EP3816327A1 - 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 PDFInfo
- Publication number
- EP3816327A1 EP3816327A1 EP20460021.7A EP20460021A EP3816327A1 EP 3816327 A1 EP3816327 A1 EP 3816327A1 EP 20460021 A EP20460021 A EP 20460021A EP 3816327 A1 EP3816327 A1 EP 3816327A1
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- European Patent Office
- Prior art keywords
- titanium
- mol
- oxidation
- concentration
- plasma
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010936 titanium Substances 0.000 title claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title description 25
- 230000000844 anti-bacterial effect Effects 0.000 title description 17
- 229910001069 Ti alloy Inorganic materials 0.000 title description 10
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 28
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 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
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract 2
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- 229910000153 copper(II) phosphate Inorganic materials 0.000 claims description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000011575 calcium Substances 0.000 description 14
- 239000007943 implant Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000001736 Calcium glycerylphosphate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 230000000975 bioactive effect Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 description 3
- 229940095618 calcium glycerophosphate Drugs 0.000 description 3
- 235000019299 calcium glycerylphosphate Nutrition 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000011734 sodium 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
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 208000022362 bacterial infectious disease Diseases 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000012620 biological material Substances 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
- 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
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 235000002949 phytic acid Nutrition 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
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 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
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000001185 bone marrow Anatomy 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 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
- 210000004027 cell Anatomy 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 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
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001939 inductive effect Effects 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
- 229910000150 monocalcium phosphate Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 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
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 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
- 150000003751 zinc Chemical class 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 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.
- Antibacterial properties of Ag (or Pt)-containing, calcium phosphate coatings formed by micro-arc oxidation W.H. Song, H.S. Ryu, S.H.
- 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 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.
- 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.
- Chromium(VI) compounds, fluorides and orthophosphates are not used during the process, therefore air polluting products have been limited.
- microporous coating structures with good antibacterial properties, bioactivity, corrosion resistance and abrasion resistance are obtained.
- 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.
- the titanium anodic oxidation method is described using the alkaline bath containing: 0.05 mol ⁇ dm -3 C 3 H 7 Na 2 O 6 P ⁇ 5H 2 O, 0.10 mol ⁇ dm -3 Ca(CH 3 COO) 2 ⁇ H 2 O and 0.04 mol ⁇ dm -3 Zn(CH 3 COO) 2 ⁇ 2H 2 O, as well as the acid bath containing: 85% H 3 PO 4 and 500 g of dissolved Zn(NO 3 ) 2 ⁇ 6H 2 O.
- the patent no. CN 107376897 describes the method of plasma oxidation of electrochemical titanium in the electrolyte containing zinc nanoparticles.
- 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 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 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 cooper(II) phosphate Cu 3 (PO 4 ) 2 , silver(I) phosphate Ag 3 PO 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.
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Abstract
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 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 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 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 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-3 Na3PO4, 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. 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(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·dff-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
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 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(CH3COO)2·H2O, 6.3 g·dm-3 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 PL 225227 PL 396115 PL 214630 - 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(H2PO2)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 Cu3(PO4)2, silver(I) phosphate Ag3PO4 or zinc phosphate Zn3(PO4)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(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 (4)
- The method of titanium surface modification by plasma electrochemical oxidation in 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 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.
- According to patent claim 1, the process is characteristic because the aqueous salt solution contains copper(II) phosphate Cu3(PO4)2 at a concentration from 1 g·dm-3 to 400 g·dm-3.
- According to patent claim 1, the process is characteristic because the aqueous salt solution contains silver(I) phosphate Ag3PO4 at a concentration from 1 g·dm-3 to 400 g·dm-3.
- According to patent claim 1, the process is characteristic because the aqueous salt solution contains zinc phosphate Zn3(PO4)2 at a concentration from 1 g·dm-3 to 400 g·dm-3.
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PL3816327T3 (en) | 2024-03-18 |
EP3816327B8 (en) | 2023-12-20 |
PL239584B1 (en) | 2021-12-20 |
EP3816327B1 (en) | 2023-10-18 |
PL430374A1 (en) | 2020-07-13 |
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