CA2416201C - Bioactive calcium phosphate composite layers electrochemically deposited on implants - Google Patents

Bioactive calcium phosphate composite layers electrochemically deposited on implants Download PDF

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Publication number
CA2416201C
CA2416201C CA002416201A CA2416201A CA2416201C CA 2416201 C CA2416201 C CA 2416201C CA 002416201 A CA002416201 A CA 002416201A CA 2416201 A CA2416201 A CA 2416201A CA 2416201 C CA2416201 C CA 2416201C
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Canada
Prior art keywords
calcium
implant
bone
phosphate
implants
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Expired - Fee Related
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CA002416201A
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French (fr)
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CA2416201A1 (en
Inventor
Hans-Georg Neumann
Peter Zeggel
Petra Becker
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DOT GmbH
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DOT GmbH
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2002/3092Special external or bone-contacting surface, e.g. coating for improving bone ingrowth having an open-celled or open-pored structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389The prosthesis being coated or covered with a particular material
    • A61F2310/00592Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Cardiology (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

The invention relates to calcium phosphate composite layers which are electrochemically deposited on bone implants. Implants which are coated in such a way are implanted without cement and are characterised by improved growing-in behaviour. Said highly porous composite layers on implants are made of at least two calcium phosphate phases of different solubility. The highly porous structure of said layers facilitates the immobilisation of cells from which new bone tissue can be made. The different solubility of the individual layer components ensures local concentration of calcium and phosphate ions which accelerates the incorporation process and which adapts to said process over the course of time.

Description

BIOACTIVE CALCIUM PHOSPHATE COMPOSITE LAYERS ELECTROCHEMICALLY
DEPOSITED ON IMPLANTS

For about 10 years investi.gations on c;alc::.iLir phosphate layers electrochemically deposited ori k~,anr~~ im.pl,!:rnts have been carried out with the objective to improve the compound between the bone tissue and implant (Redepenning, J. et aL.: Chem. Mater.
2(1990) 625-7; Redepenning, J.G.: US 5, 3]..0, 464, US 5, 413, 693;
Teller, J. et al. :]aE 4 431 862, EP 774 ')82, US 5, 759, 3"76;.
Kumar, M. et al.: J. Fiiomed. Mat. Res. 4!::; t 1.999 ) 302-10) , Calcium phosphates as miner.a:l. c.onst:..it.uerlt:s of the bone tissue have bioactive properties, ie. they assist the bone formation.
The genesis of calcium phosphate layers trom electrolytic baths deposited on implants are ve.ry simi.lar t::,o the processes proceeding during the bone cfrowt.:lr. 'I't-iei;_ r=,i..cr_oporous structure encourages the immobi.lizat--.ion of ce_L1s,, whi.crl leads to :caew bone tissue being allowed to forn ar~Gd to k,n_i :. together with the bone tissue surrounditZg the implant such as with normal wound healing.

In the literature, besides the preparatiari of phase-pur.e calcium phosphates it. is also known to h.ave composite layers electrochemically deposited on irnpiants. US :'atent 5, 20'>, 921 (Shirkhanzadeh, M.) and DE Patent 4, 43:1., 862 ;7:'eller, J. et.
al.) describe the electrochemical nepostt.l_on of calc.ium phosphate composite layers from t:.r (:.ait.iuiTl prioUphate and Y Y p from more :(-.ralf. a~.~1u~ible c~al~,iun;
h drox la atite ftwo mo.rE, dii'!"':E. ~
phosphate phases. DE 19 504 386 (Scharnweuer, D. et_ al.) deals with an electrochenlical method fcx~ the preparation of a refined adhesive-proof coating from Ual.ci.um pnosphat.e and metal oxide phases on titanium implants by a mutua;l cathodic and anodic polarization. Another method for the preparation of adhesive-proof hydroxylapatite/cobalt composites uses electrochemically deposited brushite layers which are chemically convertESd into hydroxylapatite ard are subsequent-1y c_:oat:ed with cobalt: in another bath (Zhar:,g J.M. et. al.. J. Mat. ;>>c;i.. Lett. 11 (1998) 1077-9) . With the difficult so.l.cable calcium phosphate phases, in particular hydroxylapat.ite, one seeks by the preparation of these composite layexs to achieve a possibly great, similarity to the structure of natural fuL1 developc.,d bone, and this will encourage the implant to be het.lc,:!d int:c) i::he b~:)ne. It can be assumed that due to its low so:i_:ibil:it.y the hyd.r.(:)xylapatite remains on the implant, and thus a ciurab:l_e improvement of the interaction between the implant surtace arid biological system will be achieved. Also, attempLs to compLetely convert brushite layers electrochemically depos,ited orr irti}->.lants into hy(droxylapatite are made with the ok).,jecr.ive to arti.ficially develop bone similiar rel.at.:.c:>n:-, cri the ir ipl.ant::, forever.
Although the body thus is offered :a sur_t;~~~~ace known to it, such layers have a disadvantage in Lhat due to their low solubility they only excite the bone moderatei.y for the endogenous osteosynthesis.

From the literature it has been known for several years that the grade of bioactivity of a:layer grows with its instability in a physiological ambiance. Good conditions for the reproduction and differentiation of the osteoblasts responsible for bone formation are provideci by a local L'lcrease of ':-he concentration of calci_um and ph,'-3slahaC:.e i.ars Ln the hea:1_;ing zorle of the implant. (Ducheyne, P. 1i:ioma:verials 11(1990) 531-40) . Calcium phosphates with a so.luatdli.r-y very mucl-I higher than that of brushite and monet.i.te in corr:parison with hydroxylapatite thus have a paz_.icular importance, especially for the healing phase of the implant ;irct.c the bone.
Hence, the present invention seeks to deposa.t a layer on the bone implant which optimally assists heali.ng the implant into the bone, which then wi li be eritirc:ly resorbed and thus enables the immediate and complet.e frict.:i.on--fit contact of the bone with the i.mplant.

According to the inventiori, a bone irnplant (.~omprises an i_mplant body and an electrochemicaliy se=j~:)a:rated, bicoact.:ivE~~, calcium-phosphate composition layE,,r on t.}ze i.rnpl.arit k.~)ody, the composite layer being fully absorbable an(i comprises i:reely soluble calcium-phosphate phases of young bone 'vissue and less soluble calcium-phosphate phases of mo.,_e developt~d x;,one, wherein the composite layer has a mi.cropor,:)_a:., The composite layer according to the invention especially includes the more easily solubie phases of the young bone tissue in addition to the more di.ff icõult c~;oluab:Le calcium phosphate phaes of the more developed b~.:)ne. Tn particuar, the easily soluble phases of brushi_te and monetite are allowed to actively assist the endogenous osteUgene:ais by locally increased calcium and phosj,:>hat_ c7 c f=r,r t t,icn:> since the reproduction and matur.ati,Dn of osteobla:at:.cs required for the osteogenesis is accelerated under these condit;.ons. After the dissolution of the more easily soluble p},ases has taken place the more difficult soluble phases erisure a s:Liyhtly increased concentration of calcium and pl tosphat.e :i.c,ns Over a longer time period in the healing zone of the -impl.arit, thus encouraging the enlargement and st3biLization of the new bone tissue.

Due to the high-porous st.ructuz:'(~ aci.justak;~l.e by t:he pararnet.ers of the electrochem.icai. depos:i_t.:ic3n, the corrpos:i.t:e layer is not allowed to serve and does not serve as a barrier betwee:i the implant and bone. However, the coiTrposi.tr~ l.ayer serves as a harmonizing factor or host with e.ndc~genous structuring ~.:)f the boundary layer between the imp:i.ara.k: and b(:)rie. 'i'he high bioactivity of this spongy comi;, .itF inani.te: ts, ;itsel.f iii excellent moistening due to the body f1,iid F.,re.sent in the wound bed of the bone and the adhesi<:;n c.r)nnc~c.~~r,<:i therewith due to the contents of this fluid, and in st.i.rculati.nq the ost.eogenesis.

The composite layers c:an be adapted tU zespect:ive irnplant and the bone surrounding the i.crtplant wi.th xe.spect to the structure, compositiori and t:hickne.;s.

The preparation of this composite is carried out so that the individual phases are simuitanF-~oi.~,sly or ~uk:,sequent::ly deposited as well, the portions of orie pPaaFe, e.g of the more soi_uble calcium phosphate phase, respe~~tivel.y ar~, ccnvF_ rted into a less soluble phase by means of a c:.herrr.ica.l re.ak:t::i.on. With this method, superficially i_t is ro': :interided provide a v,~rtical solubility gradient i.n the composi_t:e. ln.>tead, the different phases laterally develop side t,y side and di s_-.olve agair after iplantation. Then, the porosity of the composite first will increase due to the decrease ot- the more easi:ly soluble phases, and this will make room for new borie tissue until the entire composite is converted into borie tissue after dissolving the less soluble calcium phosphate phases. from first coritacts of the immobilized cel1.:: with irrrpl.ant via the pores of the compos.ite, a c,:nnncct ion between the bone and implant deve7_ops rz--om 1:1;e k>egi rirl i_r.q by tlie proc.eeding dissolution of the :i.ndivi.dua1. phases.

The time history of ttie dissoli..at::iori. of the composite layer_ can be simply characerized by thref:-~ phases. Izl phase I, the greatest local increase of t:t- e concentraÃ.::i.on o:t: calcium and phosphate ions available in the boundary Layer between the implant and bone is s;.zbstant.i.a:L:l_y :.:!etc.:r:rni.ned by the more easily soLuble phases. In this section it must ;:>c, ensured that a fibrous encapsulation of the implant dcc=;-~ r,c t: ~::ac::cur, thus enablirig its immediate oster>~~ni.~ gra.t...ion, 1:n phase II th~> more difficult soluble compsite po t:ion wi:L~l. determine the local ion budget, and in paritcular will assist the mineralization of the new bone tissue. In phase III t.i-ie ent::i.z--c-'. composite is (lissolved and substituted by a new l,-)orre.. '['he implc,r-st. Ls healed :i.r:to thE?

bone in a frictiorl-fit manner.

In case of need, osteoinductive additives and/or antim1.crobial agents carl also be released frorn the c:;ompos:t e.

Claims (5)

1. A bone implant comprising:
an implant body; and an electrochemically separated, bioactive, calcium-phosphate composite layer on said implant body, said composite layer being absorbable in use and comprising calcium-phosphate phases of relatively high solubility in body fluids to which said implant will be exposed in use and calcium-phosphate phases of lower solubility in said body fluids, wherein said composite layer has a microporous structure, wherein said calcium-phosphate phases of relatively high solubility comprise monetite and/or brushite and wherein said calcium-phosphate phases of lower solubility comprise hydroxyapatite.
2. A bone implant according to claim 1, wherein said composite layer is completely dissolved and substituted by new bone in use.
3. A bone implant according to any one of claims 1 to 2, wherein said composite layer further comprises osteoinductive additives.
4. A bone implant according to any one of claims 1 to 3 wherein said composite layer further comprises antimicrobial agents.
5. A process for producing a bone implant, said process comprising the deposit of calcium- phosphate phases of relatively high solubility in body fluids to which said implant will be exposed in use on an implant body and partially converting same to calcium-phosphate phases of lower solubility body fluids to which said implant will be exposed in use to produce an electrochemically separated, bioactive calcium-phosphate layer on said bone implant body, said layer having a microporous structure, said calcium-phosphate phases of relatively high solubility in body fluids comprising monetite and/or brushite and said calcium-phosphate phases of lower solubility in body fluids comprising hydroxyapatite.
CA002416201A 2000-07-17 2000-07-17 Bioactive calcium phosphate composite layers electrochemically deposited on implants Expired - Fee Related CA2416201C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2000/006838 WO2002005862A1 (en) 2000-07-17 2000-07-17 Bioactive calcium phosphate composite layers electrochemically deposited on implants

Publications (2)

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CA2416201A1 CA2416201A1 (en) 2003-01-15
CA2416201C true CA2416201C (en) 2008-11-18

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CA002416201A Expired - Fee Related CA2416201C (en) 2000-07-17 2000-07-17 Bioactive calcium phosphate composite layers electrochemically deposited on implants

Country Status (6)

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EP (1) EP1301220A1 (en)
JP (1) JP2004503333A (en)
AU (2) AU5985500A (en)
CA (1) CA2416201C (en)
HK (1) HK1060070A1 (en)
WO (1) WO2002005862A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006007730A1 (en) * 2004-07-21 2006-01-26 The University Of British Columbia Method of electrolytically depositing a pharmaceutical coating onto a conductive osteal implant
US11278642B2 (en) 2006-09-08 2022-03-22 Takao Hotokebuchi Bioimplant with evanescent coating film
US10610614B2 (en) 2006-09-08 2020-04-07 Kyocera Corporation Bioimplant with evanescent coating film
WO2008029612A1 (en) * 2006-09-08 2008-03-13 Japan Medical Materials Corporation Bioimplant
DE102012001260B4 (en) * 2012-01-23 2015-04-02 Dot Gmbh Antibacterial and osteoinductive implant coating

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5205921A (en) * 1991-02-04 1993-04-27 Queen's University At Kingston Method for depositing bioactive coatings on conductive substrates
DE19504386C2 (en) * 1995-02-10 1997-08-28 Univ Dresden Tech Process for the production of a graded coating from calcium phosphate phases and metal oxide phases on metallic implants
EP0806212B1 (en) * 1996-05-10 2003-04-02 IsoTis N.V. Device for incorporation and release of biologically active agents
US6045683A (en) * 1997-12-01 2000-04-04 University Of Alabama In Huntsville Modified brushite surface coating, process therefor, and low temperature conversion to hydroxyapatite
AU766735B2 (en) * 1998-09-15 2003-10-23 Isotis N.V. Osteoinduction

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Publication number Publication date
AU2000259855B2 (en) 2006-02-02
WO2002005862A1 (en) 2002-01-24
CA2416201A1 (en) 2003-01-15
HK1060070A1 (en) 2004-07-30
AU5985500A (en) 2002-01-30
WO2002005862A8 (en) 2002-05-30
EP1301220A1 (en) 2003-04-16
JP2004503333A (en) 2004-02-05
AU2000259855A1 (en) 2002-05-02

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