Materials Letters 74 (2012) 8184

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Processing of 45S5 Bioglass by lithography-based additive manufacturing

Passakorn Tesavibul a,, Ruth Felzmann a, Simon Gruber a, Robert Liska b, Ian Thompson c, Aldo R. Boccaccini d, Jrgen Stamp a
a

Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstrae 9-11/E308, A-1040 Vienna, Austria Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/E163, 1060 Vienna, Austria Dental Institute, Biomaterials Unit, King's College London, London SE1 9RT, UK d Institute of Biomaterials, Department of Materials Science and Engineering, University of Erlangen-Nuremberg, Cauerstr. 6, 91058 Erlangen, Germany
b c

a r t i c l e

i n f o

a b s t r a c t
Lithography-based Additive Manufacturing Technologies (AMTs) were used for fabricating cellular structures made of 45S5 Bioglass. Using AMTs it is possible to design and fabricate cellular structures with a resolution of around 40 m and wall thicknesses down to 200 m. The presented process relies on selectively polymerizing a photosensitive, ceramic-lled resin with a dynamic mask. The dynamic mask is based on a digital mirror array which projects blue light (light emitting diodes with a wavelength of 460 nm) onto the resin. The mechanical properties of sintered bulk samples (biaxial strength) and cylindrical cellular structures (compressive strength) were determined. The biaxial strength of the manufactured samples was 40 MPa, and the compressive strength of the cellular structure was 0.33 MPa, which is slightly lower than the strength of porous Bioglass structures made by the foam replica method. Lithography-based AMT offers an excellent alternative to existing bone implant and scaffold fabrication methods providing accurate control of 3D morphology and pore architecture. 2012 Elsevier B.V. All rights reserved.

Article history: Received 5 October 2011 Accepted 5 January 2012 Available online 12 January 2012 Keywords: Biomaterials Biomimetic Porous materials Structural

1. Introduction Bone tissue engineering (BTE) requires scaffolds (3D porous structures) fabricated with materials which exhibit high surface reactivity in physiological uids leading to the formation of strong bonds to bone tissue [1,2]. These scaffolds must exhibit high and interconnected porosity, and in combination with relevant cells and signaling molecules, should promote the regeneration of new vascularized bone tissue [2,3]. Bioactive silicate glasses, originally developed by Hench et al. 40 years ago [4], represent attractive materials for the development of BTE scaffolds due to their proven in vitro and in vivo bioactivity [5]. The application of bioactive glasses in BTE is an expanding research eld, with more than 100 papers being published each year (based on a search in Web of Science using the combined keywords bioactive glass and scaffold), and the latest innovations in the eld have been comprehensively covered in recent review papers [68]. Not only the chemical composition of the scaffold material but also the microstructure and 3D morphology of the scaffold, characterized by a highly interconnected pore network, as well as the mechanical competence of the structure and the macroscopic shape determine the suitability of a scaffold for BTE [13]. The analysis of the literature reveals that there are still considerable research efforts related to identifying suitable manufacturing methods for BTE scaffolds based

Corresponding author. Tel.: + 43 1 58801 30857; fax: + 43 1 58801 30895. E-mail address: ptesavib@mail.tuwien.ac.at (P. Tesavibul). 0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2012.01.019

on bioactive glasses exhibiting the required porosity, pore structure, mechanical integrity as well as for obtaining parts with complex shapes and reproducible properties [68]. In this context, rapid prototyping methods for bioactive glass scaffolds have started to be investigated, including fused deposition modeling and 3D printing [9,10], direct ink writing [11], solid freeform fabrication (e.g. freeze extrusion) [12], and rapid prototyping based on laser cladding [13]. In the present investigation we have explored for the rst time the application of lithography-based additive manufacturing techniques (AMTs), a special additive manufacturing method, to produce Bioglass based scaffolds. AMTs are a group of manufacturing methods suitable for the fabrication of cellular solids. Especially in cases where high feature resolution and small pore sizes are requested, lithographybased AMTs [14] offer several benets in comparison with alternative AMTs (selective laser sintering [15], powder-based 3D-printing). For applications in regenerative medicine of hard tissues, ceramic scaffolds with pore sizes between 100 m and 500 m are usually required, a size regime that ts well into the capabilities of lithography-based AMTs. For obtaining glass or ceramic parts with lithography-based AMTs it is necessary to process a photopolymer which is lled with large amounts of glass or ceramic particles (typically 4060 vol% solid loading). Commercially available processes like stereolithography or digital light processing (DLP) can be modied in order to be capable to process such highly lled, viscous photopolymers [1619]. A recently developed DLP-based process [20] has been used for the rst time in this work to fabricate bulk and cellular structures made from 45S5 Bioglass. The structures were characterized in

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terms of macrostructure visualization and microstructure analysis, and in case of scaffolds, also in terms of mechanical properties. 2. Material and methods 2.1. Fabrication 45S5 Bioglass powder of particle size in the range 530 m was mixed with acrylate-based monomer, an organic solvent (polypropylene glycol), light absorber and photoinitiator at 43% of solid loading, leading to a photosensitive slurry. Then, the above mentioned system (DLP) was used to solidify the Bioglass slurry in a layer by layer fashion resulting in free forming the geometry of the Bioglass green part with high resolution, such as 25 m in layer thickness and 50 m in the x/y-plane, as illustrated in Fig. 1. With a certain level of light intensity, 0.05 wt% of photoinitiator and 5 s of exposure time, Bioglass green part samples can be fabricated. After that, a thermal treatment process was applied for removing the solvent, decomposing the polymeric binder and sintering the samples. The program for thermal treatment was developed based on TGA measurement, with a lower heating rate in regions of high weight loss. Finally, the part was sintered for 1 hour at 1000 C to obtain a partially crystallized Bioglass product. 2.2. Characterization The viscosity of the slurry was determined by a rheometer (MCR 300 from Anton Paar, Austria). The produced parts were visually inspected and samples are depicted in Fig. 2. The primary characterization carried out was in terms of mechanical properties. Biaxial strength samples (13 mm in diameter and 2 mm thickness) and

Fig. 2. Bioglass parts fabricated by lithography-based AMT after sintering: (a) cylindrical cellular structure (scaffold) used for compressive strength testing and (b) customized bone implant.

cylindrical cellular structures (9.8 mm in diameter and 11.6 mm height) for compressive strength testing were fabricated. The 3Dmodels of the samples were designed by CAD software (Magics from Materialise, Leuven, Belgium). The biaxial strength test was performed according to the DIN EN ISO 6872 standard. The biaxial and the compressive strength tests were performed with 1 mm/min cross head speed using a universal mechanical testing machine (Zwick-Z050, Germany). The density of the solid sample was measured and compared with that of fully dense 45S5 Bioglass. 3. Results and discussion Typical Bioglass parts fabricated by the present lithographybased AMT are shown in Fig. 2. A microscopy image of the cylindrical cellular structure for compressive test is indicated in Fig. 2a. The customized Bioglass component for orthopedic implant in the maxillofacial area, which can be designed and fabricated with accurate shape and dimensions, is shown in Fig. 2b. The characterization results are shown in Table 1. The density of the solid samples were measured using Archimedes's method, and a result of 2.45 g/cm was obtained, which corresponds to 91% of the theoretical density of the 45S5 Bioglass (2.7 g/cm 3) [5]. The SEM images are shown in Fig. 3. Clearly, sintering for 1 hour at 1000 C has not led to full densication of the material. In previous studies, the sintering of bioactive glass powder has been investigated showing

Fig. 1. Digital light processing system for processing highly lled photosensitive slurries: (a) photograph of the device, and (b) schematic setup of the utilized machine.

P. Tesavibul et al. / Materials Letters 74 (2012) 8184 Table 1 Summary of material properties of 45S5 Bioglass specimens processed by lithographybased AMT. Density of solid sample (g/cm3) Biaxial strength (MPa) Compressive strength of cellular structure (MPa) Porosity of the cellular structure (%) 2.45 40 0.33 50

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that attainment of full densication is impaired by the simultaneous crystallization that occurs at temperature >600 C [21]. The strength from biaxial testing (see Table 1) is comparable to the exural strength of traditionally processed Bioglass, which was reported to be 42 MPa [22]. This result conrms that the sintered structure with a relative density of 91% is sufciently uniform, e.g. no large voids

or defects (microcracks) are present which would detrimentally affect the mechanical strength. As indicated by Fig. 3 the residual micro-porosity originates from small pores which probably are caused by insufcient deagglomeration during the mixing-process of the slurry. The compressive strength of the cellular structure is, however, rather low in comparison with equivalent bioactive glass scaffolds reported in literature [68]; hence optimization of the sintering parameters will need to be carried out in following experiments. The viscosity of the Bioglass slurry used in the present study was measured at 7.3 Pa s which is rather high compared to photosensitive slurries used in conventional lithography-based AMT systems. Nevertheless, by utilizing the modied DLP-process described in Section 2 these slurries can be processed on a routine basis. The ability to utilize such high viscosity slurries allows the process to be applied to fabricate parts from various ceramic and glass powders with sufciently high solids loading. AMT will facilitate fabrication of parts with patientspecic geometries as well as structures whose cellular architecture (porosity, pore size, pore geometry) has been optimized for providing suitable mechanical properties as well as biological performance tailored for the specic application in BTE. 4. Conclusions It has been shown for the rst time that 45S5 Bioglass powder can be processed using lithography-based additive manufacturing to form 3D parts with predetermined shape and tailored macroscopic and microstructural features. Using the presented AMT it is possible to fabricate Bioglass-based cellular structures with arbitrary porosity and pore sizes of the order of 500 m, which is similar to the pore dimensions in trabecular bone. The method offers thus a convenient alternative technology for the design of patient-specic bone implants and scaffold architectures which could be benecial in BTE and bone replacement strategies, especially considering the highly bioactive behavior and bone bonding ability of Bioglass. Acknowledgements Financial support by The European Union (FP7 260043 PHOCAM) is gratefully acknowledged. References
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Fig. 3. SEM images of biaxial testing specimen in various magnications: (a) 61, (b) 350, and (c) 1000.

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P. Tesavibul et al. / Materials Letters 74 (2012) 8184 [18] Halloran JW, Tomeckova V, Gentry S, Das S, Cilino P, Yuan D, et al. Photopolymerization of powder suspensions for shaping ceramics. J Eur Ceram Soc 2011;31: 26139. [19] Chu TG, Orton DG, Hollister SJ, Feinberg SE, Halloran JW. Mechanical and in vivo performance of hydroxyapatite implants with controlled architectures. Biomaterials 2002;23:128393. [20] Liska R, Patzer J, Stamp J, Wachter W, Appert C, Technische Universitt Wien. Device and method for processing light-polymerizable material for building up an object in layers. WO 2010/045951 A1; 2010. [21] Bretcanu O, Chatzistavrou X, Paraskevopoulos K, Conradt R, Thompson I, Boccaccini AR. Sintering and crystallisation of 45S5 Bioglass powder. J Eur Ceram Soc 2009;29:3299306. [22] Hench LL, Kokubo T. Properties of bioactive glasses and glass-ceramics. In: Black J, Hastings G, editors. Handbook of biomaterial properties. London: Chapman & Hall; 1998. p. 35563.

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