AccScience Publishing / IJB / Volume 8 / Issue 1 / DOI: 10.18063/ijb.v8i1.503
Cite this article
51
Download
1640
Views
Journal Browser
Volume | Year
Issue
Search
News and Announcements
View All
RESEARCH ARTICLE

3D Printing of a Graphene-Modified Photopolymer Using Stereolithography for Biomedical Applications: A Study of the Polymerization Reaction

S. Lopez de Armentia1* S. Fernández-Villamarín1 Y. Ballesteros1 J. C. del Real1 N. Dunne2,3,4,5,6,7,8,9 E. Paz1*
Show Less
1 Department of Mechanical Engineering, Institute for Research in Technology, Universidad Pontificia Comillas, Alberto Aguilera 25, 28015 Madrid, Spain
2 School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9, Ireland
3 Centre for Medical Engineering Research, School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9, Ireland
4 School of Pharmacy, Queen’s University of Belfast, 97 Lisburn Road, Belfast BT9 7BL, United Kingdom
5 Department of Mechanical and Manufacturing Engineering, School of Engineering, Trinity College Dublin, Dublin 2, Ireland
6 Advanced Manufacturing Research Centre (I-Form), School of Mechanical and Manufacturing Engineering, Dublin City University, Glasnevin, Dublin 9, Ireland
7 Advanced Materials and Bioengineering Research Centre (AMBER), Royal College of Surgeons in Ireland and Trinity College Dublin, Dublin 2, Ireland
8 Advanced Processing Technology Research Centre, Dublin City University, Dublin 9, Ireland
9 Trinity Centre for Biomedical Engineering, Trinity Biomedical Sciences Institute, Trinity College Dublin, Dublin 2, Ireland
Submitted: 20 September 2021 | Accepted: 19 December 2021 | Published: 13 January 2022
© 2022 by the Author(s). This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution 4.0 International License ( https://creativecommons.org/licenses/by/4.0/ )
Abstract

Additive manufacturing is gaining importance thanks to its multiple advantages. Stereolithography (SLA) shows the highest accuracy and the lowest anisotropy, which has facilitated the emergence of new applications as dentistry or tissue engineering. However, the availability of commercial photopolymers is still limited, and there is an increasing interest in developing resins with properties adapted for these new applications. The addition of graphenebased nanomaterials (GBN) may provide interesting advantages, such as improved mechanical properties and bioactivity. However, there is a lack of knowledge regarding the effect of GBNs on the polymerization reaction. A photopolymerizable acrylic resin has been used, and the effect of the addition of 0.1wt% of graphene (G); graphene oxide (GO) and graphite nanoplatelets (GoxNP) on printability and polymerization have been investigated. It was observed that the effect depended on GBN type, functionalization and structure (e.g., number of layers, size, and morphology) due to differences in the extent of dispersion and light absorbance. The obtained results showed that GO and GoxNP did not significantly affect the printability and quality of the final structure, whilst the application of G exhibited a negative effect in terms of printability due to a reduction in the polymerization degree. GO and GoxNP-loaded resins showed a great potential to be used for manufacturing structures by SLA.

Keywords
Nanocomposites
Graphene-based nanomaterials
Stereolithography
Photocurable polymer
Printing accuracy
References

1. Borrello J, Nasser P, Iatridis JC, et al., 2018, 3D Printing a Mechanically-Tunable Acrylate Resin on a Commercial DLP-SLA Printer. Addit Manuf, 23:374–80. https://doi.org/10.1016/j.addma.2018.08.019

2. Borrello J, Backeris P, 2017, Rapid Prototyping Technologies. In: Rapid Prototyping in Cardiac Disease: 3D Printing the Heart, p41–9. https://doi.org/10.1007/978-3-319-53523-4_5

3. Vasamsetty P, Pss T, Kukkala D, et al., 2020, 3D Printing in Dentistry-Exploring the New Horizons. Mater Today, 26:838–41. https://doi.org/10.1016/j.matpr.2020.01.049

4. Baumgartner S, Gmeiner R, Schönherr JA, et al., 2020, Stereolithography-Based Additive Manufacturing of Lithium Disilicate Glass Ceramic for Dental Applications. Mater Sci Eng C, 116:111180. https://doi.org/10.1016/j.msec.2020.111180

5. Schüller-Ravoo S, Teixeira SM, Feijen J, et al., 2013, Flexible and Elastic Scaffolds for Cartilage Tissue Engineering Prepared by Stereolithography Using Poly (Trimethylene Carbonate)-Based Resins. Macromol Biosci, 13:1711–9. https://doi.org/10.1002/mabi.201300399

6. Sodian R, Loebe M, Hein A, et al., 2002, Application of Stereolithography for Scaffold Fabrication for Tissue Engineered Heart Valves. ASAIO J, 48:12–6. https://doi.org/10.1097/00002480-200201000-00004

7. Lee KW, Wang S, Fox BC, et al., 2007, Poly (Propylene Fumarate) Bone Tissue Engineering Scaffold Fabrication using Stereolithography: Effects of Resin Formulations and Laser Parameters. Biomacromolecules, 8:1077–84. https://doi.org/10.1021/bm060834v

8. Lu F, Wu R, Shen M, et al., 2021, Rational Design of Bioceramic Scaffolds with Tuning Pore Geometry by Stereolithography: Microstructure Evaluation and Mechanical Evolution. J Eur Ceram Soc, 41:1672–82. https://doi.org/10.1016/j.jeurceramsoc.2020.10.002

9. Dabbagh SR, Sarabi MR, Rahbarghazi R, et al., 2020, 3D-Printed Microneedles in Biomedical Applications. iScience, 24:102012. https://doi.org/10.1016/j.isci.2020.102012

10. Xenikakis I, Tzimtzimis M, Tsongas K, et al., 2019, Fabrication and Finite Element Analysis of Stereolithographic 3D Printed Microneedles for Transdermal Delivery of Model Dyes Across Human Skin In Vitro. Eur J Pharm Sci, 137:104976. https://doi.org/10.1016/j.ejps.2019.104976

11. Wang J, Goyanes A, Gaisford S, et al., 2016, Stereolithographic (SLA) 3D Printing of Oral Modified-Release Dosage Forms. Int J Pharm, 503:207–212. https://doi.org/10.1016/j.ijpharm.2016.03.016

12. Karakurt I, Aydoğdu A, Çıkrıkcı S, et al., 2020, Stereolithography (SLA) 3D Printing of Ascorbic acid Loaded Hydrogels: A Controlled Release Study. Int J Pharm, 584:119482. https://doi.org/10.1016/j.ijpharm.2020.119428

13. Chen X, Ware HO, Baker E, et al., 2017, The Development of an All-polymer-based Piezoelectric Photocurable Resin for Additive Manufacturing. Procedia CIRP, 65:157–62. https://doi.org/10.1016/j.procir.2017.04.025

14. Cheng WT, Chih YW, Yeh WT, 2007, In Situ Fabrication of Photocurable Conductive Adhesives with Silver Nano-Particles in the Absence of Capping Agent. Int J Adhes Adhes, 27:236–43. https://doi.org/10.1016/j.ijadhadh.2006.05.001

15. Sciancalepore C, Moroni F, Messori M, et al., 2017, Acrylate-Based Silver Nanocomposite by Simultaneous Polymerization-Reduction Approach via 3D Stereolithography. Compos Commun, 6:11–6. https://doi.org/10.1016/j.coco.2017.07.006

16. Scordo G, Bertana V, Scaltrito L, et al., 2019, A Novel Highly Electrically Conductive Composite Resin for Stereolithography. Mater Today Commun, 19:12–7. https://doi.org/10.1016/j.mtcomm.2018.12.017

17. Mu Q, Wang L, Dunn CK, et al., 2017 Digital Light Processing 3D Printing of Conductive Complex Structures. Addit Manuf, 18:74–83. https://doi.org/10.1016/j.addma.2017.08.011

18. Szaloki M, Gall J, Bukovinszki K, et al., 2013, Synthesis and Characterization of Cross-Linked Polymeric Nanoparticles and their Composites for Reinforcement of Photocurable Dental Resin. React Funct Polym, 73:465–73. https://doi.org/10.1016/J.REACTFUNCTPOLYM.2012.11.013

19. dos Santos MN, Opelt CV, Lafratta FH, et al., 2011, Thermal and Mechanical Properties of a Nanocomposite of a Photocurable Epoxy-Acrylate Resin and Multiwalled Carbon Nanotubes. Mater Sci Eng A, 528:4318–24. https://doi.org/10.1016/j.msea.2011.02.036

20. Zhang J, Huang D, Liu S, et al., 2019, Zirconia Toughened Hydroxyapatite Biocomposite Formed by a DLP 3D Printing Process for Potential Bone Tissue Engineering. Mater Sci Eng C, 105:110054. https://doi.org/10.1016/j.msec.2019.110054

21. Markandan K, Lai CQ, 2020, Enhanced Mechanical Properties of 3D Printed Graphene-Polymer Composite Lattices at Very Low Graphene Concentrations. Compos A Appl Sci Manuf, 129:105726. https://doi.org/10.1016/j.compositesa.2019.105726

22. Zhou X, Nowicki M, Cui H, et al., 2017, 3D Bioprinted Graphene Oxide-Incorporated Matrix for Promoting Chondrogenic Differentiation of Human Bone Marrow Mesenchymal Stem Cells. Carbon, 116:615–24. https://doi.org/10.1016/j.carbon.2017.02.049

23. Chung CM, Kim JG, Kim MS, et al., 2002, Development of a New Photocurable Composite Resin with Reduced Curing Shrinkage. Dent Mater, 18:174–8. https://doi.org/10.1016/S0109-5641(01)00039-2

24. Iqbal AA, Sakib N, Iqbal AP, et al., 2020, Graphene-Based Nanocomposites and their Fabrication, Mechanical Properties and Applications. Materialia, 12:100815. https://doi.org/10.1016/j.mtla.2020.100815

25. Azizi-Lalabadi M, Jafari SM, 2021, Bio-Nanocomposites of Graphene with Biopolymers; Fabrication, Properties, and Applications. Adv. Coll Interface Sci, 292:102416. https://doi.org/10.1016/j.cis.2021.102416

26. Li Y, Feng Z, Huang L, et al., 2019, Additive Manufacturing High Performance Graphene-Based Composites: A Review. Compos A Appl Sci Manuf, 124:105483. https://doi.org/10.1016/j.compositesa.2019.105483

27. Guo S, Lu Y, Wan X, et al., 2020, Preparation, Characterization of Highly Dispersed Reduced Graphene Oxide/Epoxy Resin and Its Application in Alkali-Activated Slag Composites. Cem Concr Compos, 105:103424. https://doi.org/10.1016/j.cemconcomp.2019.103424

28. Pour ZS, Ghaemy M, 2016, Polymer Grafted Graphene Oxide: For Improved Dispersion in Epoxy Resin and Enhancement of Mechanical Properties of Nanocomposite. Compos Sci Technol, 136:145–57. https://doi.org/10.1016/j.compscitech.2016.10.014.

29. Al-Asadi AS, Hassan QM, Abdulkader AF, et al., 2019, Formation of Graphene Nanosheets/Epoxy Resin Composite and Study Its Structural, Morphological and Nonlinear Optical Properties. Opt Mater, 89:460–467. https://doi.org/10.1016/j.optmat.2019.01.078

30. Kilic U, Sherif MM, Ozbulut OE, 2019, Tensile Properties of Graphene Nanoplatelets/Epoxy Composites Fabricated by Various Dispersion Techniques. Polym Test, 76:181–91. https://doi.org/10.1016/j.polymertesting.2019.03.028

31. Wang X, Tang F, Qi X, et al., 2019, Mechanical, Electrochemical, and Durability Behavior of Graphene Nano-Platelet Loaded Epoxy-Resin Composite Coatings. Compos B Eng, 176:107103. https://doi.org/10.1016/j.compositesb.2019.107103

32. Sánchez-Hidalgo R, Yuste-Sanchez V, Verdejo R, et al., 2018, Main Structural Features of Graphene Materials Controlling the Transport Properties of Epoxy Resin-Based Composites. Eur Polym J, 101:56–65. https://doi.org/10.1016/j.eurpolymj.2018.02.018

33. Moriche R, Prolongo SG, Sánchez M, et al., 2015, Morphological Changes on Graphene Nanoplatelets Induced during Dispersion into an Epoxy Resin by Different Methods. Compos B Eng, 72:199–205. https://doi.org/10.1016/j.compositesb.2014.12.012

34. Fang F, Ran S, Fang Z, et al., 2019, Improved Flame Resistance and Thermo-Mechanical Properties of Epoxy Resin Nanocomposites from Functionalized Graphene Oxide Via Self-Assembly in Water. Compos B Eng, 165:406–16. https://doi.org/10.1016/j.compositesb.2019.01.086

35. Kugler S, Kowalczyk K, Spychaj T, 2015, Hybrid Carbon Nanotubes/Graphene Modified Acrylic Coats. Progress Org Coat, 85:1–7. https://doi.org/10.1016/j.porgcoat.2015.02.019

36. Baig Z, Mamat O, Mustapha M, et al., 2018, Investigation of Tip Sonication Effects on Structural Quality of Graphene Nanoplatelets (GNPs) for Superior Solvent Dispersion. Ultrason Sonochem, 45:133–49. https://doi.org/10.1016/j.ultsonch.2018.03.007

37. Lin D, Jin S, Zhang F, et al., 2015, 3D Stereolithography Printing of Graphene Oxide Reinforced Complex Architectures. Nanotechnology, 26:434003. https://doi.org/10.1088/0957-4484/26/43/434003

38. Feng Z, Li Y, Hao L, et al., 2019, Graphene-Reinforced Biodegradable Resin Composites for Stereolithographic 3D Printing of Bone Structure Scaffolds. J Nanomater, 2019:1–13. https://doi.org/10.1155/2019/9710264

39. Manapat JZ, Mangadlao JD, Tiu BD, et al., 2017, High-Strength Stereolithographic 3D Printed Nanocomposites: Graphene Oxide Metastability. ACS Appl Mater Interface, 9:10085–93. https://doi.org/10.1021/acsami.6b16174

40. Lipovka A, Rodriguez R, Bolbasov E, et al., 2020, Time-Stable Wetting Effect of Plasma-Treated Biodegradable Scaffolds Functionalized with Graphene Oxide. Surf Coat Technol, 388:125560. https://doi.org/10.1016/j.surfcoat.2020.125560

41. Lim SM, Shin BS, Kim K, 2017, Characterization of Products Using Additive Manufacturing with Graphene/Photopolymer- Resin Nano-Fluid. J Nanosci Nanotechnol, 17:5492–55. https://doi.org/10.1166/jnn.2017.14159

42. Moriche R, Artigas J, Reigosa L, et al., 2019, Modifications Induced in Photocuring of Bis-GMA/TEGDMA by the Addition of Graphene Nanoplatelets for 3D Printable Electrically Conductive Nanocomposites. Compos Sci Technol, 184:107876. https://doi.org/10.1016/j.compscitech.2019.107876

43. Weng Z, Zhou Y, Lin W, et al., 2016, Structure-Property Relationship of Nano Enhanced Stereolithography Resin for Desktop SLA 3D Printer. Compos A Appl Sci Manuf, 88:234–42. https://doi.org/10.1016/j.compositesa.2016.05.035

44. Paz E, Ballesteros Y, Abenojar J, et al., 2019, Graphene Oxide and Graphene Reinforced PMMA Bone Cements: Evaluation of Thermal Properties and Biocompatibility. Materials, 12:3146. https://doi.org/10.3390/ma12193146. 

45. Abenojar J, Del Real JC, Ballesteros Y, et al., 2018, Kinetics of Curing Process in Carbon/Epoxy Nano-Composites. IOP Conf Ser Mater Sci Eng, 369:012011. https://doi.org/10.1088/1757-899X/369/1/012011

46. Liang H, Bu Y, Zhang Y, et al., 2015, Graphene Oxide as Efficient High-Concentration Formaldehyde Scavenger and Reutilization in Supercapacitor. J Coll Interface Sci, 444:109–14. https://doi.org/10.1016/j.jcis.2014.12.063

47. Xia W, Xue H, Wang J, et al., 2016, Functionlized Graphene Serving as Free Radical Scavenger and Corrosion Protection in Gamma-Irradiated Epoxy Composites. Carbon, 101:315–23. https://doi.org/10.1016/j.carbon.2016.02.004

48. Martin-Gallego M, Hernández M, Lorenzo V, et al., 2012, Cationic Photocured Epoxy Nanocomposites Filled with Different Carbon Fillers. Polymer, 53:1831–8. https://doi.org/10.1016/j.polymer.2012.02.054

49. Paz E, Forriol F, del Real JC, et al., 2017, Graphene Oxide Versus Graphene for Optimisation of PMMA Bone Cement for Orthopaedic Applications. Mater Sci Eng C, 77:1003–11. https://doi.org/10.1016/j.msec.2017.03.269

50. Courtecuisse F, Karasu F, Allonas X, et al., 2016, Confocal Raman Microscopy Study of Several Factors Known to Influence the Oxygen Inhibition of Acrylate Photopolymerization Under LED. Progress Org Coat, 92:1–7. https://doi.org/10.1016/j.porgcoat.2015.11.020

51. Zhou ZX, Buchanan F, Lennon A, et al., 2014, Investigating Approaches for Three-Dimensional Printing of Hydroxyapatite Scaffolds for Bone Regeneration. Key Eng Mater, 631:306–11. https://doi.org/10.4028/www.scientific.net/kem.631.306

52. Hakvoort G, van Reijen L, 1985, Measurement of the Thermal Conductivity of Solid Substances by DSC. Thermochim Acta, 93:317–20.

53. Sousa I, Mendes A, Pereira RF, et al., 2014, Collagen Surface Modified Poly (ε-Caprolactone) Scaffolds with Improved Hydrophilicity and Cell Adhesion Properties. Mater Lett, 134:263–7. https://doi.org/10.1016/j.matlet.2014.06.132

54. Merkel TC, Freeman BD, Spontak RJ, et al., 2002, Ultrapermeable, Reverse-Selective Nanocomposite Membranes. Science, 296:519–22. https://doi.org/10.1126/science.1069580

55. Vicard C, de Almeida O, Cantarel A, et al., 2017, Experimental Study of Polymerization and Crystallization Kinetics of Polyamide 6 Obtained by Anionic Ring Opening Polymerization of ε-Caprolactam. Polymer, 132:88–97. https://doi.org/10.1016/j.polymer.2017.10.039

56. Tudorachi N, Bunia I. 2015, Synthesis and Thermal Investigation by TG-FTIR-MS Analysis of Some Functionalized Acrylic Copolymers and Magnetic Composites with Fe3O4. J Anal Appl Pyrolysis, 116:190–201. https://doi.org/10.1016/j.jaap.2015.09.010

57. Ortiz-Herrero L, Cardaba I, Setien S, et al., 2019, OPLS Multivariate Regression of FTIR-ATR Spectra of Acrylic Paints for Age Estimation in Contemporary Artworks. Talanta, 205:120114. https://doi.org/10.1016/j.talanta.2019.120114

58. Chiappone A, Roppolo I, Naretto E, et al., 2017, Study of Graphene Oxide-Based 3D Printable Composites: Effect of the In Situ Reduction. Compos B Eng, 124:9–15. https://doi.org/10.1016/j.compositesb.2017.05.049

59. García E, Núñez PJ, Chacón JM, et al., 2020, Comparative Study of Geometric Properties of Unreinforced PLA and PLA-Graphene Composite Materials Applied to Additive Manufacturing Using FFF Technology. Polym Test, 91:106860. https://doi.org/10.1016/j.polymertesting.2020.106860

60. Chouhan A, Mungse HP, Khatri OP, 2020, Surface Chemistry of Graphene and Graphene Oxide: A Versatile Route for their Dispersion and Tribological Applications. Adv Coll Interface Sci, 283:102215. https://doi.org/10.1016/j.cis.2020.102215

61. Miller SG, Bauer JL, Maryanski MJ, et al., 2010, Characterization of Epoxy Functionalized Graphite Nanoparticles and the Physical Properties of Epoxy Matrix Nanocomposites. Compos Sci Technol, 70:1120–5. https://doi.org/10.1016/j.compscitech.2010.02.023

62. Jain S, Goossens JG, Peters GW, et al., 2008, Strong Decrease in Viscosity of Nanoparticle-Filled Polymer Melts through Selective Adsorption. Soft Matter, 4:1848–54. https://doi.org/10.1039/b802905a

63. Mackay M., Dao T., Tuteja A, et al., 2003, Nanoscale Effects Leading to Non-Einstein-Like Decrease in Viscosity. Nat Mater, 2:762–66.

64. Rafiee M, Nitzsche F, Laliberte J, et al., 2019, Thermal Properties of Doubly Reinforced Fiberglass/Epoxy Composites with Graphene Nanoplatelets, Graphene Oxide and Reduced-Graphene Oxide. Compos B Eng, 164:1–9. https://doi.org/10.1016/j.compositesb.2018.11.051

65. Sun Y, Tang B, Huang W, et al., 2016, Preparation of Graphene Modified Epoxy Resin with High Thermal Conductivity by Optimizing the Morphology of Filler. Appl Therm Eng, 103:892–900. https://doi.org/10.1016/j.applthermaleng.2016.05.005

66. Aradhana R, Mohanty S, Nayak SK, 2018, Comparison of Mechanical, Electrical and Thermal Properties in Graphene Oxide and Reduced Graphene Oxide Filled Epoxy Nanocomposite Adhesives. Polymer, 141:109–23. https://doi.org/10.1016/j.polymer.2018.03.005

67. Huang T, Zeng X, Yao Y, et al., 2016, Boron nitride@graphene Oxide Hybrids for Epoxy Composites with Enhanced Thermal Conductivity. RSC Adv, 6:35847–54. https://doi.org/10.1039/c5ra27315c

68. Wang J, Li JJ, Weng GJ, et al., 2020, The Effects of Temperature and Alignment State of Nanofillers on the Thermal Conductivity of Both Metal and Nonmetal Based Graphene Nanocomposites. Acta Mater, 185:461–73. https://doi.org/10.1016/j.actamat.2019.12.032

69. Xue G, Zhong J, Gao S, et al., 2016, Correlation between the Free Volume and Thermal Conductivity of Porous Poly (Vinyl Alcohol)/Reduced Graphene Oxide Composites Studied by Positron Spectroscopy. Carbon, 96:871–8. https://doi.org/10.1016/j.carbon.2015.10.041

70. Li J, Yu Y, Chen D, et al., 2020, Hydrophilic Graphene Aerogel Anodes Enhance the Performance of Microbial Electrochemical Systems. Bioresour Technol, 304:122907. https://doi.org/10.1016/j.biortech.2020.122907

71. Hou Y, Wang W, Bártolo P, 2020, Investigating the Effect of Carbon Nanomaterials Reinforcing Poly (ε-Caprolactone) Printed Scaffolds for Bone Repair Applications. Int J Bioprint, 6:1–9. https://doi.org/10.18063/ijb.v6i2.266

72. Yang S, Sha S, Lu H, et al., 2021, Graphene Oxide and Reduced Graphene Oxide Coated Cotton Fabrics with Opposite Wettability for Continuous Oil/Water Separation. Sep Purif Technol, 259:118095. https://doi.org/10.1016/j.seppur.2020.118095

Share
Back to top
International Journal of Bioprinting, Electronic ISSN: 2424-8002 Print ISSN: 2424-7723, Published by AccScience Publishing