EP3816327B1 - The formation method of porous antibacterial coatings on titanium and titanium alloys surface - Google Patents

The formation method of porous antibacterial coatings on titanium and titanium alloys surface Download PDF

Info

Publication number
EP3816327B1
EP3816327B1 EP20460021.7A EP20460021A EP3816327B1 EP 3816327 B1 EP3816327 B1 EP 3816327B1 EP 20460021 A EP20460021 A EP 20460021A EP 3816327 B1 EP3816327 B1 EP 3816327B1
Authority
EP
European Patent Office
Prior art keywords
titanium
mol
oxidation
plasma
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20460021.7A
Other languages
German (de)
French (fr)
Other versions
EP3816327A1 (en
EP3816327B8 (en
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
Original Assignee
Politechnika Slaska im Wincentego Pstrowskiego
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Politechnika Slaska im Wincentego Pstrowskiego filed Critical Politechnika Slaska im Wincentego Pstrowskiego
Publication of EP3816327A1 publication Critical patent/EP3816327A1/en
Publication of EP3816327B1 publication Critical patent/EP3816327B1/en
Application granted granted Critical
Publication of EP3816327B8 publication Critical patent/EP3816327B8/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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, copper or zinc compounds, the obtained oxide layers are intended to be characterized 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 implantation processes.
  • 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 the implant for bone tissue.
  • a titanium alloy intended for use as the implant for bone tissue.
  • Cimenoglu Materials Science and Engineering, 71 (2017)565 presents the method of plasma electrochemical oxidation using the bath containing Na 2 SiO 3 , NaOH and CH 3 COOAg.
  • 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 behaviour of Zn-incorporated antibacterial TiO2 porous coating on titanium (X. Zhang, H. Wang, J. Li, X. He, R. Hang, X. Huang, L. Tian, B.
  • the patent no. CN103911644 describes the plasma electrochemical oxidation of titanium alloys using baths containing phytic acid or phytate with the addition of electrolytes such as bioactive calcium, magnesium, zinc salts or with the addition of organic compounds such as tannic acid or hydroxides. Chromium(VI) compounds, fluorides and orthophosphates are not used during the process, therefore air polluting products have been limited. As a result of the process, microporous coating structures with good antibacterial properties, bioactivity, corrosion resistance and abrasion resistance are obtained. In the patent no.
  • CN1035266261 there is presented the method of obtaining ceramic membranes containing zinc on the surface of titanium or magnesium modified by plasma electrochemical oxidation process using electrolytes containing soluble compounds of zinc and calcium, titanium or magnesium as anodes and stainless steel as cathode.
  • the obtained ceramic membranes increase the bioactivity of the titanium or magnesium surface. Additionally, they degrade in the human body environment, causing the increase in immunity of human organism to bacterial infections and supporting the cell growth process in vitro.
  • Antibacterial activity and increased bone marrow stem cell functions of Zn-incorporated TiO2 coatings on titanium H. Hu, W. Zhang, Y. Qiao, X. Jiang, X. Liu, C.
  • CN 107376897 describes the method of plasma oxidation of electrochemical titanium in the electrolyte containing zinc nanoparticles.
  • Preparation and photocatalytic performance of ZnO/WO3/TiO2 composite coatings formed by plasma electrolytic oxidation Q. Honglei, L. Chen, Y. Xiwen, W. Mingyue, Y. Zongcheng, "Journal of Materials Science: Materials in Electronics "(29 (2018) 2060 ) there is known the method of plasma oxidation of electrochemical titanium in the electrolyte containing zinc nanoparticles.
  • Sopchenski, K. Popat, P. Soares, "Thin Solid Films” presents the method of anodic electrochemical oxidation in the bath containing Ca(CH 3 COO) 2 , calcium glycerophosphate and Zn(CH 3 COO) 2 .
  • the patent no. PL 225226 descibes the method of anodic electrochemical oxidation of tantalum, niobium and zirconium in the suspension of insoluble CaSiO 3 at a concentration of 1-300 g ⁇ dm -3 at the temperature of 15-50°C at the anodic current density of 5-200 mA ⁇ cm -2 and applied voltage of 100-650 V for 1-60 minutes.
  • PL 225227 there is presented the method of electrochemical oxidation of plasma titanium and its alloys in a suspension of CaSiO 3 at a concentration of 1-300 g ⁇ dm -3 at the temperature of 15-50°C, at the anodic current density of 5-200 mA ⁇ cm -2 and applied voltage of 100-650 V in time 1-60 minutes.
  • PL 396115 there is described the method of electrochemical oxidation of plasma titanium and its alloys in suspension containing ZrSiO 4 at the concentration of 1-100 g ⁇ dm -3 with the addition of the alkali metal hydroxide at the concentration of 5-100 g ⁇ dm -3 at the temperature of 15-50°C, at the anodic current density 5-500 mA ⁇ cm -2 and 1-600 V for 1-30 minutes.
  • PL 214630 describes the method of electrochemical plasma oxidation of Ti-xNb-yZr alloys in the Ca(H 2 PO 2 ) 2 solution at the concentration of 1-150 g ⁇ dm -3 or in a NaH 2 PO 2 solution at a concentration of 1-250 g ⁇ dm -3 at the temperature of 15-50°C, at the anodic current density of 5-5000 mA ⁇ cm -2 and applied voltage of 100-650 V for 1-60 minutes.
  • the paper " Surface characterisation of Ti-15Mo alloy modified by a PEO process in various suspensions" (A.Kazek-Kesik, G. Dercz, I. Kalemba, K.Suchanek, A. Kukharenko, D. Korotin, J.
  • the surface microstructure (SEM, cross-section of coating), roughness and chemical composition (energy dispersive X-ray spectroscopy, thin layer X-ray diffraction, X-ray photo electron 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 a method of titanium surface modification by plasma electrochemical oxidation in aqueous Ca(H 2 PO 2 ) 2 baths at a concentration from 0.01 mol ⁇ dm -3 to 5 mol ⁇ dm -3 with an 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 solution, characterized in that the bath comprises insoluble particles of metal phosphate at a concentration from 1 g ⁇ dm -3 to 400 g ⁇ dm -3 , and the aqueous salt solution contains copper(II) phosphate Cu 3 (PO 4 ) 2 at a concentration from 1 g ⁇ dm -3 to 400 g ⁇ dm -3 or the aqueous salt solution contains silver(I) phosphate Ag 3 PO 4 at a concentration from 1 g ⁇ dm -3 to 400 g ⁇ dm -3 or
  • 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.
  • An 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 I 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 3 PO 4 .
  • 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.
  • 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 the suspension of 100 g ⁇ dm -3 Cu 3 (PO 4 ) 2 . 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 Zn 3 (PO 4 ) 2 . 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prostheses (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Materials For Medical Uses (AREA)

Description

  • 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, copper or zinc compounds, the obtained oxide layers are intended to be characterized 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. During the implantation process, there is a risk of human tissues septic inflammation occurrence. Therefore, patients are being treated with bactericides such as antibiotics. However, because of the increasing resistance of bacteria to antibiotics, there are being carried out the studies of the alternative antibacterial agents. 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 AgNO3, 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 implantation processes. The thickness of the coating formed on the surface of the titanium alloy measured 50-85 µm, 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 TiO2 and silver nanoparticles on the surface of a titanium alloy intended for use as the implant for bone tissue. In the paper "Antibacterial properties of Ag (or Pt)-containing calcium phosphate coatings formed by micro-arc oxidation" (W.H. Song, H.S. Ryu, S.H. Hong, Journal of Biomedical Materials Research Part A, 88 (1) (2009) 246) there is known the method of plasma electrochemical oxidation using the bath containing: 0.04 mol·dm-3 C3H7Na2O6P·5H2O, 0.40 mol·dm-3 (CH3COO)2Ca·H2O and AgNO3 or CH3COOAg in the concentration range 0.00003-0.00400 mol·dm-3 at 250-450 V. The manuscript "Antibacterial titanium surfaces for medical implants" (S. Ferraris, S. Spriano, Materials Science and Engineering, 61 (2016) 965) presents the method of plasma electrochemical oxidation using the bath containing 7-25 nm silver nanoparticles, (CH3COO)2Ca and calcium glycerophosphate. The paper "Fabrication of oxide layer on zirconium by micro-arc oxidation: Structural and antimicrobial characteristics" (S. Fidan, F. Muhaffel, M. Riool, G. Cempura, L. de Boer, S. A. J Zaat, A. Czyrska- Filemonowicz, H. Cimenoglu, Materials Science and Engineering, 71 (2017)565) presents the method of plasma electrochemical oxidation using the bath containing Na2SiO3, NaOH and CH3COOAg. In 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. 307 (2016)308) there is known the method of plasma electrochemical oxidation in the bath containing Na2HPO4, Ca(CH3COO)2·H2O and AgNO3 in concentrations 0.1 g·dm-3 or 0.4 g·dm-3. In the manuscript "Corrosion Resistance and Antibacterial Properties of Ag-Containing MAO Coatings on AZ31 Magnesium Alloy Formed by Microarc Oxidation" (S. Ryu, SH Hong, Journal of Electrochemical Society, 157 (2010) 131), the method of plasma electrochemical oxidation in bath containing Na2SiO3 and AgNO3 is known. The paper "High-current anodization: A novel strategy to functionalize titanium-based biomaterials" (C. Chang, X. Huang, Y. Liu, L. Bai, X. Yang, R. Hang, B. Tang, PK Chu, Electrochimica Acta, 173 (2015) 345) presents the method of plasma electrochemical oxidation in the bath containing 7.6 g·dm-3Na3PO4, 9.4 g·dm-3 Ca(NO3)2 and 1.0 g·dm-3 AgNO3. The publication "In vitro antibacterial activity of porous TiO2-Ag composite layers against methicillin-resistant Staphylococcus ureus" (B.S. Necula, L.E. Fratila-Apachitei, S.A. Zaat, I. Apachitei, J. Duszczyk, Acta Biomaterialia, 5 (2009) 3573) presents the method of plasma electrochemical oxidation in the bath containing 0.15 mol·dm-3 Ca(CH3COO)2 or 0.02 mol·dm-3 calcium glycerophosphate with the addition of 0.03 g·dm-3 of nanoparticles Ag. The manuscript "Characteristics of multi-layer coating formed on commercially pure titanium for biomedical applications" (D. Teker, F. Muhaffel, M. Menekse, NG Karaguler, M. Baydogan, H. Cimenoglu, Materials Science and Engineering C, 48 (2015) 579) presents the method of anodic electrochemical oxidation using the bath containing Na2HPO4, Ca(CH3COO)2 and 0.0025 mol·dm-3 CH3COOAg. In the paper "Corrosion behaviour of Zn-incorporated antibacterial TiO2 porous coating on titanium" (X. Zhang, H. Wang, J. Li, X. He, R. Hang, X. Huang, L. Tian, B. Tang, Ceramic International, 32 (2016) 919) there is presented the method of anodic electrochemical oxidation in the bath consisting of 0.02 mol·dm-3 sodium β-glycerophosphate, 0.1 mol·dm-3 Ca(CH3COO)2, 0.1 mol·dm-3 Zn(CH3COO)2 and 6 g·dm-3 of nanoparticles Ag.
  • In the manuscript "Energy-Dispersive X-Ray Spectroscopy Mapping of Porous Coatings Obtained on Titanium by Plasma Electrolytic Oxidation in a Solution Containing Concentrated Phosphoric Acid with Copper Nitrate" (K. Rokosz, T. Hryniewicz, L. Dudek, A. Schutz, J. Heeg and M. Wienecke, Advances in Materials Science, 16 (2016) 15) there is presented the method of anodic oxidation of titanium using the bath containing Cu(NO3)2. 1 dm3 of bath may contain 85% H3PO4 and 600 g of dissolved Cu(NO3)2. The process can be carried out at 450 V. In the work "Catalytically active cobalt-copper-oxide layers on aluminium and titanium" (I.V. Lukiyanchuk, I.V. Chernykh, V.S. Rudnev, A. Yu Ustinov, L.M. Tyrina, P.M. Nedozorov, E.E. Dmitrieva, Protection of Metals and Physical Chemistry of Surfaces, 50 (2014) 209) there is known the method of obtaining oxide layers on the titanium surface by the plasma electrolytic oxidation treatment, followed by the modification of the obtained oxide layers with copper and cobalt by impregnation in solutions of soluble copper and cobalt salts. The manuscript "Biological Activity and Antibacterial Property of Nano-structured TiO2 Coating Incorporated with Cu Prepared by Micro-arc Oxidation" (W. Zhu, Z. Zhang, B. Gu, J. Sun, L. Zhu, Journal of Materials Science & Technology, 29 (2013) 237) describes the plasma electrochemical oxidation method using the bath containing 0.05 mol·dm-3 sodium β-glycerophosphate, 0.1 mol·dm-3 Ca(CH3COO)2 and 0.05 mol·dm-3 (CH3COO)2Cu. The publication "SEM, EDS and XPS Analysis of the Coatings Obtained on Titanium after Plasma Electrolytic Oxidation in Electrolytes Containing Copper Nitrate" (K. Rokosz, T. Hryniewicz, D. Matysek, S. Raaen, J. Validek, L. Dudek, M. Harničárová, Materials, 9 (2016) 318) there is known the method of anodic oxidation of titanium from the bath containing Cu(NO3)2. 1 dm3 of bath may contain 85% H3PO4 and 10-600 g of dissolved Cu(NO3)2. In the paper "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. Tang, Applied Surface Science , 292 (2014) 944) there is known the method of plasma electrochemical oxidation in the bath containing 2 g·dm-3 NaOH, 15 g·dm-3 NaH2PO4 and 3 g·dm-3 Cu nanoparticles. In the manuscript "One-step fabrication of cytocompatible micro/nano-textured surface with TiO2 mesoporous arrays on titanium by high current anodization" (X. Huang, Y. Liu, H. Yu, X. Yang, Y. Wang, R. Hang, B. Tang, Electrochimica Acta, 199 (2016) 116) there is known the method of anodic electrochemical oxidation using the bath containing 3.8-7.6 g·dm-3 Na3PO4 and 1.0-8.0 g·dm-3 Cu(NO3)2. The paper "The dual function of Cu-doped TiO2 coatings on titanium for application in percutaneous implants" (L. Zhang, J. Guo, X. Huang, Y. Zhang, Y. Han, Journal of Materials Chemistry, 4 (2016 ) 3788) presents the method of anodic electrochemical oxidation using the bath containing 0.02 mol·dm-3 sodium β-glycerophosphate, 0.02 mol·dm-3 Ca(CH3COO)2 and 0.00125-0.005 mol·dm-3 Cu(CH3COO)2.
  • The patent no. CN103911644 describes the plasma electrochemical oxidation of titanium alloys using baths containing phytic acid or phytate with the addition of electrolytes such as bioactive calcium, magnesium, zinc salts or with the addition of organic compounds such as tannic acid or hydroxides. Chromium(VI) compounds, fluorides and orthophosphates are not used during the process, therefore air polluting products have been limited. As a result of the process, microporous coating structures with good antibacterial properties, bioactivity, corrosion resistance and abrasion resistance are obtained. In the patent no. CN1035266261 there is presented the method of obtaining ceramic membranes containing zinc on the surface of titanium or magnesium modified by plasma electrochemical oxidation process using electrolytes containing soluble compounds of zinc and calcium, titanium or magnesium as anodes and stainless steel as cathode. The obtained ceramic membranes increase the bioactivity of the titanium or magnesium surface. Additionally, they degrade in the human body environment, causing the increase in immunity of human organism to bacterial infections and supporting the cell growth process in vitro. In the publication "Antibacterial activity and increased bone marrow stem cell functions of Zn-incorporated TiO2 coatings on titanium" (H. Hu, W. Zhang, Y. Qiao, X. Jiang, X. Liu, C. Ding, "Acta Biomaterialia" (8 (2012) 904) there is known the method of plasma electrochemical oxidation of titanium using the baths containing zinc. The bath containing 0.1 mol·dm-3 C4H6O4Ca·H2O, 0.05 mol·dm-3 C3H7Na2O6P·5H2O and Zn(CH3COO)2·2H2O in the concentration range 0.02-0.06 mol·dm-3 has been used. In the paper "SEM and EDS Characterization of Porous Coatings Obtained On Titanium by Plasma Electrolytic Oxidation in Electrolyte Containing Concentrated Phosphoric Acid with Zinc Nitrate" (K. Rokosz, T. Hryniewicz, K. Pietrzak, W. Malorny, "Advances in Materials Science" (17 (2017) 41), the titanium anodic oxidation method is described using the alkaline bath containing: 0.05 mol·dm-3 C3H7Na2O6P·5H2O, 0.10 mol·dm-3 Ca(CH3COO)2·H2O and 0.04 mol·dm-3 Zn(CH3COO)2·2H2O, as well as the acid bath containing: 85% H3PO4 and 500 g of dissolved Zn(NO3)2·6H2O. The patent no. CN 107376897 describes the method of plasma oxidation of electrochemical titanium in the electrolyte containing zinc nanoparticles. In the manuscript "Preparation and photocatalytic performance of ZnO/WO3/TiO2 composite coatings formed by plasma electrolytic oxidation" (Q. Honglei, L. Chen, Y. Xiwen, W. Mingyue, Y. Zongcheng, "Journal of Materials Science: Materials in Electronics "(29 (2018) 2060) there is known the method of plasma oxidation of electrochemical titanium in the electrolyte containing zinc nanoparticles.
  • In the paper "Enhanced corrosion resistance and in-vitro biodegradation of plasma electrolytic oxidation coatings prepared on AZ91 Mg alloy using ZnO nanoparticlesincorporated electrolyte" (A. Bordbar-Khiabani, B. Yarmand, M. Mozafari, Surface and Coatings Technology (360 (2019) 153) there is described the method of plasma electrochemical oxidation in the bath containing 4.5 g·dm-3 of ZnO nanoparticles. In the manuscript "The effect of applied voltages on the structure, apatite-inducing ability and antibacterial ability of micro arc oxidation coating formed on titanium Surface" (Q. Du, D. Wei, Y. Wang, S. Cheng, S. Liu, Y. Zhou, D. Jia, Bioactive Materials (3 (2018) 426) there is presented the method of plasma electrochemical oxidation using the bath consisting of 15 g·dm-3 EDTA, 8.8 g·dm-3 Ca(CH3COO)2·H2O, 6.3 g·dm3 Ca(H2PO4)2·H2O, 7.1 g·dm-3 Na2SiO3·9H2O, 5 g·dm-3 NaOH, 6 mL·dm-3 H2O2 and 8.5 g·dm-3 Zn(CH3COO)2. The publication "Bactericidal activity and cytotoxicity of a zinc doped PEO titanium coating" (L. Sopchenski, K. Popat, P. Soares, "Thin Solid Films" (660 (2018) 477) presents the method of anodic electrochemical oxidation in the bath containing Ca(CH3COO)2, calcium glycerophosphate and Zn(CH3COO)2. The patent no. PL 225226 descibes the method of anodic electrochemical oxidation of tantalum, niobium and zirconium in the suspension of insoluble CaSiO3 at a concentration of 1-300 g·dm-3 at the temperature of 15-50°C at the anodic current density of 5-200 mA·cm-2 and applied voltage of 100-650 V for 1-60 minutes. In the patent no. PL 225227 there is presented the method of electrochemical oxidation of plasma titanium and its alloys in a suspension of CaSiO3 at a concentration of 1-300 g·dm-3 at the temperature of 15-50°C, at the anodic current density of 5-200 mA·cm-2 and applied voltage of 100-650 V in time 1-60 minutes. In the patent no. PL 396115 there is described the method of electrochemical oxidation of plasma titanium and its alloys in suspension containing ZrSiO4 at the concentration of 1-100 g·dm-3 with the addition of the alkali metal hydroxide at the concentration of 5-100 g·dm-3 at the temperature of 15-50°C, at the anodic current density 5-500 mA·cm-2 and 1-600 V for 1-30 minutes. The patent no. PL 214630 describes the method of electrochemical plasma oxidation of Ti-xNb-yZr alloys in the Ca(H2PO2)2 solution at the concentration of 1-150 g·dm-3 or in a NaH2PO2 solution at a concentration of 1-250 g·dm-3 at the temperature of 15-50°C, at the anodic current density of 5-5000 mA·cm-2 and applied voltage of 100-650 V for 1-60 minutes. The paper "Surface characterisation of Ti-15Mo alloy modified by a PEO process in various suspensions" (A.Kazek-Kesik, G. Dercz, I. Kalemba, K.Suchanek, A. Kukharenko, D. Korotin, J. Michalska, A. Krzqkala, J.Piotrowski, E. Kurmaev, S. Cholakh, W. Simka, Materials science and engineering, vol.39 (2014)) reports on the surface modification of a Ti-15Mo alloy by plasma electrolyticoxidation (PEO). This process was carried out in solutions of 0.1 M 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 photo electron 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 a method of titanium surface modification by plasma electrochemical oxidation in aqueous Ca(H2PO2)2 baths at a concentration from 0.01 mol·dm-3 to 5 mol·dm-3 with an 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(H2PO2)2 solution, characterized in that the bath comprises insoluble particles of metal phosphate at a concentration from 1 g·dm-3 to 400 g·dm-3, and the aqueous salt solution contains copper(II) phosphate Cu3(PO4)2 at a concentration from 1 g·dm-3 to 400 g·dm-3 or the aqueous salt solution contains silver(I) phosphate Ag3PO4 at a concentration from 1 g·dm-3 to 400 g·dm-3 or the aqueous salt solution contains zinc phosphate Zn3(PO4)2 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. An 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 I: 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(H2PO2)2 and the suspension of 10 g·dm-3 Ag3PO4. 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(H2PO2)2 and the suspension of 100 g·dm-3 Cu3(PO4)2. 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(H2PO2)2 and the suspension of 200 g·dm-3 Zn3(PO4)2. 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.

Claims (1)

  1. The method of titanium surface modification by plasma electrochemical oxidation in aqueous Ca(H2PO2)2 baths at a concentration from 0.01 mol·dm-3 to 5 mol·dm-3 with an anodic current density from 1 mA·cm-2 to 250 mA·cm-2 and applied voltage from 50 V to 600 V is by immersing the element which surface is to be modified in the aqueous Ca(H2PO2)2 solution characterized in that the bath comprises insoluble particles of metal phosphate at a concentration from 1 g·dm-3 to 400 g·dm-3, and the aqueous salt solution contains copper(II) phosphate Cu3(PO4)2 at a concentration from 1 g·dm-3 to 400 g·dm-3 or the aqueous salt solution contains silver(I) phosphate Ag3PO4 at a concentration from 1 g·dm-3 to 400 g·dm-3 or the aqueous salt solution contains zinc phosphate Zn3(PO4)2 at a concentration from 1 g·dm-3 to 400 g·dm-3.
EP20460021.7A 2019-06-25 2020-05-05 The formation method of porous antibacterial coatings on titanium and titanium alloys surface Active EP3816327B8 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL430374A PL239584B1 (en) 2019-06-25 2019-06-25 Method of obtaining porous antibacterial coatings on the surface of titanium and its alloys

Publications (3)

Publication Number Publication Date
EP3816327A1 EP3816327A1 (en) 2021-05-05
EP3816327B1 true EP3816327B1 (en) 2023-10-18
EP3816327B8 EP3816327B8 (en) 2023-12-20

Family

ID=69740320

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20460021.7A Active EP3816327B8 (en) 2019-06-25 2020-05-05 The formation method of porous antibacterial coatings on titanium and titanium alloys surface

Country Status (2)

Country Link
EP (1) EP3816327B8 (en)
PL (2) PL239584B1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL240205B1 (en) * 2019-06-23 2022-02-28 Osteoplant Res And Development Spolka Z Ograniczona Odpowiedzialnoscia Method for modifying the surface of implants made of titanium or titanium alloys

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL128024B1 (en) 1980-06-26 1983-12-31 Ct Kt Maszyn Gorniczych Komag Mechanized roof support of high supporting capacity
PL128693B1 (en) 1980-06-26 1984-02-29 Zaklady Wytworcze Urzadzen Syg Stabilized power pack
RU2075872C1 (en) * 1994-07-27 1997-03-20 Институт химии Дальневосточного отделения РАН ELECTROLYTE FOR MICROARC OXIDATION OF TITANIUM AND ITS ALLOYS
CN101899700B (en) 2009-05-25 2011-12-07 佳木斯大学 Preparation method of ultrasonic microarc oxidation silver-carrying antibiotic bioactive coating on magnesium and titanium surface
PL214958B1 (en) * 2010-03-22 2013-10-31 Politechnika Slaska Im Wincent Method for modification of the surface layer of titanium and its alloys with calcium and phosphorus by electrochemical plasma oxidation
PL214630B1 (en) 2010-03-22 2013-08-30 Politechnika Slaska Im Wincent Method for modification of the surface layer of Ti-xNb-yZr alloys with calcium and phosphorus by electrochemical plasma oxidation
PL396115A1 (en) 2011-08-29 2013-03-04 Politechnika Slaska Method for anodic passivation of the vanadium-free titanium Ti-xNb-yZr alloys
CN102677125B (en) * 2012-06-13 2014-12-17 西北有色金属研究院 Preparation method of active antibacterial composite coating on surface of titanium and titanium alloy medical instrument
CN103526261A (en) 2013-10-17 2014-01-22 赵全明 Preparation method of zinc-containing micro-arc oxidation electrolyte and zinc-containing biological ceramic membrane
CN103911644B (en) 2014-04-09 2016-10-05 江西科技师范大学 Titanium alloy micro-arc oxidation electrolyte and differential arc oxidation method
CN107376897B (en) 2017-06-27 2020-02-18 华南理工大学 Oxidation catalysis film containing trimetal and preparation method and application thereof
CN108543109B (en) 2018-03-13 2020-09-18 淮阴工学院 Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL240205B1 (en) * 2019-06-23 2022-02-28 Osteoplant Res And Development Spolka Z Ograniczona Odpowiedzialnoscia Method for modifying the surface of implants made of titanium or titanium alloys

Also Published As

Publication number Publication date
PL3816327T3 (en) 2024-03-18
PL239584B1 (en) 2021-12-20
PL430374A1 (en) 2020-07-13
EP3816327A1 (en) 2021-05-05
EP3816327B8 (en) 2023-12-20

Similar Documents

Publication Publication Date Title
Durdu et al. The tribological properties of bioceramic coatings produced on Ti6Al4V alloy by plasma electrolytic oxidation
US8545559B2 (en) Modified metal materials, surface modifications to improve cell interactions and antimicrobial properties, and methods for modifying metal surface properties
KR100910064B1 (en) Implant material with excellent antibacterial and biocompatible properties and Manufacturing method thereof
Makurat-Kasprolewicz et al. Recent advances in electrochemically surface treated titanium and its alloys for biomedical applications: A review of anodic and plasma electrolytic oxidation methods
Harun et al. Hydroxyapatite-based coating on biomedical implant
Kazek-Kęsik et al. Surface characterisation of Ti–15Mo alloy modified by a PEO process in various suspensions
US20210338889A1 (en) Implant with ceramic coating, method of forming an implant, and method of applying a ceramic coating
Fialho et al. Surface engineering of nanostructured Ta surface with incorporation of osteoconductive elements by anodization
Simka et al. Modification of a Ti–Mo alloy surface via plasma electrolytic oxidation in a solution containing calcium and phosphorus
US20200289710A1 (en) Products of manufacture having enhanced biocompatibility and antibacterial properties and methods of making and using them
Simka et al. Formation of bioactive coatings on Ti–13Nb–13Zr alloy for hard tissue implants
WO2020067500A1 (en) Antimicrobial material, layered body, antimicrobial layered body, medical member, antimicrobial material production method, antimicrobial layered body production method, and antimicrobial method
CN108939155A (en) A kind of magnesium-based tissue engineering material antimicrobial coating and preparation method thereof
Mousa et al. Surface modification of magnesium and its alloys using anodization for orthopedic implant application
Mahmud et al. Recent developments in hydroxyapatite coating on magnesium alloys for clinical applications
Jarosz et al. Anodization of titanium alloys for biomedical applications
Safavi et al. Improved osteogenic activity of NiTi orthopedic implant by HAp-Nb2O5 composite coatings: Materials and biological points of view
EP3816327B1 (en) The formation method of porous antibacterial coatings on titanium and titanium alloys surface
Peng et al. Hydrothermal growth of hydroxyapatite and ZnO bilayered nanoarrays on magnesium alloy surface with antibacterial activities
TWI532883B (en) Titanium or titanium alloy having antibacterial surface and method for manufacturing the same
Acar et al. Improving the wettability and corrosion behavior of Cp-Ti by applying anodization surface treatment with the addition of boric acid, graphene oxide and hydroxyapatite
Kazek‐Kęsik et al. In vitro bioactivity investigations of T i‐15 M o alloy after electrochemical surface modification
EP3757257B1 (en) The formation method of porous antibacterial coatings on titanium and titanium alloys surface
Kim et al. Effect of surface pretreatment and pack cementation on bioactivity of titanium dental implant
Vangolu et al. Corrosion and wear performances of hydroxyapatite and boron-containing TiO2 composite coatings on Ti6Al7Nb alloy

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20211027

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230322

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020019409

Country of ref document: DE

GRAT Correction requested after decision to grant or after decision to maintain patent in amended form

Free format text: ORIGINAL CODE: EPIDOSNCDEC

REG Reference to a national code

Ref country code: CH

Ref legal event code: PK

Free format text: BERICHTIGUNG B8

Ref country code: CH

Ref legal event code: PK

Free format text: BERICHTIGUNG PRIORITAET

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20231018

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1622537

Country of ref document: AT

Kind code of ref document: T

Effective date: 20231018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240218

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240119

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240118

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240118

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231018

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20240123

Year of fee payment: 5