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EP3757257B1 - Procédé de formation de revêtements antibactériens poreux sur une surface de titane et d'alliages de titane - Google Patents

Procédé de formation de revêtements antibactériens poreux sur une surface de titane et d'alliages de titane Download PDF

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Publication number
EP3757257B1
EP3757257B1 EP20460020.9A EP20460020A EP3757257B1 EP 3757257 B1 EP3757257 B1 EP 3757257B1 EP 20460020 A EP20460020 A EP 20460020A EP 3757257 B1 EP3757257 B1 EP 3757257B1
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EP
European Patent Office
Prior art keywords
titanium
mol
oxidation
bath
plasma
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EP20460020.9A
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German (de)
English (en)
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EP3757257A1 (fr
Inventor
Wojciech Simka
Alicja Kazek-Kesik
Katarzyna Lesniak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Politechnika Slaska im Wincentego Pstrowskiego
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Politechnika Slaska im Wincentego Pstrowskiego
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

Definitions

  • the subject of this invention is a formation method of the porous oxide layers on the surface of titanium and titanium alloys by plasma electrochemical oxidation. Due to the oxidation in baths containing suspended, insoluble particles of silver and copper compounds, the obtained oxide layers are intended to be characterized by antimicrobial and/or bacteriostatic properties.
  • Titanium and titanium alloys are used as long-term implant materials characterized by good biocompatibility with hard and soft tissue of the human body.
  • bactericides such as antibiotics.
  • a good example of different than antibiotics bactericides can be the modified implant biomaterials containing silver or copper in their composition. So far in the literature, there are known studies of obtaining layers containing silver or copper compounds formed from soluble forms of these elements compounds.
  • the patent no. CN 101899700 describes the method of obtaining bioactive coatings on the surface of titanium and magnesium alloys by the plasma electrochemical oxidation using bath consisting of AgNO 3 , which results in the formation of porous oxide layers containing calcium, phosphorus and silver improving the bioactivity of the coatings, as well as their corrosion resistance and decreasing the risk of bacterial infections caused by the implantation process.
  • the thickness of the coating formed on the surface of the titanium alloy measured 50-85 ⁇ m, the porosity of the coating was in the range from 20% to 30%, and the determined adhesion of the coating to the substrate was 23-40 MPa.
  • the patent no. CN 108543109 describes the formation method of composite materials with antibacterial properties.
  • the composite consists of ceramic TiO 2 and silver nanoparticles on the surface of a titanium alloy intended for use as an implant for bone tissue.
  • a titanium alloy intended for use as an implant for bone tissue.
  • Cimenoglu Materials Science and Engineering, 71 (2017) 565
  • Cimenoglu Materials Science and Engineering, 71 (2017) 565
  • the manuscript "Characteristics of multi-layer coatings synthesized on Ti6Al4V alloy by micro-arc oxidation in silver nitrate added electrolytes" ( F. Muhaffel, G. Cempura, M. Menekse, A. Czyrska-Filemonowicz, N. Karaguler, H. Cimenoglu, Surface and Coating Technology.
  • Cimenoglu Materials Science and Engineering C, 48 (2015) 579
  • Corrosion behavior of Zn-incorporated antibacterial TiO2 porous coating on titanium (X. Zhang, H. Wang, J. Li, X. He, R. Hang, X. Huang, L. Tian, B.
  • Harni árová, Materials, 9 (2016) 318) describes the method of anodic oxidation of titanium from the bath containing Cu(NO 3 ) 2 .
  • 1 dm 3 of bath may contain 85% H 3 PO 4 and 10-600 g of dissolved Cu(NO 3 ) 2 .
  • Microstructure and antibacterial properties of Cu-doped TiO2 coating on titanium by micro-arc oxidation (X. Yao, X. Zhang, H. Wu, L. Tian, Y. Ma, B.
  • the patent no. PL 396115 present the method of plasma electrochemical oxidation of titanium and its alloys in suspension ZrSiO 4 at a concentration of 1-100 g ⁇ dm -3 with the addition of an alkali metal hydroxide at a concentration of 5-100 g ⁇ dm -3 , temperature of 15-50°C, anodic current density 5-500 mA ⁇ dm -2 and applied voltage 1-600 V for 1-30 minutes.
  • an alkali metal hydroxide at a concentration of 5-100 g ⁇ dm -3
  • temperature of 15-50°C anodic current density 5-500 mA ⁇ dm -2
  • applied voltage 1-600 V for 1-30 minutes.
  • PL 214630 there is presented the method of electrochemical plasma oxidation of Ti-xNb-yZr alloys in a Ca(H 2 PO 2 ) 2 solution at a concentration of 1-150 g ⁇ dm -3 or in a NaH 2 PO 2 solution at a concentration of 1-250 g ⁇ dm -3 , temperature in the range of 15-50°C, anodic current density of 5-5000 mA ⁇ dm -2 and applied voltage of 100-650 V for 1-60 minutes.
  • This process was carried out in solutions of 0.1M Ca(H2PO2)2 with various concentrations of tricalcium phosphate (Ca3(PO4)2), wollastonite (CaSiO3), or silica (SiO2) using voltages of up to 350V.
  • the surface microstructure (SEM, cross-section of coating), roughness and chemical composition (energy-dispersive X-ray spectroscopy, thin layer X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy) of the porous oxide layers were investigated.
  • the concentration of powder added to the solution changed the chemical composition and morphology of PEO coatings on the Ti-15Mo alloy surface. Calcium and phosphorous compounds were detected in the coatings formed on the substrate by the PEO process at 300V.
  • the aim of the invention is to develop a method allowing to obtain the porous oxide layers with incorporated compounds with antibacterial properties.
  • the essence of the invention is the surface modification by plasma electrochemical oxidation in aqueous Ca(H 2 PO 2 ) 2 bath at the concentration from 0.01 mol ⁇ dm -3 to 5 mol ⁇ dm -3 with the anodic current density from 1 mA ⁇ cm -2 to 250 mA ⁇ cm -2 and applied voltage from 50 V to 600 V by immersing the element which surface is to be modified in the aqueous Ca(H 2 PO 2 ) 2 bath solution characterized in that the bath comprises insoluble particles of silver(I) oxide Ag 2 O, copper(I) oxide Cu 2 O or copper(II) oxide CuO at a concentration from 1 g ⁇ dm -3 to 400 g ⁇ dm -3 .
  • the invention describes the method of the plasma electrochemical oxidation of titanium and its titanium alloys in suspensions containing insoluble silver or copper compounds in the form of the oxides. In this way, it is possible to obtain porous oxide layers incorporated with particles of compounds characterised by the antibacterial properties.
  • the addition of mentioned silver and copper suspension compounds can be a one-step modification of the surface of titanium and its alloys. Thanks to this, there is a chance to eliminate the necessity of high, oral antibiotic delivery route, which is the main cause of increasing bacteria resistance to antibiotics. Additionally, the number of side effects and allergic reactions related to antibiotic treatment can be reduced.
  • the surfaces anodised via plasma electrolytic oxidation process are porous and rough, which promotes the proliferation of living cells and supports the osseointegration process.
  • Example 1 The titanium implant, pre-treated by polishing, degreasing, etching and rinsing in demineralised water is placed in the solution containing 0.1 mol ⁇ dm -3 Ca(H 2 PO 2 ) 2 and the suspension of 10 g ⁇ dm -3 Ag 2 O. After placing the implant in the anodising bath, the electrolytic plasma oxidation process is carried out by polarizing it with the anodic current density of 150 mA ⁇ cm -2 . The process is carried out for 5 minutes, with the maximum voltage of 300 V. After the process, the implant is rinsed in demineralised water and air-dried at 45°C.
  • Example II The implant made of Ti-13Nb-13Zr alloy, mechanically pre-treated, degreased, etched and rinsed in demineralised water is placed in the anodising bath containing 0.01 mol ⁇ dm -3 Ca(H 2 PO 2 ) 2 and a suspension of 100 g ⁇ dm -3 Cu 2 O. After placing the implant in the bath, the electrolytic plasma oxidation process is carried out by polarizing it with the anodic current density of 100 mA ⁇ cm -2 . The process is carried out for 7 minutes, with the maximum voltage of 350 V. After the process, the implant is rinsed in demineralised water and air-dried at 45°C.
  • Example III The implant made of Ti-15Mo alloy, mechanically pre-treated, degreased, etched and rinsed in demineralised water is placed in the anodising bath containing 5 mol ⁇ dm -3 Ca(H 2 PO 2 ) 2 and the suspension of 200 g ⁇ dm -3 CuO. After placing the implant in the bath, the electrolytic plasma oxidation process is carried out by polarizing it with the anodic current density of 200 mA ⁇ cm -2 . The process is carried out for 5 minutes, with the maximum voltage of 400 V. After the process, the implant is rinsed in demineralised water and air-dried at 45°C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Claims (1)

  1. La méthode de modification de la surface du titane par oxydation électrochimique par plasma dans un bain aqueux de Ca(H2PO2)2 à une concentration de 0.01 mol-dm-3 à 5 mol dm-3 avec une densité de courant anodique de 1 mA cm-2 à 250 mA cm-2 et une tension appliquée de 50 V à 600 V en immergeant l'élément dont la surface doit être modifiée dans la solution aqueuse du bain de Ca(H2PO2)2 caractérisée par le fait que le bain comprend des particules insolubles d'oxyde d'argent (I) Ag2O, d'oxyde de cuivre (1) Cu2O ou d'oxyde de cuivre (II) CuO à une concentration de 1 g dm-3 à 400 g dm-3.
EP20460020.9A 2019-06-25 2020-04-27 Procédé de formation de revêtements antibactériens poreux sur une surface de titane et d'alliages de titane Active EP3757257B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL430375A PL239585B1 (pl) 2019-06-25 2019-06-25 Sposób otrzymywania porowatych powłok antybakteryjnych na powierzchni tytanu i jego stopów

Publications (2)

Publication Number Publication Date
EP3757257A1 EP3757257A1 (fr) 2020-12-30
EP3757257B1 true EP3757257B1 (fr) 2023-08-16

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PL (1) PL239585B1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL247456B1 (pl) * 2022-06-13 2025-07-07 Politechnika Warszawska Sposób modyfikacji powierzchni azotowanego tytanu TiO2+TiN+Ti2N+αTi(N) powłoką tlenkową domieszkowaną fosforanami wapnia przy wykorzystaniu metody plazmowego utleniania elektrochemicznego oraz powłoka tlenkowa na powierzchni azotowanego tytanu TiO2(Ca,P)+Ti2N+αTi(N) wytworzona tym sposobem
CN116115836A (zh) * 2023-02-02 2023-05-16 扬州钛博医疗器械科技有限公司 一种提高纯钛或钛合金表面抗菌性能的表面涂层、制备方法及应用
CN119507002A (zh) * 2024-11-01 2025-02-25 大连大学 一种可调控生成氧化亚铜的微弧氧化膜层及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL128693B1 (en) 1980-06-26 1984-02-29 Zaklady Wytworcze Urzadzen Syg Stabilized power pack
PL128024B1 (en) 1980-06-26 1983-12-31 Ct Kt Maszyn Gorniczych Komag Mechanized roof support of high supporting capacity
RU2075872C1 (ru) * 1994-07-27 1997-03-20 Институт химии Дальневосточного отделения РАН Электролит для микродугового оксидирования титана и его сплавов
CN101899700B (zh) 2009-05-25 2011-12-07 佳木斯大学 镁、钛表面超声微弧氧化载银抗菌生物活性涂层制备方法
PL214958B1 (pl) * 2010-03-22 2013-10-31 Politechnika Slaska Im Wincent Sposób modyfikacji warstwy wierzchniej tytanu i jego stopów fosforem lub wapniem i fosforem metodą elektrochemicznego utleniania plazmowego
PL214630B1 (pl) 2010-03-22 2013-08-30 Politechnika Slaska Im Wincent Sposób modyfikacji warstwy wierzchniej stopów tytanu typu Ti-xNb-yZr wapniem lub wapniem i fosforem metodą elektrochemicznego utleniania plazmowego
PL396115A1 (pl) 2011-08-29 2013-03-04 Politechnika Slaska Sposób pasywacji anodowej bezwanadowych stopów tytanu typu Ti-xNb-yZr
CN102677125B (zh) * 2012-06-13 2014-12-17 西北有色金属研究院 钛及钛合金医疗器械表面活性抗菌复合涂层的制备方法
CN108543109B (zh) 2018-03-13 2020-09-18 淮阴工学院 低磨双重抗菌钛基纳米复合材料骨植入体及其成形方法

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Publication number Publication date
PL239585B1 (pl) 2021-12-20
EP3757257A1 (fr) 2020-12-30
PL430375A1 (pl) 2020-07-13

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