SI23312A - Bioactive and photocatalytic coating on metal orthopaedic and dental implants and procedure of preparation - Google Patents
Bioactive and photocatalytic coating on metal orthopaedic and dental implants and procedure of preparation Download PDFInfo
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Bioaktivna in fotokatalitska prevleka na kovinskih ortopedskih in dentalnih vsadkih in postopek pripraveBioactive and photocatalytic coating on metal orthopedic and dental implants and preparation process
Predmet izuma je bioaktivna in fotokatalitska prevleka na kovinskih ortopedskih in dentalnih vsadkih in postopek priprave prevleke. Prevleka na osnovi titanovega oksida, ki se jo s postopkom hidrotermalne sinteze nanese na gladko, hrapavo ali makroporozno površino kovinskih ortopedskih ali dentalnih vsadkov za trajno ali začasno oporo skeletu ali pa kot nadomestek manjkajočega dela skeleta, je biokompatibilna, bioaktivna, hidrofilna in fotokatalitska, česar ne združuje nobena znana prevleka na vsadkih.The subject of the invention is a bioactive and photocatalytic coating on metal orthopedic and dental implants and a process for preparing the coating. Titanium oxide coating applied by hydrothermal synthesis to a smooth, rough or macroporous surface of metal orthopedic or dental implants for permanent or temporary skeletal support, or as a substitute for the missing skeleton, is biocompatible, bioactive, hydrophilic and photophilic does not combine any known implant coatings.
Znano stanjeKnown state
Večina dentalnih in ortopedskih vsadkov, ki služijo kot trajna ali začasna opora skeletu ali pa nadomeščajo del kosti, je kovinskih, saj so kovine v primerjavi z drugimi materiali bistveno bolj odporne proti zlomom. V dentalni in ortopedski rekonstrukciji so titan in njegove zlitine hitro pridobile veliko prednost pred ostalimi kovinami in zlitinami, saj jih zaradi relativno dobre korozijske odpornosti in biokompatibilnosti po izsledkih kliničnih raziskav telo boljše prenaša, kot druge kovine in zlitine. Značilno pa kovine in zlitine za vsadke, npr. različna jekla, zlitine Co-Cr in zlitine na osnovi titana, za povečanje mehanske trdnosti vsebujejo tudi elemente, ki so citotoksični ali nevrotoksični. V zadnjem času kot material za vsadke prevladuje zlitina Ti6A14V, ki je cenejša in mehansko odpornejša od čistega titana, vendar pa je tudi njena slabost prisotnost aluminija in vanadija, ki sta za organizem toksična.Most dental and orthopedic implants that serve as a permanent or temporary support to the skeleton or that replace part of the bone are metal, since metals are significantly more resistant to fractures than other materials. In dental and orthopedic reconstruction, titanium and its alloys quickly gained a great advantage over other metals and alloys, because of their relatively good corrosion resistance and biocompatibility, according to clinical research, they are better tolerated by the body than other metals and alloys. Typically, metals and implants for implants, e.g. various steels, Co-Cr alloys and titanium alloys also contain elements that are cytotoxic or neurotoxic to increase mechanical strength. Recently, the implant material has been dominated by Ti6A14V alloy, which is less expensive and more mechanically resistant than pure titanium, but its disadvantage is the presence of aluminum and vanadium, which are toxic to the body.
Slabost kovin je tudi ta, da v stiku s telesno tekočino korodirajo, da kovinski atomi difundirajo v okolico in povzročajo različne negativne odzive organizma in da se okolišnje tkivo relativno slabo prirašča na vsadek. Pogosta so tudi vnetja, ki so v veliki meri posledica prisotnosti bakterij med kirurškim posegom, kar lahko posledično vodi v razmajanje vsadka, zato je potrebna zamenjava vsadka, torej ponovna operacija. Možne so tudi alergične reakcije na elemente v kovini, ki difundirajo v okolišnje tkivo, kar povzroča različne zdravstvene težave, včasih pa zahteva celo odstranitev vsadka.The disadvantage of metals is that in contact with body fluid they corrode, that metal atoms diffuse into the environment and cause various negative responses of the organism and that the surrounding tissue grows relatively poorly at the implant. There are also frequent inflammations that are largely due to the presence of bacteria during surgery, which can in turn lead to implant malfunction, which requires replacement of the implant, ie reoperation. Allergic reactions to elements in the metal that diffuse into the surrounding tissue are also possible, causing various health issues, sometimes requiring even removal of the implant.
Ker je osteointegracija, t.j. zraščanje kosti in vsadka kovin slabša kot pri drugih materialih, npr. pri hidroksiapatitu in bioaktivnem steklu, so bile razvite številne tehnike modificiranjaBecause osteointegration, i.e. bone healing and metal implantation worse than other materials, e.g. for hydroxyapatite and bioactive glass, many modification techniques have been developed
-2površine kovin za kostne vsadke. Z namenom izboljšati osteointegracijo so bili razviti vsadki, npr. kolčne proteze s hrapavo površino, npr. z brazdami, z nanosom kovinskih kroglic ali porozne kovinske prevleke, s peskanjem, itd. Slabost takih prevlek je, poleg difuzije kovinskih atomov v organizem, da jih krvna plazma relativno slabo omaka, kar zmanjšuje hitrost adsorbcije proteinov medceličnine na vsadek. Za hitro, čvrsto in trajno osteointegracijo kostnega vsadka je namreč pomembna hitra vezava proteinov, npr. fibronektina, takoj ko pride vsadek v stik z medceličnino.-2 Surfaces of metal for bone implants. In order to improve osteointegration, implants have been developed, e.g. hip joints with a rough surface, e.g. with furrows, metal beads or porous metal coating, sandblasting, etc. The disadvantage of such coatings is that in addition to the diffusion of metal atoms into the body, they are relatively poorly absorbed by the blood plasma, which reduces the rate of adsorption of intercellular proteins to the implant. For fast, firm and permanent osteointegration of the bone implant, it is important to quickly bind proteins, e.g. fibronectin as soon as the implant contacts the intracellular.
Na kostne vsadke se nanaša tudi nekovinske prevleke, npr. SiC, diamantu podobne prevleke »DLC«, TiN, AI2O3, izotropen pirolitski grafit in druge nekovinske prevleke. Pomanjkljivost teh prevlek je, da bodisi niso bioaktivne, jih krvna plazma slabo omaka, npr. DLC, vsebujejo citotoksične ali nevrotokosične elemente, npr. A12O3, ali pa niso trdno vezane na podlago in se z nje luščijo, npr. nekatere vrste prevlek iz titanovega oksida.Bone implants are also referred to as non-metallic coatings, e.g. SiC, diamond-like "DLC" coatings, TiN, AI2O3, isotropic pyrolytic graphite and other non-metallic coatings. The disadvantage of these coatings is that they are either not bioactive, poorly dipped in blood plasma, e.g. DLCs contain cytotoxic or neurotoxic elements, e.g. A12O3, or are not firmly attached to and exfoliate from the substrate, e.g. some types of titanium oxide coatings.
Delno izboljšanje osteointegracije je bilo doseženo z nanosom biokompatibilnih in bioaktivnih prevlek na osnovi hidroksiapatita, ki je po sestavi podoben mineralnemu delu kosti in je zato zelo bioaktiven, kar močno pospeši proces tvorbe mineralnega tkiva na stiku z vsadkom. Vendar je zaradi biorazgradljivosti hidroksiapatita izboljšanje le začasno, poleg tega pa je zmanjšanje negativnih učinkov sproščanja in širjenja kovinskih ionov v telo le začasno.Partial improvement of osteointegration was achieved by applying biocompatible and bioactive coatings based on hydroxyapatite, which is similar in composition to the mineral part of the bone and is therefore highly bioactive, which greatly accelerates the process of mineral tissue formation upon contact with the implant. However, due to the biodegradability of hydroxyapatite, the improvement is only temporary and the negative effects of the release and propagation of metal ions into the body are only temporary.
Znana je tudi kompozitna bioaktivna prevleka iz titanovega oksida in hidroksiapatita, ki je pripravljena s kombiniranim postopkom, pri čemer se najprej nanese hidroksiapatit, temu pa sledi postopek »micro are anodisation« oz. MAO. Namen je dopiranje titanovega oksida s kalcijem in fosforjem za izboljšanje osteointegracije in celične aktivnosti. Slabost take prevleke je, daje zaradi resorpcije hidroksiapatita velika verjetnost sproščanja delcev titanovega oksida.Also known is a composite bioactive coating of titanium oxide and hydroxyapatite, which is prepared by a combined process, first applying hydroxyapatite, followed by the procedure "micro are anodisation" or. MAO. The purpose is to dop titanium oxide with calcium and phosphorus to improve osteointegration and cellular activity. The disadvantage of this coating is that due to the resorption of hydroxyapatite, the release of titanium oxide particles is high.
Nekoliko podobna predlagani rešitvi je prevleka iz kalcijevega titanata, ki je bila pripravljena s hidrotermalnim postopkom v raztopini CaO in je opisana v članku Kenichi Hamada, Masayuki Kon, Takao Hanawa, Kenichi Yokoyama, Youji Miyamoto, Kenzo Asaoka, Hydrothermal modification of titanium surface in calcium Solutions, Biomaterials 23 (2002) 2265-2272 in patentu W0/2007/040298. Pripravlja se po podobnem postopku kot rešitev po izumu Bioaktivna in fotokatalitska prevleka na kovinskih vsadkih in postopek priprave, le da se uporabljajo drugačne sestavine in je zato drugačna tudi sestava prevleke. Prevleka izSomewhat similar to the proposed solution is a calcium titanate coating that was prepared by a hydrothermal process in CaO solution and is described in an article by Kenichi Hamada, Masayuki Kon, Takao Hanawa, Kenichi Yokoyama, Youji Miyamoto, Kenzo Asaoka, Hydrothermal modification of titanium surface in calcium Solutions, Biomaterials 23 (2002) 2265-2272 and Patent W0 / 2007/040298. It is prepared by a similar process to the solution of the invention Bioactive and photocatalytic coating on metal implants and the preparation process, except that different ingredients are used and therefore the composition of the coating is different. Cover from
-3kalcijevega titanata je po navedbah bioaktivna, saj na njej v 30 dneh zraste apatit, je trdno vezana na podlago, ni pa hidrofilna in fotokatalitska.Calcium titanate is said to be bioactive, as apatite grows on it within 30 days, is firmly bound to the substrate, but is not hydrophilic and photocatalytic.
Znane so tudi prevleke na osnovi titanovega oksida, ki jih nanašajo na površino kovinskih vsadkov s postopki, ki so navedeni v nadaljevanju.Also known are titanium oxide based coatings which are applied to the surface of metal implants by the procedures described below.
Večina znanih postopkov priprave prevlek na osnovi titanovega oksida vključuje segrevanje na temperature, pri katerih pa običajno nastane najbolj stabilna, vendar za biomedicinsko uporabo manj primerna oblika titanovega oksida - rutil. Anataz, ki je ena od treh kristalnih oblik titanovega oksida - rutil, anataz, brukit, je znan po svojih posebnih lastnostih, med katerimi v literaturi ločeno poročajo o biokompatibilnosti, bioaktivnosti, fotoaktivnosti in superhidrofilnosti. Predlagani postopek nanašanja prevleke na osnovi titanovega oksida s hidrotermalno obdelavo kovinskih vsadkov poteka pri temperaturah, kjer do prehoda ne pride, zato je prevleka pretežno v obliki anataza. Anataz značilno tvori koničasto oblikovane kristale, kar zaradi neugodnega celičnega odziva negativno vpliva na osteointegracijo.Most of the known processes for the preparation of titanium oxide coatings involve heating to temperatures at which usually the most stable but less suitable form of titanium oxide, rutile, is produced for biomedical use. Anatase, which is one of the three crystalline forms of titanium oxide - rutile, anatase, brokite, is known for its special properties, among which biocompatibility, bioactivity, photoactivity and superhydrophilicity are reported separately in the literature. The proposed process for the application of a titanium oxide coating by hydrothermal treatment of metal implants is carried out at temperatures where no transition occurs, so the coating is predominantly in the form of anatases. Anatase typically forms spike-shaped crystals, which adversely affect osteointegration due to the unfavorable cellular response.
Ena od značilnih lastnosti nanokristaliničnega titanovega oksida v obliki anataza je fotokatalitičnost, ki se izkorišča na različnih področjih, npr. za samočistilne prevleke, dodatke v kozmetičnih sredstvih in drugje. Fotokatalitičnost je mogoče med drugim izkoristiti za biološko dekontaminacijo površin (npr. organske nečistoče, mikroorganizmi kot so virusi, bakterije, spore plesni in gliv). Sterilizacijski učinek prevleke iz titanovega oksida, pripravljene po sol-gel postopku, na aluminijevih vlaknih je opisan v članku L. Luo, L. Miao, S. Tanemura, M. Tanemura, Photocatalytic sterilization of TiO2 films coated on Al fiber, Materials Science and Engineering: B, 148 (2008) 183-186.One of the characteristic properties of anatase nanocrystalline titanium oxide is the photocatalyticity utilized in various fields, e.g. for self-cleaning coatings, additives in cosmetics and elsewhere. Photocatalyticity can be used, inter alia, for the biological decontamination of surfaces (eg organic impurities, microorganisms such as viruses, bacteria, mold spores and fungi). The sterilization effect of a titanium oxide coating prepared by the sol-gel process on aluminum fibers is described in an article by L. Luo, L. Miao, S. Tanemura, M. Tanemura, Photocatalytic sterilization of TiO 2 films coated on Al fiber, Materials Science and Engineering: B, 148 (2008) 183-186.
Poročajo tudi o bioaktivnosti prevleke iz titanovega oksida, nanešenega s plazemskim naprševanjem, po obsevanju z UV svetlobo, kar ni značilno za neobsevan titanov dioksid.The bioactivity of the plasma titanium oxide coating after irradiation with UV light is also reported, which is not typical for unshaded titanium dioxide.
Članki poročajo tudi o superhidrofilnosti, ki jo pripisujejo fotokatalitski aktivnosti titanovega oksida. Učinek se v odsotnosti UV svetlobe s časom manjša, ga je pa mogoče podaljšati z dodatkom silicijevega oksida. V članku S. Permpoon, M. Houmard, D. Riassetto, L. Rapenne, G. Berthome, B. Baroux, J.C. Joud, M. Langlet, Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films, Thin Solid Films 516 (2008) 957-966, je opisana • ·The articles also report superhydrophilicity attributed to the photocatalytic activity of titanium oxide. The effect diminishes over time in the absence of UV light, but can be prolonged by the addition of silica. In article S. Permpoon, M. Houmard, D. Riassetto, L. Rapenne, G. Berthome, B. Baroux, J.C. Joud, M. Langlet, Natural and persistent superhydrophilicity of SiO2 / TiO2 and TiO2 / SiO2 bi-layer films, Thin Solid Films 516 (2008) 957-966, is described • ·
-4dvoslojna prevleka iz titanovega in silicijevega oksida, pripravljena po sol-gel postopku, kjer naj bi prisotnost silicijevega oksida prispevala k trajnejšemu fotokatalitskemu učinku. Take prevleke na kostnih nadomestkih še niso bile opisane.-4 Two-layer titanium and silica coating prepared by sol-gel process where the presence of silicon oxide is expected to contribute to a more lasting photocatalytic effect. Such bone replacement coatings have not yet been described.
Glede na sestavo so znane prevleke na osnovi titanovega oksida, značilno čisti titanov oksid ali pa kompozit titanovega oksida s silicijem oksidom ali hidroksiapatitom. Nobena od prevlek na osnovi titanovega oksida ne vsebuje esencialnih elementov, ki pomembno vplivajo na osteointegracijo in sicer kalcija, silicija, fosforja, stroncija in cinka, ki imajo sledečo vlogo: Silicij znižuje zmanjšuje absorpcijo aluminija in ima ključno vlogo pri nastanku kostnine in povezovalnega tkiva, stroncij stimulira rast osteoblastov, poveča produkcijo kostnine in inhibira osteoklaste, ki razgrajujejo kostnino, cink pospešuje sintezo kolagena, ki je ključna sestavina kostnine, kalcij in fosfor pa sta glavni sestavini mineralnega dela kosti in zato najpomembnejša elementa za sestavo kostnine.Depending on the composition, titanium oxide based coatings, typically pure titanium oxide or a composite of titanium oxide with silicon oxide or hydroxyapatite, are known. None of the titanium oxide coatings contain essential elements that significantly affect osteointegration, namely calcium, silicon, phosphorus, strontium and zinc, which have the following role: Silicon reduces the absorption of aluminum and plays a key role in bone and connective tissue formation, Strontium stimulates osteoblast growth, increases bone production and inhibits bone-breaking osteoclasts, zinc promotes collagen synthesis, which is a key component of bone, and calcium and phosphorus are the main components of bone mineral and therefore the most important elements of bone composition.
Kot je opisano zgoraj, je znanih vrsta različnih prevlek, ki pa imajo pomanjkljivosti, ki so deloma povezane tudi s postopkom priprave prevleke. Znani so sledeči postopki za pripravo prevleke na osnovi titanovega oksida na kovinskih vsadkih:As described above, a number of different coatings are known, but they have disadvantages that are also partly related to the coating preparation process. The following procedures are known for preparing a titanium oxide coating on metal implants:
Titanov oksid nastane na titanu spontano z oksidacijo že pri normalnih pogojih, vendar je plast nastalega oksida pretanka, da bi služila kot zaščita oz. prepreka za difuzijo kovinskih atomov, prav tako naravno oksidirana površina titana ni bioaktivna, fotokatalitska in hidrofilna.Titanium oxide is formed on the titanium spontaneously by oxidation under normal conditions, but the oxide layer formed is too thin to serve as a protective or protective agent. barrier to diffusion of metal atoms, nor is the naturally oxidized surface of titanium bioactive, photocatalytic and hydrophilic.
Debelejša plast nastane pri termični obdelavi v kisikovi atmosferi - plast se običajno relativno slabo drži podlage, zato za vsadke ni primerna.A thicker layer results from thermal treatment in an oxygen atmosphere - the layer is usually relatively poorly adhered to the substrate, so it is not suitable for implants.
- Znana je tudi elektrokemijska oksidacija (anodizacija) v raztopini. Tako pripravljene prevleke nimajo lastnosti prevleke po tem izumu.- Electrochemical oxidation (anodization) in solution is also known. The coatings thus prepared do not have the coating properties of the present invention.
- Za nanašanje prevlek titanovega oksida se uporablja tudi naprševanje v plazmi (»sputter deposition«), ki pa je precej drago. Prevleke niso bioaktivne in fotokatalitične.- Sputter deposition is also used to apply titanium oxide coatings, which is quite expensive. Coatings are not bioactive and photocatalytic.
- Znan je tudi postopek za nanašanje prevlek iz titanovega oksida na različne podlagae s sol-gel sintezo, kjer se kot prekurzor uporablja titanov (IV) propoksid in Ti (IV) butoksid, lahko pa tudi anorganski prekurzor. Po hidrolizi, kondenzaciji in polimerizaciji je potrebna še termična obdelava, ki povzroči kristalizacijo nastalega gela. Postopek ni primeren za- A process for applying titanium oxide coatings to various sol-gel synthesis substrates is also known, using titanium (IV) propoxide and Ti (IV) butoxide as precursors, but may also be an inorganic precursor. After hydrolysis, condensation and polymerization, a thermal treatment is required which results in the crystallization of the resulting gel. The process is not suitable for
-5podlage, ki jih iz kakršnegakoli razloga ne smemo segreti na temperaturo, potrebno za kristalizacijo, prevleke pa nimajo vseh ciljnih lastnosti.-5 Substrates which for any reason should not be heated to the temperature required for crystallization but the coatings do not have all the desired properties.
- Znan je tudi postopek kemijskega nanašanja v parni fazi (CVD), kjer organski prekurzor ob stiku s podlago razpade in tvori oksidno plast. Prevleke nimajo vseh ciljnih lastnosti.- The process of chemical vapor deposition (CVD) is also known, in which the organic precursor decomposes upon contact with the substrate and forms an oxide layer. Covers do not have all the target properties.
- Znan je tudi postopek »Ion-beam-assisted sputter deposition (IBASD). Tako pripravljene prevleke nimajo lastnosti prevleke po tem izumu.- The "Ion-beam-assisted sputter deposition (IBASD)" procedure is also known. The coatings thus prepared do not have the coating properties of the present invention.
Postopek, ki je delno podoben predlaganemu in je opisan v članku K. Hmada et al., Biomaterials 23 (2002) 2265-2272, je hidrotermalna obdelava kovine v prisotnosti Ca(OH)2, ki ji sledi segrevanje za povečanje kristaliničnosti prevleke pri 600 °C v vakuumu. Tako pripravljena prevleka sestoji iz kalcijevega titanata, ki je bioaktiven, nima pa drugih lastnosti, ki jih ima predlagana prevleka na osnovi titanovega oksida.The process, which is partially similar to the one proposed and described in the article by K. Hmada et al., Biomaterials 23 (2002) 2265-2272, is hydrothermal treatment of the metal in the presence of Ca (OH) 2 followed by heating to increase the crystallinity of the coating at 600 ° C under vacuum. The coating thus prepared consists of calcium titanate, which is bioactive but does not have the other properties of the proposed titanium oxide based coating.
Problem, ki ni zadovoljivo rešenA problem that is not satisfactorily resolved
Kot je opisano, je sicer znanih več vrst prevlek z različno kemijsko sestavo, vključno s titanovim oksidom, vendar nobena ne združuje vseh želenih lastnosti, to je zmanjševanje difuzije kovinskih atomov v telo, biokompatibilnost, bioaktivnost, hidrofilnost in fotokatalitičnost. Najbolj podoben postopek predlaganemu je hidrotermalna obdelava kovinskih vsadkov v raztopini CaO, katere produkt pa ni titanov oksid, ampak CaTiO3, ki nima lastnosti titanovega oksida. Nobena od prevlek na osnovi titanovega oksida ne vsebuje elementov, ki pomembno vplivajo na osteointegracijo in sicer kalcija, silicija, stroncija, cinka, magnezija in fosforja.Although described, several types of coatings with different chemical composition, including titanium oxide, are known, but none combines all the desired properties, i.e. reduction of diffusion of metal atoms into the body, biocompatibility, bioactivity, hydrophilicity and photocatalytic. The most similar process to the proposed method is the hydrothermal treatment of metal implants in CaO solution, the product of which is not titanium oxide but CaTiO3, which has no titanium oxide properties. None of the titanium oxide coatings contain elements that significantly affect osteointegration, namely calcium, silicon, strontium, zinc, magnesium and phosphorus.
Cilj izuma je izboljšanje kovinskih vsadkov z nanosom tanke biokompatibilne, bioaktivne, hidrofilne in fotokatalitske prevleke na osnovi titanovega oksida v prevladujoči modifikaciji anataza s pinakoidno obliko zrn z dodatkom esencialnih elementov in z lastnostmi, ki prispevajo k izboljšanju oprijemljivosti vsadka s kostnim tkivom, zmanjšanju možnosti vnetja in zmanjšanju negativnih učinkov difuzije kovinskih ionov v telesu.The aim of the invention is to improve metal implants by applying a thin biocompatible, bioactive, hydrophilic and photocatalytic coating based on titanium oxide in the predominant modification of anatases with pinakoid grain form with the addition of essential elements and with features that contribute to improving the adhesion of the implant with bone and reducing the negative effects of diffusion of metal ions in the body.
Predlagana rešitevProposed solution
Po izumu se na kovinsko podlago iz titana, titanove zlitine ali druge kovinske podlage nanese prevleko iz titanovega oksida v obliki anataza s pinakoidnimi zrni, vanjo pa se vgradijoAccording to the invention, a titanium oxide coating in the form of anatase with pinakoid grains is applied to a metal base made of titanium, titanium alloy or other metal substrate and embedded therein
-6elementi za izboljšanje osteointegracije Ca, Si, P, Mg, Sr in/ali Zn. Taka prevleka prepreči neposreden stik z za telo škodljivimi kovinskimi ioni in zmanjšuje difuzijo kovinskih ionov v telo, poleg tega pa je, pripravljena po predlaganem postopku, to je hidrotermalni sintezi pri pogojih, opisanih v nadaljevanju, bioaktivna, hidrofilna in fotokatalitična. V primerjavi z znanimi postopki nanašanja prevleke na osnovi titanovega oksida je predlagani postopek preprost in poceni, na ta način pripravljena prevleka pa združuje lastnosti, ki jih ne dosega nobena znana prevleka na kovinskih vsadkih.-6elements for enhancing osteointegration of Ca, Si, P, Mg, Sr and / or Zn. Such coating prevents direct contact with body-harmful metal ions and reduces the diffusion of metal ions into the body and, in addition, is prepared by the proposed process, ie hydrothermal synthesis under the conditions described below, bioactive, hydrophilic and photocatalytic. Compared to the known titanium oxide coating methods, the proposed process is simple and inexpensive, and the coating thus prepared combines features not achieved by any known metal implant coating.
Opis postopkaProcedure description
Postopek priprave biokompatibilne, bioaktivne in fotokatalitske prevleke na osnovi TiO2 na površini kovinskih vsadkov, namenjenih za trajno ali začasno oporo skeletu ali kot nadomestek manjkajočega dela skeleta in njene lastnosti so podrobneje opisani v nadaljevanju:The process of preparing a biocompatible, bioactive and photocatalytic TiO2-based coating on the surface of metal implants intended to permanently or temporarily support the skeleton or to replace the missing part of the skeleton and its properties is described in more detail below:
- Pripravi se nasičena vodna raztopina titanovih ionov. Raztopini se doda anorgansko ali organsko bazo in sicer NaOH, KOH, Ca(0H)2, NH40H ali tetraalkil-amonijev hidroksid, citronsko in fosforno kislino za uravnavanje pH na vrednost v območju 3 do 12. Poleg tega se doda 0,05 do 1 utežnega deleža CaF2 ali SrF2 ali MgF2 ali ZnO ali drugo dvovalentno sol in 0,001 do 0,1% SiO2 na maso vode. Mešanica se pripravi v posodi ali zlije v posodo z notranjo oblogo iz titana ali teflona ali drugega termično obstojnega in kemijsko inertnega polimera. Kovinski vsadek se potopi v pripravljeno mešanico.- Prepare a saturated aqueous solution of titanium ions. To the solution is added an inorganic or organic base, namely NaOH, KOH, Ca (0H) 2, NH40H or tetraalkyl ammonium hydroxide, citric and phosphoric acid to adjust the pH to a value in the range 3 to 12. In addition, 0.05 to 1 is added. by weight of CaF2 or SrF2 or MgF2 or ZnO or other divalent salt and 0.001 to 0.1% SiO2 by weight of water. The mixture is prepared in a container or poured into a container with an inner lining of titanium or teflon or other thermally stable and chemically inert polymer. The metal implant is immersed in the prepared mixture.
- Posoda se tesno zapre in segreje na temperaturo 100 do 300 °C s hitrostjo 2 do 10 °C/min. Pri tej temperaturi se drži 6 do 96 ur, nato se samodejno ohladi na sobno temperaturo.- Close the container tightly and heat to 100 to 300 ° C at a speed of 2 to 10 ° C / min. It is kept at this temperature for 6 to 96 hours, then automatically cooled to room temperature.
- Posodo se odpre in vzame kovinski vsadek s prevleko iz mešanice, vsadek se nato temeljito spere pod tekočo vodo ali v ultrazvočni kopeli in v acetonu ali alkoholu, da se odstranijo neporabljeni reagenti. Očiščeni vsadki se sušijo samodejno pri sobni temperaturi ali pri temperaturi do 150 °C.- The container is opened and the metal implant coated with the mixture is opened and the implant is then thoroughly rinsed under running water or in an ultrasonic bath and in acetone or alcohol to remove unused reagents. The cleaned implants are automatically dried at room temperature or up to 150 ° C.
- Vsadek se lahko dodatno očisti in sterilizira z obsevanjem v UV svetlobi valovne dolžine 300-400 nm.- The implant can be further cleaned and sterilized by irradiation in the UV light of a wavelength of 300-400 nm.
Postopek priprave bioaktivne in fotokatalitske prevleke na kovinskih vsadkih je značilen po tem, da se vsadke potopi v nasičeno raztopino, ki vsebuje ione Ti, Ca, Mg, P, Si, Zn in/ali Sr in ima pH 3 do 12, 6 do 96 ur se jih segreva v tesno zaprtem avtoklavu pri temperaturi 100-300 °C, nato pa se jih vzame iz avtoklava in ohladi na sobno temperaturo, opere in posuši, • ·The process of preparing bioactive and photocatalytic coatings on metal implants is characterized in that the implants are immersed in a saturated solution containing Ti, Ca, Mg, P, Si, Zn and / or Sr ions having a pH of 3 to 12, 6 to 96 for hours they are heated in a tightly closed autoclave at 100-300 ° C and then taken out of the autoclave and cooled to room temperature, washed and dried, • ·
-Ίlahko se jih tudi obseva v UV svetlobi. Postopek omogoča nanašanje prevlek na različne materiale in na vsadke z gladko ali zelo hrapavo površino.-It can also be irradiated in UV light. The process allows the coating of various materials and implants with a smooth or very rough surface.
Prevleka po izumu in izdelana po opisanem postopku sestoji iz do 5 mikrometrov debele plasti titanovega oksida v pretežni obliki pinakoidalnega anataza z dodatkom esencialnih elementov in je trdno vezana na podlago. Prevleka je hidrofilna, preprečuje direkten stik krvne plazme s citotoksičnimi in alergenimi kovinami, npr. z aluminijem in vanadijem v Ti6A14V in je bioaktivna - v simulirani telesni tekočini se na površini v 2 do 3 tednih tvori hidroksiapatit. Prevleka je fotokatalitična - pri obsevanju z UV svetlobo valovne dolžine 300-400 nm se organske in biološke nečistoče razgradijo in vsadek se sterilizira.The coating according to the invention and manufactured according to the described procedure consists of up to 5 micrometers of a thick layer of titanium oxide in a predominantly pinakoidal anatase form with the addition of essential elements and is firmly attached to the substrate. The coating is hydrophilic, preventing direct contact of blood plasma with cytotoxic and allergenic metals, e.g. with aluminum and vanadium in Ti6A14V and is bioactive - hydroxyapatite forms on the surface in 2 to 3 weeks in the simulated body fluid. The coating is photocatalytic - when irradiated with UV light of a wavelength of 300-400 nm, organic and biological impurities are degraded and the implant is sterilized.
Bioaktivna in fotokatalitska prevleka na kovinskih vsadkih je značilna po tem, da ima sestavo in lastnosti, ki pospešijo in izboljšajo osteointegracijo vsakov in sicer je bioaktivna in se na njej v medceličnini tvori hidroksiapatit, fotokatalitska in se pri obsevanju v UV svetlobi na njej tvorijo radikali, ki razgradijo organske in biološke nečistoče, prevleka se na ta način sterilizira, je hidrofilna, zato jo medceličnina hitro in popolno oblije in tako omogoči hitro adsorpcijo proteinov.Bioactive and photocatalytic coating on metal implants is characterized in that it has a composition and properties that promote and enhance osteointegration of each, namely it is bioactive and forms hydroxyapatite in it, photocatalytic and radicals upon irradiation in UV light. which break down organic and biological impurities, the coating is sterilized in this way, it is hydrophilic, and therefore the cell is quickly and completely enveloped by the cell to allow rapid protein adsorption.
Izum bo v nadaljnem nadaljevanju podrobno opisan na osnovi izvedbenih primerov:The invention will hereinafter be described in detail based on embodiments:
Izvedbeni primer 1:Example 1:
V 100 ml destilirane vode se doda 5 g prahu titanovega oksida z velikostjo delcev 50 nm in 0,1 g ZnO in 0,1 g SrF2. Z dodatkom Ca(OH)2, NaOH, TMAH in citronske kisline se pH nastavi na 10. Suspenzija se prelije v posodo iz teflona in vanjo se potopi kovinski vsadek iz zlitine Ti6A14V. Posodo se tesno zapre, segreje na 200 °C in segreva 36 ur. Posodo se nato samodejno ohladi pri sobni temperaturi, odpre, prevlečeni vsadek pa spira 1 uro pod tekočo vodo in 1 h v ultrazvočni kopeli z destilirano vodo in 1 h v ultrazvočni kopeli z etanolom, pri čemer se zagotovi dotok sveže vode ali etanola. Vsadek se 3 ure suši v pretoku vročega zraka pri temperaturi 150 °C, nato se ga ohladi in 12 ur obseva z UV svetlobo valovne dolžine 300-400 nm.In 100 ml of distilled water, 5 g of titanium oxide powder with a particle size of 50 nm and 0.1 g of ZnO and 0.1 g of SrF2 are added. With the addition of Ca (OH) 2, NaOH, TMAH and citric acid, the pH was adjusted to 10. The suspension was poured into a Teflon container and a metal Ti6A14V alloy implant was immersed therein. The container is sealed tightly, heated to 200 ° C and heated for 36 hours. The vessel is then automatically cooled to room temperature, opened, and the coated implant is rinsed for 1 hour under running water and 1 hour in an ultrasonic bath with distilled water and 1 hour in an ultrasonic bath with ethanol, ensuring fresh water or ethanol inflow. The implant is dried for 3 hours in a stream of hot air at 150 ° C, then cooled and irradiated for 12 hours with UV light of 300-400 nm.
• ·• ·
Izvedbeni primer 2:Example 2:
V 100 ml destilirane vode se doda 1 g prahu titana z velikostjo delcev 500 nm in 0,5 g CaF2 in 0,1 g SiO2. Z dodatkom NaOH, TMAH, fosforne in citronske kisline se nastavi pH na 11. Suspenzija se prelije v posodo iz titana in vanjo se potopi kovinski vsadek iz zlitine Ti6A14V. Posodo se tesno zapre, segreje na 150 °C in segreva 48 ur. Posodo se nato samodejno ohladi pri sobni temperaturi, odpre, prevlečeni vsadek pa spira 1 uro pod tekočo vodo in 1 h v ultrazvočni kopeli z destilirano vodo in 1 h v ultrazvočni kopeli z etanolom, pri čemer se zagotovi dotok sveže vode ali etanola. Vsadek se 3 ure suši v pretoku vročega zraka pri temperaturi 100 °C, nato se ga ohladi in 12 ur obseva z UV svetlobo valovne dolžine 300-400 nm.To 100 ml of distilled water is added 1 g of titanium powder with a particle size of 500 nm and 0.5 g of CaF2 and 0.1 g of SiO2. With the addition of NaOH, TMAH, phosphoric and citric acid, the pH was adjusted to 11. The suspension was poured into a titanium vessel and a metal Ti6A14V implant was immersed therein. The container is sealed tightly, heated to 150 ° C and heated for 48 hours. The vessel is then automatically cooled to room temperature, opened, and the coated implant is rinsed for 1 hour under running water and 1 hour in an ultrasonic bath with distilled water and 1 hour in an ultrasonic bath with ethanol, ensuring fresh water or ethanol inflow. The implant is dried for 3 hours in a flow of hot air at 100 ° C, then cooled and irradiated for 12 hours with UV light of 300-400 nm.
Vsadek po izumu je prekrit s trdno vezano prevleko na osnovi titanovega oksida, ki tvori bariero med kovinskim vsadkom in medceličnino in tako dolgotrajno prepreči direkten stik kovine s kostjo in omeji ali prepreči prehajanje kovinskih ionov, razen titana, v organizem. Prevleka na osnovi titanovega oksida vsebuje tudi esencialne elemente, ki pospešujejo osteointegracijo. Prevleka je tudi bioaktivna in se na njej v medceličnini tvori hidroksiapatit, kar pospeši osteointegracijo. Prevleka je fotokatalitska in se pri obsevanju v UV svetlobi na njej tvorijo radikali, ki razgradijo organske in biološke nečistoče, prevleka se na ta način sterilizira. Prevleka je tudi hidrofilna, zato jo medceličnina hitro in popolno oblije in tako omogoči hitro adsorpcijo proteinov.The implant according to the invention is coated with a tightly bound titanium oxide based coating, which forms a barrier between the metal implant and the intercellular, thus preventing direct contact of the metal with bone for a long time and restricting or preventing the passage of metal ions other than titanium into the body. Titanium oxide based coating also contains essential elements that promote osteointegration. The coating is also bioactive and hydroxyapatite forms on the intercellular surface, which accelerates osteointegration. The coating is photocatalytic and, when irradiated in UV light, radicals are formed on it, which break down organic and biological impurities, the coating being sterilized in this way. The coating is also hydrophilic, so it is quickly and completely enveloped by the intercellulose to allow rapid protein adsorption.
Bioaktivna in fotokatalitska prevleka na kovinskih ortopedskih in dentalnih vsadkih po izumu je značilna po tem, da sestoji iz do 5 mikrometrov debele plasti titanovega oksida v pretežni obliki pinakoidalnega anataza z dodatkom esencialnih elementov in je trdno vezana na kovinsko podlago. Prevleka ima sestavo in lastnosti, ki pospešijo in izboljšajo osteointegracijo vsakov in sicer je bioaktivna in se na njej v medceličnini tvori hidroksiapatit, fotokatalitska in se pri obsevanju v UV svetlobi na njej tvorijo radikali, ki razgradijo organske in biološke nečistoče, prevleka se na ta način sterilizira, je hidrofilna, zato jo medceličnina hitro in popolno oblije in tako omogoči hitro adsorpcijo proteinov. Postopek priprave bioaktivne in fotokatalitske prevleke na kovinskih ortopedskih in dentalnih vsadkih po izumu je značilen po tem, da se vsadke potopi v nasičeno raztopino, ki vsebuje ione Ti, Ca, Mg, P, Si, Zn in/ali Sr in ima pH 3 do 12, nato pa se jih 6 do 96 ur segreva v tesno zaprtem avtoklavu pri temperaturi 100-300 °C, nato pa se jih vzame iz avtoklava in ohladi na sobno temperaturo, opere in posuši, • · ·«· <The bioactive and photocatalytic coating on metal orthopedic and dental implants according to the invention is characterized by the fact that it consists of up to 5 micrometers of a thick layer of titanium oxide in a predominantly pinakoidal anatase form with the addition of essential elements and is firmly bonded to the metal substrate. The coating has a composition and properties that accelerate and enhance the osteointegration of each, namely, it is bioactive and forms hydroxyapatite in the intercellular space, photocatalytic and, when irradiated in UV light, it forms radicals that break down organic and biological impurities. it is sterilized, hydrophilic, so the cell is quickly and completely enveloped by the cell to allow rapid protein adsorption. The process of preparing a bioactive and photocatalytic coating on metal orthopedic and dental implants according to the invention is characterized in that the implants are immersed in a saturated solution containing Ti, Ca, Mg, P, Si, Zn and / or Sr ions having a pH of 3 to 12, then heated for 6 to 96 hours in a tightly closed autoclave at 100-300 ° C and then taken out of the autoclave and cooled to room temperature, washed and dried, • · · «· <
-9lahko se jih tudi obseva v UV svetlobi. Bioaktivna in fotokatalitska prevleka na kovinskih ortopedskih vsadkih je izdelana po postopku po zahtevku 3.-9can also be irradiated in UV light. The bioactive and photocatalytic coating on metal orthopedic implants is made according to the method of claim 3.
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9713655B2 (en) | 2014-06-13 | 2017-07-25 | Acuitive Technologies, Inc. | Joint replacement or joint resurfacing devices, systems and methods |
| CN112126926A (en) * | 2020-08-17 | 2020-12-25 | 南京医科大学附属口腔医院 | Preparation method for synchronously loading bioactive zinc ions on titanium surface modified nano structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9713655B2 (en) | 2014-06-13 | 2017-07-25 | Acuitive Technologies, Inc. | Joint replacement or joint resurfacing devices, systems and methods |
| US10272177B2 (en) | 2014-06-13 | 2019-04-30 | Acuitive Technologies, Inc. | Joint replacement or joint resurfacing devices, systems and methods |
| CN112126926A (en) * | 2020-08-17 | 2020-12-25 | 南京医科大学附属口腔医院 | Preparation method for synchronously loading bioactive zinc ions on titanium surface modified nano structure |
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