EP3757257A1 - 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 PDFInfo
- Publication number
- EP3757257A1 EP3757257A1 EP20460020.9A EP20460020A EP3757257A1 EP 3757257 A1 EP3757257 A1 EP 3757257A1 EP 20460020 A EP20460020 A EP 20460020A EP 3757257 A1 EP3757257 A1 EP 3757257A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- sup
- sub
- mol
- oxidation
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000010936 titanium Substances 0.000 title claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title description 17
- 230000000844 anti-bacterial effect Effects 0.000 title description 13
- 229910001069 Ti alloy Inorganic materials 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 17
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 abstract description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 17
- 239000007943 implant Substances 0.000 description 14
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001736 Calcium glycerylphosphate Substances 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- AVPCPPOOQICIRJ-UHFFFAOYSA-L sodium glycerol 2-phosphate Chemical compound [Na+].[Na+].OCC(CO)OP([O-])([O-])=O AVPCPPOOQICIRJ-UHFFFAOYSA-L 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 description 2
- 229940095618 calcium glycerophosphate Drugs 0.000 description 2
- 235000019299 calcium glycerylphosphate Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229940127249 oral antibiotic Drugs 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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
- the method of plasma electrochemical oxidation using the bath containing Na 2 SiO 3 , NaOH and CH 3 COOAg 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 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.
- 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.
- 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 baths containing Ca(H 2 PO 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 silver(I) oxide Ag 2 O, copper(I) oxide Cu 2 O or copper(II) oxide CuO 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.
- 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.
Landscapes
- 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)
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 true EP3757257A1 (fr) | 2020-12-30 |
| EP3757257B1 EP3757257B1 (fr) | 2023-08-16 |
Family
ID=69726547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20460020.9A Active EP3757257B1 (fr) | 2019-06-25 | 2020-04-27 | Procédé de formation de revêtements antibactériens poreux sur une surface de titane et d'alliages de titane |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP3757257B1 (fr) |
| PL (1) | PL239585B1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL441461A1 (pl) * | 2022-06-13 | 2023-12-18 | Politechnika Warszawska | Sposób modyfikacji powierzchni azotowanego tytanu Grade 2 powłoką tlenkową domieszkowaną fosforanami wapnia przy wykorzystaniu metody plazmowego utleniania elektrochemicznego oraz powłoka tlenkowa na powierzchni azotowanego tytanu Grade 2 wytworzona tym sposobem |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL225227A1 (fr) | 1980-06-26 | 1982-01-04 | Ct Kt Maszyn Gorniczych Komag | |
| PL225226A1 (fr) | 1980-06-26 | 1982-01-04 | Zaklady Wytworcze Urzadzen Syg | |
| RU94028190A (ru) * | 1994-07-27 | 1996-05-20 | Институт химии Дальневосточного отделения РАН | Электролит для микродугового оксидирования титана и его сплавов |
| CN101899700A (zh) | 2009-05-25 | 2010-12-01 | 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 |
| CN102677125A (zh) * | 2012-06-13 | 2012-09-19 | 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 |
| PL396115A1 (pl) | 2011-08-29 | 2013-03-04 | Politechnika Slaska | Sposób pasywacji anodowej bezwanadowych stopów tytanu typu Ti-xNb-yZr |
| 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 |
| 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 |
| CN108543109A (zh) | 2018-03-13 | 2018-09-18 | 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 |
-
2019
- 2019-06-25 PL PL430375A patent/PL239585B1/pl unknown
-
2020
- 2020-04-27 EP EP20460020.9A patent/EP3757257B1/fr active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL225227A1 (fr) | 1980-06-26 | 1982-01-04 | Ct Kt Maszyn Gorniczych Komag | |
| PL225226A1 (fr) | 1980-06-26 | 1982-01-04 | Zaklady Wytworcze Urzadzen Syg | |
| RU94028190A (ru) * | 1994-07-27 | 1996-05-20 | Институт химии Дальневосточного отделения РАН | Электролит для микродугового оксидирования титана и его сплавов |
| CN101899700A (zh) | 2009-05-25 | 2010-12-01 | 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 |
| 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 |
| 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 |
| PL396115A1 (pl) | 2011-08-29 | 2013-03-04 | Politechnika Slaska | Sposób pasywacji anodowej bezwanadowych stopów tytanu typu Ti-xNb-yZr |
| CN102677125A (zh) * | 2012-06-13 | 2012-09-19 | 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 |
| CN108543109A (zh) | 2018-03-13 | 2018-09-18 | 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 |
Non-Patent Citations (16)
| Title |
|---|
| B.S. NECULAL.E. FRATILA-APACHITEIS.A. ZAAT1. APACHITEIJ. DUSZCZYK: "In vitro antibacterial activity of porous Ti0 -Ag composite layers against methicillin-resistant Staphylococcus ureus", ACTA BIOMATERIALIA, vol. 5, 2009, pages 3573, XP026693830, DOI: 10.1016/j.actbio.2009.05.010 |
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| 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 |
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| PL239585B1 (pl) | 2021-12-20 |
| PL430375A1 (pl) | 2020-07-13 |
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