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Journal of Sol-Gel Science and Technology

, Volume 83, Issue 1, pp 143–154 | Cite as

Effects of curing and organic content on bioactivity and mechanical properties of hybrid sol–gel glass scaffolds made by indirect rapid prototyping

  • Stephan Hendrikx
  • Dzmitry Kuzmenka
  • Roberto Köferstein
  • Tobias Flath
  • Hans Uhlig
  • Dirk Enke
  • F. Peter Schulze
  • Michael C. Hacker
  • Michaela Schulz-SiegmundEmail author
Original Paper: Sol-gel and hybrid materials for biological and health (medical) applications

Abstract

We employed indirect rapid prototyping templating to fabricate bioactive and macroporous scaffolds for bone regeneration. This templating technique utilizes lost molds made of polycaprolactone by fused deposition modeling, in which the organic/ inorganic hybrid silica sol was filled and cured. Finally, the molds were dissolved and extracted, and the remaining macroporous hybrid glass constructs were recovered. The hybrid glass scaffolds offered a fully interconnected pore structure with 63–72% porosity measured by N2-pycnometry and Hg-intrusion. In bioactive sol–gel glasses one issue is the insufficient and inhomogeneous incorporation of calcium (II) ions. To address this problem we varied the curing conditions and tested the effect of the organic crosslinker on calcium retention. We strengthened the silica network by covalent crosslinking with trimethylolpropane ethoxylate which was functionalized with 3-(triethoxysilyl)propyl isocyanate. Those scaffolds showed compressive yield strengths of up to 12.7 MPa and compressive moduli between 18 and 288 MPa. Energy dispersive X-ray spectroscopy showed that a crosslinker content of 60% in the hybrids resulted in a homogeneous calcium distribution in the glass, in contrast to 40% where we found a layer of CaCl2 on the scaffold surface. The materials exhibited bioactivity in simulated body fluid which was monitored by scanning electron microscopy and X-ray powder diffraction.

Graphical Abstract

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Keywords

Binary Ternary Mechanical testing Bioactive Class-II hybrid Indirect rapid prototyping 

Notes

Acknowledgements

The authors thank Prof. Dr.-Ing. Bernhard Rieger (Department of Mechanical and Energy Engineering, HTWK Leipzig, Germany) for access to the compression testing equipment, Jörg Lenzner (Department of Experimental and Semiconductor Physics, Leipzig University) for access to SEM and EDX. The authors would also like to thank the Saxon Ministry for Science and Arts (Grant no: 4-7531.60/64/18) and the German Research Council (DFG SFB/Transregio 67 A1) for financial support.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

References

  1. 1.
    Department of Health and Human Services, Food and Drug Administration. (2004) 510(k) Summary: NovaBone-AR-Resorbable Bone Graft Substitute. https://www.accessdata.fda.gov/cdrh_docs/pdf4/K041613.pdfGoogle Scholar
  2. 2.
    Bobyn JD, Mortimer ES, Glassman AH, Engh CA, Miller JE, Brooks CE (1992) Producing and avoiding stress shielding-laboratory and clinical observations of noncemented total hip arthroplasty. Clin Orthop Relat Res 274:79–96.Google Scholar
  3. 3.
    Velasco MA, Narváez-Tovar CA, Garzón-Alvarado DA (2015) Design, materials, and mechanobiology of biodegradable scaffolds for bone tissue engineering. Bio Med Res Int 2015:729076CrossRefGoogle Scholar
  4. 4.
    Valliant EM, Jones JR (2011) Softening bioactive glass for bone regeneration: sol–gel hybrid materials. Soft Matter 7:5083–5095CrossRefGoogle Scholar
  5. 5.
    Rhee SH (2003) Effect of molecular weight of poly(ε-caprolactone) on interpenetrating network structure, apatite-forming ability, and degradability of poly(ε-caprolactone)/silica nano-hybrid materials. Biomaterials 24:1721–1727CrossRefGoogle Scholar
  6. 6.
    Gao C, Rahaman MN, Gao Q, Teramoto A, Abe K (2013) Robotic deposition and in vitro characterization of 3D gelatin−bioactive glass hybrid scaffolds for biomedical applications. J Biomed Mater Res A 101:2027–2037CrossRefGoogle Scholar
  7. 7.
    Li A, Shen H, Ren H, Wang C, Wu D, Martin RA, Qiu D (2015) Bioactive organic/inorganic hybrids with improved mechanical performance. J Mater Chem B 3:1379–1390CrossRefGoogle Scholar
  8. 8.
    Mahony O, Tsigkou O, Ionescu C, Minelli C, Ling L, Hanly R, Smith ME et al. (2010) Silica-Gelatin hybrids with tailorable degradation and mechanical properties for tissue regeneration. Adv Funct Mater 20:3835–3845CrossRefGoogle Scholar
  9. 9.
    Negahi Shirazi A, Fathi A, Suarez FG, Wang Y, Maitz PK, Dehghani F (2016) A novel strategy for softening gelatin-bioactive-glass hybrids. ACS Appl Mater Interfaces 8:1676–1686CrossRefGoogle Scholar
  10. 10.
    Zhang J, Zhao S, Zhu Y, Huang Y, Zhu M, Tao C, Zhang C (2014) Three-dimensional printing of strontium-containing mesoporous bioactive glass scaffolds for bone regeneration. Acta Biomater 10:2269–2281CrossRefGoogle Scholar
  11. 11.
    Roohani-Esfahani SI, Newman P, Zreiqat H (2016) Design and fabrication of 3D printed scaffolds with a mechanical strength comparable to cortical bone to repair large bone defects. Sci Rep 6:19468CrossRefGoogle Scholar
  12. 12.
    Fu Q, Saiz E, Rahaman MN, Tomsia AP (2013) Toward strong and tough glass and ceramic scaffolds for bone repair. Adv Funct Mater 23:5461–5476CrossRefGoogle Scholar
  13. 13.
    Hendrikx S, Kascholke C, Flath T, Schumann D, Gressenbuch M, Schulze P, Hacker MC et al. (2016) Indirect rapid prototyping of sol-gel hybrid glass scaffolds for bone regeneration - effects of organic crosslinker valence, content and molecular weight on mechanical properties. Acta Biomater 35:318–329CrossRefGoogle Scholar
  14. 14.
    Saravanapavan P, Hench LL (2001) Low-temperature synthesis, structure, and bioactivity of gel-derived glasses in the binary CaO-SiO2 system. J Biomed Mater Res A 54:608–618CrossRefGoogle Scholar
  15. 15.
    Allo BA, Rizkalla AS, Mequanint K (2012) Hydroxyapatite formation on sol–gel derived Poly(ε-Caprolactone)/bioactive glass hybrid biomaterials. ACS Appl Mater Interfaces 4:3148–3156CrossRefGoogle Scholar
  16. 16.
    Catauro M, Bollino F, Renella RA, Papale F (2015) Sol–gel synthesis of SiO2–CaO–P2O5 glasses: influence of the heat treatment on their bioactivity and biocompatibility. Ceram Int 41:12578–12588CrossRefGoogle Scholar
  17. 17.
    Kim IY, Ohtsuki C, Kawachi G, Kamitakahara M, Cho SB (2008) Preparation of bioactive microspheres of organic modified calcium silicates through sol–gel processing. J Sol–Gel Sci Technol 45:43–49CrossRefGoogle Scholar
  18. 18.
    Saravanapavan P, Jones JR, Verrier S, Beilby R, Shirtliff VJ, Hench LL, Polak JM (2004) Binary CaO-SiO2 gel-glasses for biomedical applications. Bio Med Mater Eng 14:467–486Google Scholar
  19. 19.
    Catauro M, Renella RA, Papale F, Vecchio Ciprioti S (2016) Investigation of bioactivity, biocompatibility and thermal behavior of sol–gel silica glass containing a high PEG percentage. Mater Sci Eng C Mater Biol Appl 61:51–55CrossRefGoogle Scholar
  20. 20.
    Yun HS, Kim SE, Park EK (2011) Bioactive glass–poly (ε-caprolactone) composite scaffolds with 3 dimensionally hierarchical pore networks. Mater Sci Eng C Mater Biol Appl 31:198–205CrossRefGoogle Scholar
  21. 21.
    Bosetti M, Zanardi L, Hench LL, Cannas M (2003) Type I collagen production by osteoblast-like cells cultured in contact with different bioactive glasses. J Biomed Mater Res A 64A:189–195CrossRefGoogle Scholar
  22. 22.
    O’Donnell MD, Watts SJ, Law RV, Hill RG (2008) Effect of P2O5 content in two series of soda lime phosphosilicate glasses on structure and properties–Part I: NMR. J Non-Cryst Solids 354:3554–3560CrossRefGoogle Scholar
  23. 23.
    Saravanapavan P, Jones JR, Pryce RS, Hench LL (2003) Bioactivity of gel-glass powders in the CaO-SiO2 system: a comparison with ternary (CaO-P2O5-SiO2) and quaternary glasses (SiO2-CaO-P2O5-Na2O). J Biomed Mater Res A 66:110–119CrossRefGoogle Scholar
  24. 24.
    Kaur G, Pickrell G, Kimsawatde G, Homa D, Allbee HA, Sriranganathan N (2014) Synthesis, cytotoxicity, and hydroxyapatite formation in 27-Tris-SBF for sol-gel based CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses. Sci Rep 4:4392CrossRefGoogle Scholar
  25. 25.
    Salinas AJ, Martin AI, Vallet-Regí M (2002) Bioactivity of three CaO-P 2 O 5 -SiO 2 sol-gel glasses. J Biomed Mater Res A 61:524–532CrossRefGoogle Scholar
  26. 26.
    Pereira MM, Clark AE, Hench LL (1994) Calcium phosphate formation on sol–gel-derived bioactive glasses in vitro. J Biomed Mater Res A 28:693–698CrossRefGoogle Scholar
  27. 27.
    Lin S, Ionescu C, Pike KJ, Smith ME, Jones JR (2009) Nanostructure evolution and calcium distribution in sol–gel derived bioactive glass. J Mater Chem 19:1276CrossRefGoogle Scholar
  28. 28.
    Lin S, Ionescu C, Baker S, Smith ME, Jones JR (2010) Characterisation of the inhomogeneity of sol–gel-derived SiO2–CaO bioactive glass and a strategy for its improvement. J Sol–Gel Sci Technol 53:255–262CrossRefGoogle Scholar
  29. 29.
    Messori M, Toselli M, Pilati F, Fabbri E, Fabbri P, Pasquali L, Nannarone S (2004) Prevention of plasticizer leaching from PVC medical devices by using organic–inorganic hybrid coatings. Polymer (Guildf) 45:805–813CrossRefGoogle Scholar
  30. 30.
    Kokubo T, Takadama H (2006) How useful is SBF in predicting in vivo bone bioactivity? Biomaterials 27:2907–2915CrossRefGoogle Scholar
  31. 31.
    Poologasundarampillai G, Ionescu C, Tsigkou O, Murugesan M, Hill RG, Stevens MM, Hanna JV et al. (2010) Synthesis of bioactive class II poly(γ-glutamic acid)/silica hybrids for bone regeneration. J Mater Chem 20:8952CrossRefGoogle Scholar
  32. 32.
    Poologasundarampillai G, Yu B, Tsigkou O, Valliant EM, Yue S, Lee PD, Hamilton RW et al. (2012) Bioactive silica–poly(γ-glutamic acid) hybrids for bone regeneration: effect of covalent coupling on dissolution and mechanical properties and fabrication of porous scaffolds. Soft Matter 8:4822CrossRefGoogle Scholar
  33. 33.
    He L, Li J, Zhou C, Zhu H, Cao X, Tang B (2014) Phase change characteristics of shape-stabilized PEG/SiO2 composites using calcium chloride-assisted and temperature-assisted sol gel methods. Sol Energy 103:448–455CrossRefGoogle Scholar
  34. 34.
    Brinker CJ, Scherer GW (1993) Sol-gel science: the physics and chemistry of sol-gel processing, 5th edn. Academic, Boston, MAGoogle Scholar
  35. 35.
    Pope E, Mackenzie JD (1986) Sol-gel processing of silica. J Non-Cryst Solids 87:185–198CrossRefGoogle Scholar
  36. 36.
    Keaveny TM, Wachtel EF, Ford CM, Hayes WC (1994) Differences between the tensile and compressive strengths of bovine tibial trabecular bone depend on modulus. J Biomech 27:1137–1146CrossRefGoogle Scholar
  37. 37.
    Kopperdahl DL, Keaveny TM (1998) Yield strain behavior of trabecular bone. J Biomech 31:601–608CrossRefGoogle Scholar
  38. 38.
    Wang J, Zhou B, Liu XS, Fields AJ, Sanyal A, Shi X, Adams M et al. (2015) Trabecular plates and rods determine elastic modulus and yield strength of human trabecular bone. Bone 72:71–80CrossRefGoogle Scholar
  39. 39.
    Zhou B, Liu XS, Wang J, Lu XL, Fields AJ, Guo XE (2014) Dependence of mechanical properties of trabecular bone on plate-rod microstructure determined by individual trabecula segmentation (ITS). J Biomech 47:702–708CrossRefGoogle Scholar
  40. 40.
    Brauer DS (2015) Bioactive glasses-structure and properties. Angew Chem Int Ed 54:4160–4181CrossRefGoogle Scholar
  41. 41.
    Hall BK (ed.) (1993) Mechanical properties of cortical and trabecular bone. CRC, London, TokyoGoogle Scholar
  42. 42.
    Karageorgiou V, Kaplan D (2005) Porosity of 3D biomaterial scaffolds and osteogenesis. Biomaterials 26:5474–5491CrossRefGoogle Scholar
  43. 43.
    Chen Q, Baino F, Spriano S, Pugno NM, Vitale-Brovarone C (2014) Modelling of the strength–porosity relationship in glass-ceramic foam scaffolds for bone repair. J Eur Ceram Soc 34:2663–2673CrossRefGoogle Scholar
  44. 44.
    Olmo N (2003) Bioactive sol–gel glasses with and without a hydroxycarbonate apatite layer as substrates for osteoblast cell adhesion and proliferation. Biomaterials 24:3383–3393CrossRefGoogle Scholar
  45. 45.
    Inzunza D, Covarrubias C, Marttens AV, Leighton Y, Carvajal JC, Valenzuela F, Díaz-Dosque M et al. (2014) Synthesis of nanostructured porous silica coatings on titanium and their cell adhesive and osteogenic differentiation properties. J Biomed Mater Res A 102:37–48CrossRefGoogle Scholar
  46. 46.
    Owens GJ, Singh RK, Foroutan F, Alqaysi M, Han CM, Mahapatra C, Kim HW et al. (2016) Sol–gel based materials for biomedical applications. Prog Mater Sci 77:1–79CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • Stephan Hendrikx
    • 1
  • Dzmitry Kuzmenka
    • 1
  • Roberto Köferstein
    • 2
  • Tobias Flath
    • 3
  • Hans Uhlig
    • 4
  • Dirk Enke
    • 5
  • F. Peter Schulze
    • 3
  • Michael C. Hacker
    • 1
  • Michaela Schulz-Siegmund
    • 1
    Email author
  1. 1.Pharmaceutical Technology, Institute of PharmacyLeipzig UniversityLeipzigGermany
  2. 2.Inorganic Chemistry, Institute of ChemistryMartin-Luther-University Halle-WittenbergHalle (Saale)Germany
  3. 3.Department of Mechanical and Energy EngineeringLeipzig University of Applied SciencesLeipzigGermany
  4. 4.Institute of Non-Classical Chemistry e. V. at the Leipzig UniversityLeipzigGermany
  5. 5.Institute for Chemical TechnologyLeipzig UniversityLeipzigGermany

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