RTM Dt yee BM rile g David C. Dunand Porous Metals and Metallic FoamsPreparation of Bioactive Porous Ti-Sn-Nb Alloy for Biomedical Applications ‘A. NOURI, X. CHEN, P.D. HODGSON, J.M. LONG, C. WEN Centre for Material and Fibre Innovation, Deakin University, Geelong, Victoria 3217, Australia ABSTRACT ‘A porous Ti-16Sn-4Nb alloy with an average pore size ‘of 300 jum and porosity of 60 % was prepared by powder metallurgy, and & bone-like apatite coating was obtained by soaking the samples in a concentrated imulated body fluid (10 SBF). The changes of the microstructure and composition on the surface with soaking time were investigated by using X-ray Giffractometry (XRD), and —seanning electron microscopy equipped’ with energy dispersive spectroscopy (SEM-EDS). The bome-like apatite granules started to deposit throughout the porous Ti alloy foam after 1h soaking, and the number of granules, increased with the increase of the soaking time. A uniform bone-like apatite layer covered. the entire surface of the sample after soaking in the 10% SBF for Gh, The Ti-l6Sn-4Nb foam showed a good bioactivity after a thermochemical process and soaking into a 10% SBF INTRODUCTION Titanium (Ti) and its alloys are frequently used as implant materials in dentistry and orthopaedic surgery, due to their excellent corrosion resistance, good biocompatibility, high specific strength and relatively low elastic modulus compared 10 other metallic biomaterials [1-4]. To meet practical requirements of bone ingrowth and long-term implantation, it is necessary to develop new porous implants that mimic the architecture and low elastie modulus of natural bone, while encouraging bone to grow into the pore spaces [5] ‘A. scaffold material with a porous structure is a promising candidate to fulfil the mentioned requirements and could eliminate the problem of interfacial instability with host tissue [6-9]. However, titanium and its alloys are bioinert materials and they are generally isolated from the surrounding bone by fibrous tissues after the implantation into the living body [10,11 Apatite coating is an effective method to increase the bioactivity of implants for direct bonding with the nearby bone. Several techniques have been studied to induce bone-like apatite coatings on metallic implants, such as plasma spray coatings [12,13], sputter deposition [14], electrophoretic deposition [15], and sol- 307 Y. YAMADA Materials Research Institute for Sustainable Development, National Institute of Advanced Industrial Science and Technology, Nagoya, 463-8560, Japan gel [10,16]. However, a number of concems have been raised regarding the use of mentioned techniques in surface modification of implant materials such as cost, different structure/phase composition of the coatings from those of the natural bone and the difficulties of deposition of bone-like apatite crystals into porous or ‘complex implant geometries [17-19]. Alkali- and heat- treatment (AHT) of titanium alloys provides a suitable surface modification for implant materials and offers a promising altemative to other coating methods. The method enables the formation of biologically active bone-like apatite layer on the surface of titanium alloys by soaking the samples in a simulated body fluid (SBF) [10,18,20-21. In the present study, a porous Ti-16Sn-4Nb alloy foam \with a structure similar to human bones was prepared by powder metallurgy. ‘The bioactivity of foam was evaluated by soaking in a concentrated simulated body fluid (10 SBF), in order to improve the bone-bonding, ability between the porous Ti-16Sn-4Nb alloy foam and living bone through the AHT process. EXPERIMENTAL PROCEDURES, Commercially available elemental powders of titanium (purity 99.9%, <45 um), tin (purity 99.9%, 45 ym) and niobium (purty 99.8%, <45 jum) were mixed in the targeted composition of Ti-16Sn-4Nb (wt. %). The mixture was ball milled at room temperature for 3h in a planetary ball mill (Retsch PM 400) with stainless steel containers and balls. The ball to powder weight ratio and rotation rate of the mill were maintained at 20:1 and 200 rpm, respectively. ‘The ball milled poviders were mixed with ammonium bicarbonate particles as space holder material with a sieve size of 300-500 jun and then compacted into cylindrical bars at a pressure of 750 MPa. The green compacts were sintered in a vacuum furnace under the pressure of ~10°MPa, The sintering condition was: 1TOPC/1 h+1150°C/3 hh. Finally, open-cell Ti-16Sn-4Nb foams with 60% porosity were obtained. The detailed description of the preparation and characteristic of the porous Ti-16Sn-4Nb alloy foam can be found in our previous literature [22]The dises for the surface modification were cut from the Ti-16Sn-4Nb foam bars and ultrasonically cleaned in acetone for 30 min.The alkali treatment was performed by immersing the samples in the aqueous solution of 10M NaOH at 60 °C for 24h, The samples were washed with distilled water and dried at room temperature for 24h. The alkali-treated samples were hheat treated at 600 °C for | h in a vacuum furnace under the pressure of 1.33*10% MPa. The formation of the bbone-like apatite layer on the pre-treated surface was performed by soaking the samples in a 10x SBF at 37.0°C from 1h to 6h. The recipe of the 10* SBF is listed in Table I, and the detailed description for the preparation of the solution can be found in Ref. [23]. ‘The coated specimens were removed from the solution ata given time, rinsed with distilled water, and dried at room temperature, ‘The surfaces of the soaked specimens were characterized using X-ray diffractometry (XRD, Cu Ky radiation, 40 kV and 30 mA), scanning electron microscopy using secondary electron imaging (SEM- SED, and scanning electron microscopy equipped with an energy dispersive spectroscopy (SEM-EDS, Leica S440). RESULTS. Fig. 1 presents the morphology evolution of the apatite coating on the surface of the samples after AHT and soaking in a 10* SBF for Th to 6h. The bone-like apatite granules started to deposit throughout the foams after 1h soaking (Fig. 1(b)) and the number of the apatite granules increased with increasing soaking time (Fig, 1(@}-(€)). The coating on the surfaces of the samples soaked in the 10 SBF solution for I h and 2h ‘was heterogeneous and no apatite granule was found in some positions, as shown in Fig. 1(b) and (c). With the further soaking time to 6 h, the surface was fully covered by a uniform bone-like apatite layer, as seen in Fig. 1(e) Fig. 2 shows the EDS spectra of the coating on the surface of the samples after AHT and soaking, in the 10x SBF for 1h (o 6 h. The EDS spectra of the AHT sample revealed that the specimen contained small amount of sodium (Na) on the surface, as shown in Fig, a), TABLE |. SOLUTION PREPARATION RECIPE OF 10x SBF FOR A TOTAL VOLUME OF tL. [23] Reagent Order Amount (gr) Nac! 1 58.44 Kel 2 0.3728 CaCl,. 24,0 3 3.6754 MgCh.6H,0 4 1.0165 NaH,PO, 5 1.1998 NaHico, 6 0.840 308, Figure 1 alloy foam after (a) alkali- and heat-treatment; and soaking in the concentrated SBF for (b) 1 h; (c) 2h; (@) 4h; and (¢) 6h SEM micrographs of the porous Ti-16Sn-4Nb After soaking in the 10x SBF for 1 b, the Na peak disappeared and new calcium (Ca) and phosphate (P) peaks were observed (Fig. 2(b)-(6)). Protonging the soaking time, the intensity of Ca and P peaks increased On the contrary, the intensity of Ti peaks exhibited a rapidly decreasing trend with the increasing of soaking time. Only a minor Ti peak could be observed on the EDS spectra ofthe sample soaked in the SBF for 6h. Fig. 3 shows the XRD patterns of the samples after ANT and soaking in the 10% SBF for Ih to 6h. The peaks belong to AHT sample exhibited relatively more intensive Ti peaks compared to those of soaked in the 10x SBF (Fig. 3(a)). The peaks corresponding to the apatite crystallites emerged on the patter of the soaked samples. The intensity of apatite crystallites increased with the increasing of soaking time, accompanying with the decrease ofthe intensity of Ti peaks, as shown in Fig 3(0)-(). DISCUSSION The mechanism of apatite formation on the surface of the AHT porous Ti-16Sn-4Nb alloy foam after soaking in a SBF solution is schematically shown in Fig. 4. This, process involves the heterogeneous nucleation and the growth of bone-like apatite layer on the surface of the Porous material at physiological temperatures and under pil conditions. Firstly, the sample is subjected to alkali treatment, and the surface-passive TiO: layer partially dissolves’ into the alkaline solution to form a sodium titanate hydrogel layer. The subsequent heat treatment resulls in dehydration and densification of the sodium titanate layerFigure 2. EDS spectra of Ti-16Sn-4Nb alloy after (a) alkali and heat treatment; followed by soaking in, 10% SBF for: (b) Ih; (c) 2h; (d) 4h; and (e) 6 h. During the SBF soaking, sodium ions releases from the sample via exchange with HjO" ions resulting in the formation of a Ti-OH layer. The Ti-OH layer is negatively changed and can selectively combine with the positively changed Ca? through an electrostatic force and forms calcium titanate, Consequently, the positively charged surface combines with negatively charged phosphate ions to form amorphous caleium phosphate. Once the apatite nuclei are formed, they spontaneously grow by consuming the calcium and phosphate ions from the surrounding SBF solution [10, 24, 25] Another factor enabling the rapid formation of apatite layer on the surface of porous Ti alloy foam is the high concentration of SBF solution used in the present work (Table 1), According to Ostwald’s nucleation theory {26}, the free energy for nucleation will decrease with the increase of the supersaturation, the temperature and the reduction of the net interfacial energy. The highly supersaturated calcium and phosphate ion solution in 10% SBF results in the reduction of free energy and hence facilitates the nucleation of the apatite, Moreover, the addition of NaHCO; in 10 SBF increases pH value and supersaturation of the solution, resulting in rapid formation of a bone-like apatite layer [27] From Fig. I(a), the considerable cracks on the porous Ti alloy substrate had been formed during the heat treatmentdrying process. After soaking in the 10 SBF for Ih, the first apatite nuclei appeared as a petal-like nanocluster which gradually changed to an apatite crystal granule at longer soaking times of 4 h and 6h, -16SH-4ND jt. Intensity (au) 3040 20(dex,) Figure 3. The XRD patterns of porous Ti-16Sn-4Nb alloy after (a) alkali- and heat-treatment and soaking in the 10 SBF for: (b) 1 hy(c) 2h; (4) 4 h; (e) 6h, 308070 309 ‘SBE eae : ce a ne re | w@™ ° voy Miho Comers HA = Porous Ti-16Sn-4Nb Sey oa rer", Figue 4A sclenatiliston ofthe apatite formation on the surface of AHT porous Ti-16Sn-4Nb alloy foam soaked in SBF, shown in higher magnification images of Fig. (b)}(e). AS ‘mentioned earlier, one of the advantages of this method is that the apatite nuclei can grow into complex-shaped and/or porous materials by continuous absorbing of Ca* and HPO, from the SBF solution. However, at longer soaking time (4 h to 6 h) a fairly high obstruction of the opening of the porous surfaces was observed which consequently leads to a reduction in pore volume available for bone ingrowth. EDS results showed a minor Na spectra afer AHT suggesting the penetration of the Na into the porous Ti alloy substrate, as seen in Fig. 2(a):The decrease in TiCa (or Ti/P) ratio with the increasing of soaking time can be attributed to the formation of bone-like apatite layer on the surface of porous Ti alloy foam. The intensity of Ti peaks is greatly diminished after 6h soaking indicating the thicker apatite layer at this stage (Fig. 2(e). The presence of chlorine (CI) peaks after 2h soaking indicates the incorporation of the SBF-CT ions into the apatite layer (Fig. 2(c)-(e). The presence of apatite granules can be also corroborated by XRD analysis after soaking the samples in the 10* SBF for Th. The gradual reduction in Ti peaks (Fig, 3(b)-(6)) further indicate that the thickness of the bone-like apatite layer increases with the increasing of soaking time. However, the presence of Ti peaks in both XRD pattems and EDS spectra of the sample soaked for 6 hi indicates that the coating was not thick enough to prevent X-ray beam from penetrating up to the substrate surface. Due to higher stability of a concentrated SBF solution at low temperature, it is predicted that a lower soaking temperature provides a thicker apatite layer [27] ‘The thermochemical process applied on the porous Ti- 16Sn-4Nb alloy foam is expected to promote bone healing, leading to rapid osseointegration of the implant material In the present study, a thermochemical process was attempted (0 form a bone-like apatite coating on the surface of a porous Ti-16Sn-4Nb alloy foam. The porous samples were soaked in a concentrated SBF from | h to 6h. The main conclusions are as follows:1. 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