EP3816327B1 - Verfahren zur herstellung von porösen antibakteriellen beschichtungen auf der oberfläche von titan und titanlegierungen - Google Patents

Verfahren zur herstellung von porösen antibakteriellen beschichtungen auf der oberfläche von titan und titanlegierungen Download PDF

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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
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Prior art keywords
titanium
mol
oxidation
plasma
concentration
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French (fr)
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EP3816327A1 (de
EP3816327B8 (de
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Wojciech Simka
Alicja Kazek-Kesik
Katarzyna Lesniak
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Politechnika Slaska im Wincentego Pstrowskiego
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Politechnika Slaska im Wincentego Pstrowskiego
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    • 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.

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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)
  • Prostheses (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Materials For Medical Uses (AREA)

Claims (1)

  1. Verfahren zur Oberflächenmodifizierung von Titan durch plasmaelektrochemische Oxidation in wässrigen Ca(H2PO2)2-Bädern mit einer Konzentration von 0,01 mol/dm-3 bis 5 mol/dm-3 mit einer anodischen Stromdichte von 1 mA/cm-2 bis 250 mA/cm-2 und einer angelegten Spannung von 50 V bis 600 V durch Eintauchen des Elements, dessen Oberfläche modifiziert werden soll, in die wässrige Ca(H2PO2)2-Lösung, dadurch gekennzeichnet, dass das Bad unlösliche Metallphosphatteilchen in einer Konzentration von 1 g/dm-3 bis 400 g/dm-3 enthält, und die wässrige Salzlösung Kupfer(II)-phosphat Cu3(PO4)2 in einer Konzentration von 1 g/dm-2 bis 400 g/dm-3 oder die wässrige Salzlösung Silber(l)-phosphat Ag3PO4 in einer Konzentration von 1 g-dm" bis 400 g-dm" oder die wäßrige Salzlösung Zinkphosphat Zn3(PO4)2 in einer Konzentration von 1 g/dm-3 bis 400 g/dm-3.
EP20460021.7A 2019-06-25 2020-05-05 Verfahren zur herstellung von porösen antibakteriellen beschichtungen auf der oberfläche von titan und titanlegierungen Active EP3816327B8 (de)

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PL430374A PL239584B1 (pl) 2019-06-25 2019-06-25 Sposób otrzymywania porowatych powłok antybakteryjnych na powierzchni tytanu i jego stopów

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL240205B1 (pl) * 2019-06-23 2022-02-28 Osteoplant Res And Development Spolka Z Ograniczona Odpowiedzialnoscia Sposób modyfikacji powierzchni implantów z tytanu lub stopów tytanu

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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 (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
CN103526261A (zh) 2013-10-17 2014-01-22 赵全明 一种含锌微弧氧化电解液及其含锌生物陶瓷膜的制备方法
CN103911644B (zh) 2014-04-09 2016-10-05 江西科技师范大学 钛合金微弧氧化电解液及微弧氧化方法
CN107376897B (zh) 2017-06-27 2020-02-18 华南理工大学 一种含有三金属的氧化催化膜及其制备方法与应用
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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PL240205B1 (pl) * 2019-06-23 2022-02-28 Osteoplant Res And Development Spolka Z Ograniczona Odpowiedzialnoscia Sposób modyfikacji powierzchni implantów z tytanu lub stopów tytanu

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PL3816327T3 (pl) 2024-03-18
PL239584B1 (pl) 2021-12-20
PL430374A1 (pl) 2020-07-13
EP3816327A1 (de) 2021-05-05
EP3816327B8 (de) 2023-12-20

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