanostatic mode at two current densities (5 mA cm -2 and 25 mA cm -2 ). The surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 . Thus, processing currents were 0.04 A and 0.12 A, respectively.
  • the suitable volume of Ethaline for treatment of implants with mentioned surface area is 120 ml. The temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany). The duration of electrochemical treatment was 20 min. for each implant.
  • the result of electrochemical treatment in Ethaline under galvanostatic conditions was also evaluated by comparison of the roughness of the samples before and after electrochemical treatment.
  • the measured parameters RMS the Root Mean Square of a surfaces measured microscopic peaks and valleys
  • Electrochemical treatment procedure - potentiostatic mode
  • Potentiostatic electrochemical surface treatment of 3D printed Ti-6AI-4V alloy implants in Ethaline was carried out in a three-electrode thermostated cell using potentiostat Metrohm Autolab PGSTAT302N (Switzerland). Ti-6AI-4V alloy implants served as working electrodes, Pt-grid with surface area comparable to the workpiece was an auxiliary electrode and Ag-wire was used as a pseudo-reference electrode. Electrochemical surface treatment was done in potentiostatic mode at two chosen potentials (4 V and 15 V). The surface area of 3D printed Ti-6AI-4V alloy implants was 4 cm 2 . The suitable volume of Ethaline for treatment of implants with mentioned surface area is 120 ml. The temperature during treatment was kept at a constant value of 25 °C using a thermostat Julabo model ME v.2 (Germany). The duration of electrochemical treatment was 20 min. for each implant.
  • the potentiostatic electrochemical surface treatment in Ethaline at different potentials affects the surface roughness of titanium alloy implants.
  • the measured parameters RMS the Root Mean Square of a surfaces measured microscopic peaks and valleys
  • Example Mode of treatment Processing current density or potential (i/E, mA cm -2 , V) Surface roughness (RMS, nm) Untreated Ti-6AI-4V - - 497
  • Example 1 Galvanostatic 5 mA cm -2 1366 25 mA cm -2 183 Potentiostatic 5 V 1410 30 V 175
  • Example 2 Galvanostatic 5 mA cm -2 1245 25 mA cm -2 226 Potentiostatic 5 V 1280 30 V 220
  • Example 3 Galvanostatic 5 mA cm -2 1123 25 mA cm -2 286 Potentiostatic 5 V 1173 30 V 280

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
EP22193733.7A 2022-09-02 2022-09-02 Verfahren zur elektrochemischen oberflächenbehandlung von biomedizinischen produkten aus titan oder ti-basierten legierungen Pending EP4332278A1 (de)

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EP22193733.7A EP4332278A1 (de) 2022-09-02 2022-09-02 Verfahren zur elektrochemischen oberflächenbehandlung von biomedizinischen produkten aus titan oder ti-basierten legierungen
PCT/SK2023/050024 WO2024049360A2 (en) 2022-09-02 2023-08-24 Method for electrochemical surface treatment of biomedical products made of titanium or ti-based alloys

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Citations (2)

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Patent Citations (2)

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US20040097755A1 (en) * 2000-09-27 2004-05-20 Abbott Andrew P. Ionic liquids and their use as solvents
WO2021115698A1 (en) * 2019-12-10 2021-06-17 Biotronik Ag Novel electrolyte for electropolishing titanium alloys

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Title
B. WALIVAARA, B.O. ARONSSON, M. RODAHL, J. LAUSMAA, P. TENGVALL: "Titanium with different oxides: in vitro studies of protein adsorption and contact activation", BIOMATERIALS, vol. 15, no. 10, 1994, pages 827 - 834, XP024142220, DOI: 10.1016/0142-9612(94)90038-8
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