(200a) pp. 2079-2082 MaterialsVols.264-268 Key Engineering tilfu.net onlineat http:/lwvwtt.

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Route by a SimplePVA'Processing Preparation of PorousBioceramics

A. C. Tas
AtaturkBulvari No. 221, 06100Ankara,Turkey TurkishAcademy of Sciences, porosity, polyvinyl alcohol, calcination calciumphosphate, Kevwords: bioceramic, Abstract. A robust procedure of preparing macro- and micro-porous calcium phosphate bioceramics is presented.The method involved the simple blending of a water soluble polymer (PVA, polyvinyl alcohol) solution and a fine calcium phosphatepowder, followed by immediate in situ gelation and then calcination at high temperaturesto burn off the polymer to form the (even morselsor blocks) are obtainedwith porosity over the porosity. Porous shapes interconnected variable range of 35 to 70Vo, with macropores ranging from 100 to 1000 pm. Sample characteization was performed via X-ray diffraction, quantitative chemical analysis, optical and electronmicroscopy,and compressivestrengthmeasurements. Introduction Eighty percent of bone (whose inorganic part is mainly a phase of alkali (Na and K) and alkaline earth (Mg) element-doped, nonstoichiometric and carbonated-apatitic calcium phosphate) is comprisedof densecortical bone,within which is found the highly porous and vascularcancellous (trabecular) for 88Voof the amountof the bone is responsible However,the cancellous bone(20Vo). (100 pm< pores<1500 pm) mainly owing to its macroporous normal bone turnoveror remodeling, nature. Cancellous bone has minimal weight-bearingfunction and is mainly susceptibleto forces;i.e., it is a load distributorratherthan a weight-bearer compressive [1]. Poresof bonesare (to flow of inorganic and organic nutrients) and the vascularization perfectly interconnected allow and'the pore sizesare so adjustedthat the osteoblasts and osteoclasts, as well as the cglls pfosontin pores and easily move around.A to the lacunaof these can easily attachthemselves hUmanblOOd, bioceramic scaffold material must mimic the pore size distribution of natural bone in order to be and biocompatible.Severaltechnologiesexist today to manufacture named as osteoconductive strong and reliable porous ceramics. knportant production advantagescan be ascribed to the preparation of macroporousbioceramics through the route of gelcasting. The method we present procedure, which variantof the well-documented hereis a simplerand inexpensive [2-8] gelcasting repon here our powders Although we only of this study. the specific quite with satisfactorily works (TCP: that phosphate we have seen Ca3(POa)2), porous producing of tricalcium samples resultsin this method also worked equally well for producing porous calcium hydroxapatite (HA: CaroeO4)6(OH)z), calcium pyrophosphate (Ca2PzO), and for even all the desired bi-phasic calcium phosphatephases,which are of the aforementioned mixtures (e.g.,HA-TCP, TCP-CazPzOz) able to withstand the high+emperature calcination without undergoing a change in their stoichiometry. Experimental Concentratedsolutions (140 gfi-) of PVA (MW: 15000, Fluka-Chemika) were first prepared by dissolving polymer powders in distilled water. Appropriate amountsof the PVA solution were then physically mixed with sub-micron particulated calcium phosphatepowders (such as, commercial being equal to TCP, Cat. No. 1.02143,Merck), namely,with the ratio of PVA solution-to-powder 0.68 mUg, in a kitchen blender for few minutes. The viscous ceramer (or gel) was then poured into to an Al2O3mold. The cast gel was immediately heated(in an electrical furnace, in air atmosphere) 500"C in I h, held at 500"C for 15 minutes,then ramped up to 1295'C in 3.5 h, soakedat that

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temperaturefor 6 h, followed by cooling back to RT in 6 h. The porous chunk obtained was cut into **ull"t pieces by using a diamond saw to produce the desired shapes. Compressive strength ,rrrasu."m"nts on the cut samples were performed with an Instron machine, and morphology and phaseconstinrdonof thosewere evaluatedby using scanningelectronmicroscopy (JSM-640' Jeol) respectively. and powder XRD (D-5000, Siemens),

Results
Macro- and micro-porosity on the fracture surfaces of the p-TcP ('\ilhitlockite) samples produced by using the above procissing recipe are shown in Figure I below. The characteristiccellular morpnology with smaller holes presentin each cell facilitate s the interconnectivity of the pores. The dense-loofing walls (as seen in Figs. la and lb) are also porous as depicted by the higber of Figs' lc and ld. magnification photomicrographs

(c) wall area macropores, Figure LSEM picturesof porousTCP blocks;(a) and (b) interconnected another from one macropores the separate (d) walls enlarged, microporous chunkhas blocks(2 x 2 x 1 cm) cut from the calcinedgel-cast of rectangUlar strength Compressive (2 to 10MPa), bones trabecular of strength to the [9] tobe 24 * 3 MPa.In comparison been-found of its high in spite quite strong being this porousWhitlockite materialhas the unique featureof technique by theArchimedes' [10]' measured poroiity (around 65-70Vo),

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The raw material we used in producing the bioresorbable (higher than 60Voin vivo resorption in 4 months and more than 85Vo in around 1 year) B-TCP samples was a chemically processed, commercially available (Article 1.02143,Merck KGaA) submicroncalcium phosphatepowder with a Ca/P molar ratio in the vicinity of 1.50, whose XRD data is shown in Fig. 2 by the bottom trace (a). The raw material actually consists of two phases, CaHPO+ and microcrystalline calciumPorous blocks (whose SEM pictures deficient hydroxyapatite (CDHA: Cas(HPO+XPO4)5(OH)). were given in Fig.l) obtainedwere single-phase B-TCP, as shown by the middle trace (b) inFig.2.

29

30 2 theta

Figure 2.XRD data: (a) raw material used for the data shown in this article, * indicatesthe peaksof the phaseCaHPO+,remaining peaksare of CDHA, (b) data for porous blocks producedas described in the experimentalsection,single-phase B-TCP, (c) data for porous blocks quenchedfrom the high o-TCP single-phase temperature,

B-TCP is known to resorb quite fast in the body, owing to its high solubility. However, the highpolymorph of TCP, namely, a-TCP, doesnot resorb as fast as B-TCP [11]. Alpha-TCP temperature has another interesting property, and it hydrolyzes itself in human plasma (and in general, in aqueoussystems)into CDHA [12]. Whence this transformation(in vitro or in vivo) is significantly complete, the product will not simply dissolve away (as does B-TCP) within the first few months following the implantation. Therefore, porous cI-TCP based implants will transform themselves into CDHA while retaining their macro-porous structure, and they will resorb in vivo by the osteoclastic action, which takes place at a pH value of 3 to 4. If an implant material is just dissolving at the bone defect-sitewithin a short period of time, then it will obviously be quite far from providing a biomechanicallysoundhealing phaseduring the bone remodeling process.

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transitionfrom o-TCP to B-TCP occursat around 1l80oC, upon cooling t131. The crystallographic o-TCP (as We have been able to totally convert the porous materialsof this study into single-phase just (c) quenching material from 1295"C to the in Fig.2), by shown by the XRD trace labeledas 900'C in 10 minutes. The compressive strength of porous o-TCP blocks (9 ! 2 MPa) were and this is due to the microcracks[11] to be much lower thanthoseof B-TCP,as expected, observed unit cell volume difference porous from the significant quenched body, originating forming in the betweenthe orthorhombic (a) and hexagonal(B) polymorphs of TCP. The cooling/quenchingrate to be carefully adjusted and to be employed through the polymorphic transformation temperatureof TCP can in turn be used as a fine-tuning parameter in producing "c[-TCP + novel bi-phasic B-TCP" bioceramics,with variable degreesof in vivo resorbability. We that if we cooled our porousTCP samplesfrom I295"C to 900"C in 45 have found, for instance, minutes, instead of 10 minutes, the end product consistedof a phasemixture of about 70Voa- and This material doeshave a higher in vivo resorbability as comparedto pure C[-TCP. 30Vop-phases. The procedure reported here for preparing macroporous calcium phosphates has also been successfully applied to fine calcium hydroxyapatite (HA) powders, as well as submicron, chemically precipitated CuPzOt powders; the latter of these powders has a quite high in vitro powders as the starting materials were so selectedthat the solubility. The use of HA and CazPzOz easyadjustmentof the CalP molar ratio in the final product over the broad range of 1.0 through 1.6 would be feasible.

Summary polyvinylalcohol calcium solutions with submicron-particulated of concentrated blending Simple

polymerburn-out calcination stepwasfoundto provide phosphate powders, followedby a suitable bioceramic implants.This macro-and micro-porous routefor producing a robustand inexpensive simpleprocess was found to be suitable for the manufacture (or of porousTCP, HA or CazPzOz for clinicalapplications. morsels or prismatic blocks mixtures) theirbi-phasic References tll 12) t3l l4l t5l 16l t7l t8l t9l l10l t11l Il2l t13l in Spine and M. Aebi: The Useof BoneSubstitutes N. Passuti M. Szpalski, R. Gunzburg, any,2002). Germ Surgery (Springer-Verlag, Soc., andV.C. Pandolfelli: J. Am. Ceram. M.D.M.Innocentini F.S.Ortega, P. Sepulveda, (2000), p.3021. Vol.83 p.2231,. Soc., J. Eur.Ceram. Vol. 22 (2002), M. Trunec andJ. Cihlar: (1999), p. 521. Vol. 82 Soc., andJ.A.Lewis:J. Am. Ceram. S.L.Morissette p. 1957. Vol. 83 (2000), Soc., M.A. HuhaandJ.A.Lewis:J. Am. Ceram. andJ.P.Pollinger: J. Am. Ceram. Y.P.Harn,B.S.Draskovich A. Emami-Naeini, S. Ghosal, p. 513. Soc., Vol. 82(1999), p. 1395 Soc., Vol. 22 (2002), J. Eur.Ceram. P. Sepulveda andV.C.Pandolfelli: F.S.Ortega, Polym., Vol. 50 (2002),p.295. Carbohyd. M.Zhai, F. Yoshii,T. KumeandK. Hashim: p. 1581. Vol. 83(2000), Soc., N.O.Engin andA.C.Tas:J. Am. Ceram. (American for ASTM Society AnnualBookof Standards C20-00, ASTM Designation USA 2001). Testing andMaterials, and F.R.Kloss,S. Rupprecht K.A. Schlegel, S. Schultze-Mosgau, H.A. Merten, J. Wiltfang, p. 115. Res. Appl.Biomater., Vol.63 (2002), Mater. P. Kessler: J. Biomed. p.22O9. Vol. 19(1998), andP.W.Brown:Biomaterials, K.S.TenHuisen p.2245. Vol. 81(1998), Soc., J. Am. Ceram. N. KivrakandA.C.Tas: