Ceramics and Glasses

2/21/2011

Definitions
Ceramic:Inorganiccompoundsthatcontainmetallic andnonmetallicelements,forwhichinteratomic bondingisionicorcovalent,andwhichare generallyformedathightemperatures. Glass:(i)Aninorganicproductoffusionthathas cooledtoarigidconditionwithoutcrystallization; (ii)Anamorphoussolid.

2/21/2011

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

Definitions
Amorphous:(i)Lackingdetectablecrystallinity;(ii) possessingonlyshortrangeatomicorder;also glassyorvitreous Glassceramic:Polycrystallinesolidspreparedbythe controlledcrystallization(devitrification)of glasses. Bioactivematerial:Amaterialthatelicitsaspecific biologicalresponseattheinterfaceofthe material,resultingintheformationofabond betweenthetissuesandthematerial.
2/21/2011 3

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

CrystalversusGlassyCeramics
Crystallineceramicshavelongrangeorder,with componentscomposedofmanyindividually orientedgrains. Glassymaterialspossessshortrangeorder,and generallydonotformindividualgrains. Thedistinctionismadebasedonxraydiffraction characteristics. Mostofthestructuralceramicsarecrystalline.

2/21/2011

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

Materialsthatcanbeclassifiedasbioceramics include: Alumina Zirconia Calciumphosphates Silicabasedglassesorglassceramics, Pyrolytic carbons

2/21/2011

Metal CeramicComparison

Stiffness is comparable to the metal alloys The biggest problem is fracture toughness (sensitivity to flaws). Rigid plastics < Ceramics = Metals

2/21/2011

WhyUseBioceramics?

General Options

Toxic/ Imunogenic/ Disease transmission?

Mechanical Properties?

Bioactive?

Degradable?

Autograft Allograft Metals Ceramics Polymers Composites

Excellent Moderate Low

Advantages:
inertinbody(orbioactiveinbody);Chemicallyinertin manyenvironments highwearresistance(orthopedic&dentalapplications) highmodulus(stiffness)&compressivestrength estheticfordentalapplications

2/21/2011

Disadvantages
brittle(lowfractureresistance,flawtolerance) lowtensilestrength(fibersareexception) poorfatigueresistance(relatestoflawtolerance)

2/21/2011

PhysicalForms
Bioceramics areavailableas: Microspheres Thinlayersorcoatingsonametallicimplant Porousnetworks Compositeswithapolymercomponent Largewellpolishedsurfaces

2/21/2011

10

NaturesCeramicComposites
Naturalhardtissuesareceramic polymercomposites: Bones,Teeth,Shells Tissue=organicpolymerfibers+ mineral+livingcells Mineralcomponent(Ceramic) Bone:hydroxyapatite(HA) Ca5(PO4)3OH Mineralizationunderbiological conditions: Manyelementalsubstitutions Proteindirectedcrystallization Uniquecharacteristics crystal morphologyandsolubility Syntheticcalciumphosphatesareused asbiomaterials bioactive

Synthetic HA

Bone HA

11

BasicApplications:
Orthopedics: boneplatesandscrews total&partialhipcomponents(femoralhead) coatings(ofmetalprostheses)forcontrolled implant/tissueinterfacialresponse spacefillingofdiseasedbone vertebralprostheses,vertebraspacers,iliaccrest prostheses

2/21/2011

12

2/21/2011

Trends Biomater. Artif. Organs, Vol 18 (1), pp 9-17 (2004)

13

2/21/2011

14

MechanicalProperties

15

Dentistry:
dentalrestorations(crownandbridge) implantapplications(implants,implantcoatings,ridge maintenance) orthodontics(brackets) glassionomercementsandadhesives

2/21/2011

16

Veneers

2/21/2011

17

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

Beforeandafter

2/21/2011

18

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

Other:
innerearimplants(cochlearimplants) drugdeliverydevices ocularimplants heartvalves

2/21/2011

19

Ceramics
Alumina,Zirconium,Hydroxyapatite,Calcium phosphates,Bioactiveglassesarecommon Porousceramicmaterialsexhibitmuchlowerstrengths buthavebeenfoundextremelyusefulascoatingsfor metallicimplants. Thecoatingaidsintissuefixationoftheimplantby providingaporoussurfaceforthesurroundingtissueto growintoandmechanicallyinterlock. Certainceramicsareconsideredbioactiveceramicsif theyestablishbondswithbonetissue.
2/21/2011 20

Hip Implant

Osteointegration

Fast mineralization of the surface Surface colonization by the osteoblasts Stable binding between the formed mineral phase and the implant surface Structural continuity to the surrounding bone

2/21/2011

21

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

TypesofBioceramicTissue Interactions:
Dense,inert,nonporousceramicsattachtobone(ortissue) growthintosurfaceirregularitiesbypressfittingintoadefect asatypeofadhesivebond(termedmorphologicalfixation) Al2O3 Porousinertceramicsattachbyboneresultingfromingrowth (intopores)resultinginmechanicalattachmentofboneto material(termedbiologicalfixation)Al2O3 Dense,nonporoussurfacereactiveceramicsattachdirectlyby chemicalbondingwithbone(termedbioactivefixation) bioactiveglasses&Hydroxyapatite.

2/21/2011

22

http://www.bioen.utah.edu/faculty/pat/Courses/biomaterials/coursenotes.html

ProcessingofCeramics
1.Compounding Mixandhomogenizeingredientsintoawaterbasedsuspension=slurry or,intoasolidplasticmaterialcontainingwatercalledaclay 2.Forming Theclayorslurryismadeintopartsbypressingintomold(sintering).Thefine particulatesareoftenfinegrainedcrystals. 3.Drying Theformedobjectisdried,usuallyatroomtemperaturetothesocalled "green"orleatherystate. 4.Firing Heatinfurnacetodriveoffremainingwater.Typicallyproducesshrinkage,so producingpartsthatmusthavetightmechanicaltolerancerequirescare. Porouspartsareformedbyaddingasecondphasethatdecomposesathigh temperaturesformingtheporousstructure.

2/21/2011

23

Alumina (Al2O3) and Zirconia (ZrO2)

The two most commonly used structural bioceramics. Primarily used as modular heads on femoral stem hip components. Wear less than metal components, and the wear particles are generally better tolerated.

2/21/2011

24

FemoralComponent

2/21/2011

25

Alumina(Al2O3):
singlecrystalaluminareferredtoas Sapphire Rubyisaluminawithabout1%of Al3+replacedbyCr3+;yieldsred color Bluesapphireisaluminawith impuritiesofFeandTi;various shadesofblue

2/21/2011

26

StructureandProperties:
mostwidelyusedformispolycrystalline unique,complexcrystalstructure strengthincreaseswithdecreasinggrainsize elasticmodulus(E)=360380GPa

2/21/2011

27

FabricationofBiomedicaldevicesfrom Al2O3& (ZrO2):

Devicesareproducedbypressingandsinteringfine powdersattemperaturesbetween1600to1700C. AdditivessuchasMgOadded(<0.5%)tolimitgrain growth

2/21/2011

28

DentalPorcelain:
Ternarycomposition=mixtureofK2OAl2O3SiO2 made bymixingclays,feldspars,andquartz CLAY=Hydratedaluminosilicate FELDSPAR=Anhydrousaluminosilicate QUARTZ=AnydrousSilicate

2/21/2011

29

CalciumPhosphates
Calciumphosphatecompoundsareabundantinnatureandinliving systems. Biologicapatitesconstitutetheprincipalinorganicphaseinnormal calcifiedtissues(e.g.,enamel,dentin,bone)arecarbonatehydroxyapatite, CHA. Alsofoundinsomepathologicalcalcifications(e.g.,urinarystones,dental tartarorcalculus,calcifiedsofttissues heart,lung,jointcartilage)

2/21/2011

30

2/21/2011

Table from: R. LeGeros Chem. Rev., 2008, 108 (11), pp 47424753

31

CalciumPhosphates
Severalcalciumphosphateceramicsareconsideredbiocompatible.Of these,mostareresorbableandwilldissolvewhenexposedto physiologicalenvironments.Someofthesematerialsinclude,inorderof solubility: TetracalciumPhosphate(Ca4P2O9)>AmorphouscalciumPhosphate> alphaTricalciumPhosphate(Ca3(PO4)2)>betaTricalciumPhosphate (Ca3(PO4)2)>>Hydroxyapatite(Ca10(PO4)6(OH)2)

2/21/2011

32

Calciumhydroxyapatite (Ca10(PO4)6(OH)2):HA
Hydroxyapatiteistheprimarystructuralcomponentofbone. Asitsformulasuggests,itconsistsofCa2+ionssurroundedby PO42 andOH ions.

Unliketheothercalciumphosphates,hydroxyapatite doesnotbreakdownunderphysiologicalconditions.

2/21/2011

33

BoneMimicryPropertiesofCalcium Phosphates
1) InterconnectingPorosity Interconnectingmacroporosity isintroducedinsynthetic calciumphosphatesby:
Addingporogens (H2O2,polymericporogens) Foamingmethods

Microporosity dependsonsinteringtemperature
CaP sinteredat1200Cshowssignificantlylessporositythanthatsinteredat 1000C

2/21/2011

(A) Bovine bone-derived HA. (B and C) Biphasic calcium phosphate, BCP. The original interconnecting macroporosity in bone was preserved in A. Macroporsity in B and C was introduced using porogens before sintering. C shows the presence of concavities.

34

BoneMimicryPropertiesofCalcium Phosphates
1) InterconnectingPorosity Interconnectingmacroporosity isintroducedinsynthetic calciumphosphatesby:
Addingporogens (H2O2,polymericporogens) Foamingmethods

Microporosity dependsonsinteringtemperature
CaP sinteredat1200Cshowssignificantlylessporositythanthatsinteredat 1000C

SEM of BOP sintered at (A) 105000 and (B) 1200 C. Note the presence of microporosities in A and not in B.

2/21/2011

35

BoneMimicryPropertiesofCalcium Phosphates
2) Biodegradability
Invitrobiodegradationisdeterminedbysuspendingthematerialinacidicbuffer andmonitoringthereleaseofCa2+ionswithtime Theacidicbuffer,tosomeextent,mimicstheacidicenvironmentduring osteoclastic activity(boneresorption). InvitroorinvivodegradationofCaPs dependsontheircomposition,particlesize, crystallinity (reflectingcrystalsize),porosity,andpreparationconditions. Degradationorrateofdissolutionproceedsinthefollowingdecreasingorder: TCPbovineboneAp (unsintered)bovineboneAp (sintered)>corallineHA>HA. ComparingdifferentsyntheticCaPs (unsintered),thesolubilitydecreasesinthe orderACP>DCPD>OCP>CDA. Incorporationofdifferentionsapatitecanincrease(e.g.,CO32,Mg2+,orSr2+)or decrease(e.g.,F)thesolubilityoftheapatite.

2/21/2011

36

BoneMimicryPropertiesofCalcium Phosphates
3) Bioactivity
Bioactivity(propertythatallowsthe materialtodirectlybondwiththe newformingbone)wasfirst observedanddescribedbyHenchet al.inspecialsilicabasedbioactive glasses(J.Biomed.Mater.Res.1978 2117) Incontrast,anunmineralized fibrous tissueformsattheinterfaceofthe newboneandbionert materials Example:directboneattachmentis observedonaplasmasprayedHA coatedTialloysurface,whilefibrous tissueencapsulatestheuncoated

2/21/2011

Bone growth and attachment on Ti alloy cylinder grit blasted with apatitic abrasive on one side (A) and alumina abrasive on the other side (B). The side grit blasted with apatitic abrasive showed direct bone attachment (A), while the side grit blasted with alumina showed indirect bone attachment through a nonmineralized fibrous layer. (Proceedings of the 25th Annual International Society of Biomaterials; Woodhead Publishing: Cambridge, U.K. , 1998.) 37

BoneMimicryPropertiesofCalciumPhosphates
4) Osteoconductivity
Whenreferringtobiomaterials,osteoconductivity istheabilityofthematerialto serveasascaffoldortemplatetoguideformationofthenewlyformingbonealong theirsurfaces. InvivotheCHAlayerthatformsonCaP biomaterialsurfacesadsorbscirculating proteins(fromthebiologicenvironment)onwhichbonecellsattach,migrate, proliferate,anddifferentiate,leadingtomatrixproductionandbiomineralization.

Schematic representation of the dissolution/precipitation process involved in formation of CHA on CaP surfaces in vivo. Acid environment caused by cellular (macrophages, osteoclasts) activity causes partial dissolution of CaP, causing increased supersaturation of the biologic or physiological fluid, causing precipitation of CHA incorporating 38 003 and other ions and organic molecules (protein). 2/21/2011

BoneMimicryPropertiesofCalciumPhosphates
4) Osteoinductivity
Osteoinductivity istheabilityofthematerialtoinducedenovoboneformation withoutthepresenceofosteogenic factors(Adesirablepropertyinbonesubstitute materials) CaP biomaterialsaregenerallyknowntobeosteoconductive butnotosteoinductive. Osteoinductive propertiescanbeintroducedtoCaP materialsbytwomethods: (1)designingtheCaPs withappropriategeometry,topography,combined appropriatemacroporosity/microporosity andconcavitiesthatwillallowthe entrapmentandconcentrationofcirculatinggrowthfactorsorosteoprogenitor cells responsibleforboneformationor (2)combiningCaP withgrowthfactors(BMPs,mesenchymal cells)orbioactive proteins(collagen,OPs,orpeptides)

2/21/2011

39

Calciumhydroxyapatite (Ca10(PO4)6(OH)2):HA

2/21/2011

40

Calciumhydroxyapatite (Ca10(PO4)6(OH)2):HA
gainedacceptanceasbonesubstitute repairofbonydefects,repairofperiodontaldefects, maintenanceoraugmentationofalveolarridge,ear implant,eyeimplant,spinefusion,adjuvanttouncoated implants.

2/21/2011

41

HAis: Ca10(PO4)6(OH)2
SincecollageniscloselyassociatedwithHAinnormal bone,itisalogicalcandidateforinductionofahost response.Insomecasesbonegrowthinornear implantedHAismorerapidthanwhatisfoundwith controlimplants.IntheliteratureHAissometimes referredtoasan"osteoinductivematerial.However,HA doesnotseemtoinducebonegrowthinthesameway as,say,BMP.

2/21/2011

42

BioceramicCoatings
Coatingsofhydroxyapatiteareoftenappliedtometallic implants(mostcommonlytitanium/titaniumalloysand stainlesssteels)toalterthesurfaceproperties. Inthismannerthebodyseeshydroxyapatitetype materialwhichitappearsmorewillingtoaccept. Withoutthecoatingthebodywouldseeaforeignbody andworkinsuchawayastoisolateitfromsurrounding tissues. Todate,theonlycommerciallyacceptedmethodof applyinghydroxyapatitecoatingstometallicimplantsis plasmaspraying.

2/21/2011

43

BoneFillers
Hydroxyapatitemaybeemployedinformssuchas powders,porousblocksorbeadstofillbonedefectsor voids. Thesemayarisewhenlargesectionsofbonehavehadto beremoved(e.g.bonecancers)orwhenbone augmentationsarerequired(e.gmaxillofacial reconstructionsordentalapplications). Thebonefillerwillprovideascaffoldandencouragethe rapidfillingofthevoidbynaturallyformingboneand providesanalternativetobonegrafts. Itwillalsobecomepartofthebonestructureandwill reducehealingtimescomparedtothesituation,ifno

2/21/2011

44