ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSKBAHRIS..MTNORSMESMMAKHTNMD..........
J
BDM Ver 1.7.2 (20 November 2019) - 1100000/0
3816327
EUROPEAN PATENT APPLICATION
A1
20210505
EP
20460021.7
20200505
en
en
en
43037519
20190625
PL
20210505
202118
20210505
202118
C25D 11/02 20060101AFI20210401BHEP
C25D 11/26 20060101ALI20210401BHEP
de
VERFAHREN ZUR HERSTELLUNG VON PORÖSEN ANTIBAKTERIELLEN BESCHICHTUNGEN AUF DER OBERFLÄCHE VON TITAN UND TITANLEGIERUNGEN
en
THE FORMATION METHOD OF POROUS ANTIBACTERIAL COATINGS ON TITANIUM AND TITANIUM ALLOYS SURFACE
fr
PROCÉDÉ DE FORMATION DE REVÊTEMENTS ANTIBACTÉRIENS POREUX SUR UNE SURFACE DE TITANE ET D'ALLIAGES DE TITANE
Politechnika Slaska
101149273
P.430374 Phosphates2
Ul. Akademicka 2A
44-100 Gliwice
PL
Simka, Wojciech
ul. Kamienska 37
40-748 Katowice
PL
Kazek-Kesik, Alicja
ul. W. Grynia 15/12
41-310 Dabrowa Górnicza
PL
Lesniak, Katarzyna
ul. Zytnia 2
42-400 Zawiercie
PL
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
BA
ME
KH
MA
MD
TN
The method of titanium surface modification by plasma electrochemical oxidation in Ca(H_2PO_2)_2 baths at a concentration from 0.01 mol·dm^{-3} to 5mol·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 characterized by immersing the surface-modified element in an aqueous salt solution with insoluble particles of metal phosphate at a concentration from 1 g·dm^{-3} to 400 g·dm^{-3}.
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 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 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 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 TiO_2 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} C_3H_7Na_2O_6P·5H_2O, 0.40 mol·dm^{-3} (CH_3COO)_2Ca·H_2O and AgNO_3 or CH_3COOAg 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, (CH_3COO)_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 Na_2SiO_3, NaOH and CH_3COOAg. In the manuscript "Characteristics of multi-layer coatings synthesized on Ti6A14V 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 Na_2HPO_4, Ca(CH_3COO)_2·H_2O and AgNO_3 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 Na_2SiO_3 and AgNO_3 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^{-3} Na_3PO_4, 9.4 g·dm^{-3} Ca(NO_3)_2 and 1.0 g·dm^{-3} AgNO_3. 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(CH_3COO)_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 Na_2HPO4, Ca(CH_3COO)_2 and 0.0025 mol·dm^{-3} CH_3COOAg. 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(CH_3COO)_2, 0.1 mol·dm^{-3} Zn(CH_3COO)_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(NO_3)_2. 1 dm^3 of bath may contain 85% H_3PO_4 and 600 g of dissolved Cu(NO_3)_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(CH_3COO)_2 and 0.05 mol·dm^{-3} (CH_3COO)_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. Matýsek, S. Raaen, J. Valíček, L. Dudek, M. Harničárová, Materials, 9 (2016) 318) there is known the method of anodic oxidation of titanium from the bath containing Cu(NO_3)_2. 1 dm^3 of bath may contain 85% H_3PO_4 and 10-600 g of dissolved Cu(NO_3)_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·dff^{-3} NaOH, 15 g·dm^{-3} NaH_2PO_4 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} Na_3PO_4 and 1.0-8.0 g·dm^{-3} Cu(NO_3)_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(CH_3COO)_2 and 0.00125-0.005 mol·dm^{-3} Cu(CH_3COO)_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} C_4H_6O_4Ca·H_2O,
0.05 mol·dm^{-3} C_3H_7Na_2O_6P·5H_2O and Zn(CH_3COO)_2·2H_2O 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} C_3H_7Na_2O_6P·5H_2O, 0.10 mol·dm^{-3} Ca(CH_3COO)_2·H_2O and 0.04 mol·dm^{-3} Zn(CH_3COO)_2·2H_2O, as well as the acid bath containing: 85% H_3PO_4 and 500 g of dissolved Zn(NO_3)_2·6H_2O. 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/WO_3/TiO_2 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 nanoparticles-incorporated 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(CH_3COO)_2·H_2O, 6.3 g·dm^{-3} Ca(H_2PO_4)_2·H_2O, 7.1 g·dm^{-3} Na_2SiO_3·9H_2O, 5 g·dm^{-3} NaOH, 6 mL·dm^{-3} H_2O_2 and 8.5 g·dm^{-3} Zn(CH_3COO)_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(CH_3COO)_2, calcium glycerophosphate and Zn(CH_3COO)_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. In the patent no. 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. In the patent no. 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. The patent no. PL 214630 describes the method of electrochemical plasma oxidation of Ti-xNb-yZr alloys in the Ca(H_2PO_2)_2 solution at the concentration of 1-150 g·dm^{-3} or in a NaH_2PO_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 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 of titanium and titanium alloys via plasma electrochemical oxidation in the baths containing Ca(H_2PO_2)_2 at a concentration from 0.01 mol·dm^{-3} to 5 mol·dm^{-3}, at the anodic current density from 1 mA·cm^{-2} to 250 mA·cm^{-2} and applied voltage from 50 V to 600 V. The surface-modified elements are immersed in an aqueous salt solution containing insoluble cooper(II) phosphate Cu_3(PO_4)_2, silver(I) phosphate Ag_3PO_4 or zinc phosphate Zn_3(PO_4)_2 at a concentration from 1 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(H_2PO_2)_2 and the suspension of 10 g·dm^{-3} Ag_3PO_4. 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_2PO_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_2PO_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.
1. The method of titanium surface modification by plasma electrochemical oxidation in Ca(H_2PO_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 is characterized by immersing the surface-modified element in an aqueous salt solution with insoluble particles of metal phosphate at a concentration from 1 g·dm^{-3} to 400 g·dm^{-3}.
2. According to patent claim 1, the process is characteristic because 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}.
3. According to patent claim 1, the process is characteristic because the aqueous salt solution contains silver(I) phosphate Ag_3PO_4 at a concentration from 1 g·dm^{-3} to 400 g·dm^{-3}.
4. According to patent claim 1, the process is characteristic because the aqueous salt solution contains zinc phosphate Zn_3(PO_4)_2 at a concentration from 1 g·dm^{-3} to 400 g·dm^{-3}.
P.430374 Phosphates2
EP
20460021.7
Politechnika Slaska
DH
20210409
C25D
KAZEK-KESIK ALICJA ET AL
Surface characterisation of Ti-15Mo alloy modified by a PEO process in various suspens
MATERIALS SCIENCE AND ENGINEERING C
20140312
39
10.1016/J.MSEC.2014.03.008
0928-4931
259
272
XP029029210
A
1-4
* page 260, right-hand column, paragraph 2 - page 264, left-hand column, paragraph 2 *
* page 271, left-hand column, paragraph 3 *
NECULA B S ET AL
In vitro antibacterial activity of porous TiO"2-Ag composite layers against methicillin-resistant Staphylococcus aureus
ACTA BIOMATERIALIA, ELSEVIER, AMSTERDAM, NL
20091101
5
9
10.1016/J.ACTBIO.2009.05.010
1742-7061
3573
3580
XP026693830
A,D
1-4
* page 3574, left-hand column, paragraph 4 - page 3574, right-hand column, paragraph 4 *
* page 3575, right-hand column, paragraph 2 - page 3576, right-hand column, last paragraph *
PL
214958
B1
POLITECHNIKA SLASKA IM WINCENT [PL]
20131031
A
1-4
* paragraph [0003] *
* paragraphs [0006] - [0015] *
EPODOC
19960520
Database accession no. RU-94028190-A
EUROPEAN PATENT OFFICE, THE HAGUE, NL
XP002800828
A
1-4
* abstract *
RU
94028190
A
INST KHIM DAL NEVOSTOCHNOGO OTDEL RAN
19960520
* abstract *
MUHAFFEL FAIZ ET AL
Characteristics of multi-layer coatings synthesized on Ti6Al4V alloy by micro-arc oxidation in silver nitrate added electrolytes
SURFACE AND COATINGS TECHNOLOGY, ELSEVIER BV, AMSTERDAM, NL
20160901
307
10.1016/J.SURFCOAT.2016.09.002
0257-8972
308
315
XP029823815
A,D
1-4
* page 308, right-hand column, paragraph 2 - page 310, left-hand column, last paragraph *
CN
102677125
A
NW INST NON FERROUS METAL RES
20120919
A
1-4
* abstract *
Crottaz, Olivier
The Hague
20210330
PL
214958
B1
20131031
NONE
CN
102677125
A
20120919
NONE

REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description
- CN
101899700
[0003]
- CN
108543109
[0003]
- CN
103911644
[0003]
- CN
1035266261
[0003]
- CN
107376897
[0003]
- PL
225226
[0003]
- PL
225227
[0003]
- PL
396115
[0003]
- PL
214630
[0003]

Non-patent literature cited in the description
- W.H. SONG
H.S. RYU
S.H. HONG
Antibacterial properties of Ag (or Pt)-containing, calcium phosphate coatings formed by micro-arc oxidation
Journal of Biomedical Materials Research Part A
20090000
88
1
246
[0003]
- S. FERRARIS
S. SPRIANO
Antibacterial titanium surfaces for medical implants
Materials Science and Engineering
20160000
61
965
[0003]
- S. FIDAN
F. MUHAFFEL
M. RIOOL
G. CEMPURA
L. DE BOER
S. A. J ZAAT
A. CZYRSKA-FILEMONOWICZ
H. CIMENOGLU
Fabrication of oxide layer on zirconium by micro-arc oxidation: Structural and antimicrobial characteristics
Materials Science and Engineering
20170000
71
565
[0003]
- F. MUHAFFEL
G. CEMPURA
M. MENEKSE
A. CZYRSKA-FILEMONOWICZ
N. KARAGULER
H. CIMENOGLU
Characteristics of multi-layer coatings synthesized on Ti6A14V alloy by micro-arc oxidation in silver nitrate added electrolytes
Surface and Coating Technology
20160000
307
308
[0003]
- S. RYU
SH HONG
Corrosion Resistance and Antibacterial Properties of Ag-Containing MAO Coatings on AZ31 Magnesium Alloy Formed by Microarc Oxidation
Journal of Electrochemical Society
20100000
157
131
[0003]
- C. CHANG
X. HUANG
Y. LIU
L. BAI
X. YANG
R. HANG
B. TANG
PK CHU
High-current anodization: A novel strategy to functionalize titanium-based biomaterials
Electrochimica Acta
20150000
173
345
[0003]
- B.S. NECULA
L.E. FRATILA-APACHITEI
S.A. ZAAT
I. APACHITEI
J. DUSZCZYK
In vitro antibacterial activity of porous TiO2-Ag composite layers against methicillin-resistant Staphylococcus ureus
Acta Biomaterialia
20090000
5
3573
[0003]
- D. TEKER
F. MUHAFFEL
M. MENEKSE
NG KARAGULER
M. BAYDOGAN
H. CIMENOGLU
Characteristics of multi-layer coating formed on commercially pure titanium for biomedical applications
Materials Science and Engineering C
20150000
48
579
[0003]
- X. ZHANG
H. WANG
J. LI
X. HE
R. HANG
X. HUANG
L. TIAN
B. TANG
Corrosion behaviour of Zn-incorporated antibacterial TiO2 porous coating on titanium
Ceramic International
20160000
32
919
[0003]
- K. ROKOSZ
T. HRYNIEWICZ
L. DUDEK
A. SCHUTZ
J. HEEG
M. WIENECKE
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
Advances in Materials Science
20160000
16
15
[0003]
- I.V. LUKIYANCHUK
I.V. CHERNYKH
V.S. RUDNEV
A. YU USTINOV
L.M. TYRINA
P.M. NEDOZOROV
E.E. DMITRIEVA
Catalytically active cobalt-copper-oxide layers on aluminium and titanium
Protection of Metals and Physical Chemistry of Surfaces
20140000
50
209
[0003]
- W. ZHU
Z. ZHANG
B. GU
J. SUN
L. ZHU
Biological Activity and Antibacterial Property of Nano-structured TiO2 Coating Incorporated with Cu Prepared by Micro-arc Oxidation
Journal of Materials Science & Technology
20130000
29
237
[0003]
- K. ROKOSZ
T. HRYNIEWICZ
D. MATÝSEK
S. RAAEN
J. VALÍČEK
L. DUDEK
M. HARNIČÁROVÁ
SEM, EDS and XPS Analysis of the Coatings · Obtained on Titanium after Plasma Electrolytic Oxidation in Electrolytes Containing Copper Nitrate
Materials
20160000
9
318
[0003]
- X. YAO
X. ZHANG
H. WU
L. TIAN
Y. MA
B. TANG
Microstructure and antibacterial properties of Cu-doped TiO2 coating on titanium by micro-arc oxidation
Applied Surface Science
20140000
292
944
[0003]
- X. HUANG
Y. LIU
H. YU
X. YANG
Y. WANG
R. HANG
B. TANG
One-step fabrication of cytocompatible micro/nano-textured surface with TiO2 mesoporous arrays on titanium by high current anodization
Electrochimica Acta
20160000
199
116
[0003]
- L. ZHANG
J. GUO
X. HUANG
Y. ZHANG
Y. HAN
The dual function of Cu-doped TiO2 coatings on titanium for application in percutaneous implants
Journal of Materials Chemistry
20160000
4
3788
[0003]
- H. HU
W. ZHANG
Y. QIAO
X. JIANG
X. LIU
C. DING
Antibacterial activity and increased bone marrow stem cell functions of Zn-incorporated TiO2 coatings on titanium
Acta Biomaterialia
20120000
8
904
[0003]
- K. ROKOSZ
T. HRYNIEWICZ
K. PIETRZAK
W. MALORNY
SEM and EDS Characterization of Porous Coatings Obtained On Titanium by Plasma Electrolytic Oxidation in Electrolyte Containing Concentrated Phosphoric Acid with Zinc Nitrate
Advances in Materials Science
20170000
17
41
[0003]
- A. BORDBAR-KHIABANI
B. YARMAND
M. MOZAFARI
Enhanced corrosion resistance and in-vitro biodegradation of plasma electrolytic oxidation coatings prepared on AZ91 Mg alloy using ZnO nanoparticles-incorporated electrolyte
Surface and Coatings Technology
20190000
360
153
[0003]
- Q. DU
D. WEI
Y. WANG
S. CHENG
S. LIU
Y. ZHOU
D. JIA
The effect of applied voltages on the structure, apatite-inducing ability and antibacterial ability of micro arc oxidation coating formed on titanium Surface
Bioactive Materials
20180000
3
426
[0003]
- L. SOPCHENSKI
K. POPAT
P. SOARES
Bactericidal activity and cytotoxicity of a zinc doped PEO titanium coating
Thin Solid Films
20180000
660
477
[0003]