Structural, mechanical and in vitro studies on pulsed laser deposition of hydroxyapatite on additive manufactured polyamide substrate

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Hariharan Kuppuswamy, Arumaikkannu Ganesan


Additive manufacturing (AM) is an emerging field that merges engineering and life sciences to produce components that can effectively act as a replacement in the human body. This AM encompasses biofabrication using cells, biological or biomaterials as building blocks to fabricate biological and bio-application oriented substance, device and therapeutic products through a broad range of engineering and biological processes. Furthermore, bioactive coating on BAM surface facilitates biological fixation between the prosthesis and the hard tissue which increases the long term stability and integrity of the implant. In this paper, hydroxyapatite (HA) powder was coated over AM polyamide substrate using pulsed laser deposition. Coating morphology was characterised using scanning electron microscope (SEM) analysis and observed that the coating was dominated by the presence of particle droplet with different sizes. Compounds like tricalcium phosphate and a few amorphous calcium phosphates were found along with HA which was confirmed by X-ray diffraction (XRD) analysis. Fourier transform infrared spectroscopy (FTIR) techniques shows the presence of phosphate and carbonate groups in the HA structure. Nano-indentation and pull-out test reveals that the layer was strong enough and withstands higher load before it peels off. In vitro analysis was evaluated with human osteosarcoma MG-63 cells with respect to the cell viability and results shows that the good viability was observed on coated surface due to combinational effect of Ca2+ and PO43− ions. The multitude of characterisation conducted on the coating has established that coating polyamide with HA results in a positive combination for an implant.


bioadditive manufacturing; hydroxyapatite; polyamide; pulsed laser deposition; characterisation; cell line studies

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William D F, 1999, The Williams Dictionary of Biomaterials, Liverpool University Press, Liverpool.

Ramakrishna S, Mayer J, Wintermantel E, et al., 2001, Biomedical applications of polymer-composite materials: A review. Composites Science and Technology, vol.61(9): 1189–1224.

Black J, 2005, Biological Performance of Materials: Fundamentals of Biocompatibility, CRC Press, New York.

Narayan R (ed), 2012, ASM Handbook, Volume 23: Materials for Medical Devices, ASM International, Ohio.

Tyndyk M, Lohfeld S, Barron V, et al., 2006, Assessment of SLS fabricated scaffolds for skeletal reconstruction in the spine. Journal of Biomechanics, vol.39(Suppl 1): S216.

Asri R I, Harun W S, Hassan M A, et al., 2016, A review of hydroxyapatite-based coating techniques: sol–gel and electrochemical depositions on biocompatible metals. Journal of the Mechanical Behavior of Biomedical Materials, vol.57: 95–108.

Nishikawa H, Hasegawa T, Miyake A, et al., 2016, Relationship between the Ca/P ratio of hydroxyapatite thin films and the spatial energy distribution of the ablation laser in pulsed laser deposition. Materials Letters, vol.165: 95–98.

Bourne R B, Chesworth B M, Davis A M, et al., 2010, Patient satisfaction after total knee arthroplasty: Who is satisfied and who is not? Clinical Orthopaedics and Related Research, vol.468(1): 57–63.

Mahoney O M and Kinsey T, 2010, Overhang of the femoral component in total knee arthroplasty: Risk factors and clinical consequences. The Journal of Bone & Joint Surgery, vol.92(5): 1115–1121.

D’Urso P S, Effeney D J, Earwaker W J, et al., 2000, Custom cranioplasty using stereolithography and acrylic. British Journal of Plastic Surgery, vol.53(3): 200–204.

Nair L S and Laurencin C T, 2007, Biodegradable polymers as biomaterials. Progress in Polymer Science, vol.32(8): 762–798.

Nagase Y and Horiguchi K, 2011, Biocompatible polyamides and polyurethanes containing phospholipid moiety, in Fazel R (ed), Biomedical Engineering — Frontiers and Challenges, InTech.

Cerardi A, Caneri M, Meneghello R, et al., 2013, Mechanical characterization of polyamide cellular structures fabricated using selective laser sintering technolo-gies. Materials & Design, vol.46: 910–915.

Rashia Begum S and Arumaikkannu G, 2013, Design, analysis and fabrication of customised bone scaffold using RP technology. International Journal of Computer Applications in Technology, vol.47(4): 364–369.

Shtilman M I, 2003, New Concepts in Polymer Science. Polymeric Biomaterials Part 1: Polymer Implants. CRC Press, Boca Raton, FL, 52.

Chandra R and Rustgi R, 1998, Biodegradable polymers. Progress in Polymer Science, vol.23(7): 1273–1335.

Jagur-Grodzinski J, 1999, Biomedical application of functional polymers. Reactive and Functional Polymers, vol.39(2): 99–138.

Salmoria G V, Leite J L, Ahrens C H, et al., 2007, Rapid manufacturing of PA/HDPE blend specimens by selective laser sintering: microstructural characterization. Polymer Testing, vol.26(3): 361–368.

Salmoria G V, Leite J L, Paggi R A, et al., 2008, Selective laser sintering of PA12/HDPE blends: effect of components on elastic/plastic behavior. Polymer Testing, vol.27(6): 654–659.

Nouri A and Wen C, 2015, Introduction to surface coating and modification for metallic biomaterials. Surface Coating and Modification of Metallic Biomaterials: 3–60.

Parekh R B, Shetty O and Tabassum R, 2012, Surface modifications for endosseous dental implants. International Journal of Oral Implantology & Clinical Re-search, vol.3(3): 116–121.

Bosco R, Van Den Beucken J, Leeuwenburgh S, et al., 2012, Surface engineering for bone implants: A trend from passive to active surfaces. Coatings, vol.2(3): 95–119.

Oyane A, Wang X, Sogo Y, et al., 2012, Calcium phosphate composite layers for surface-mediated gene transfer. Acta Biomaterialia, vol.8(6): 2034–2046.

Bosco R, Edreira E R U, Wolke J G C, et al., 2013, Instructive coatings for biological guidance of bone implants. Surface and Coatings Technology, vol.233: 91–98.

Surmenev R A, 2012, A review of plasma-assisted methods for calcium phosphate-based coatings fabrication. Surface and Coatings Technology, vol.206(8–9): 2035– 2056.

Rautray T R, Narayanan R, Kwon T Y, et al., 2010, Surface modification of titanium and titanium alloys by ion implantation. Journal of Biomedical Materials Re-search Part B: Applied Biomaterials, vol.93B(2): 581–591.

Rahmany M B and Van Dyke M, 2013, Biomimetic approaches to modulate cellular adhesion in biomaterials: A review. Acta Biomaterialia, vol.9(3): 5431–5437.

Shapira L and Halabi A, 2009, Behavior of two osteoblast-like cell lines cultured on machined or rough titanium surfaces. Clinical Oral Implants Research, vol.20(1): 50–55.

Vahabzadeh S, Roy M, Bandyopadhyay A, et al., 2015, Phase stability and biological property evaluation of plasma sprayed hydroxyapatite coatings for orthopedic and dental applications. Acta Biomaterialia, vol.17: 47–55.

Oguchi H, Ishikawa K, Ojima S, et al., 1992, Evaluation of a high-velocity flame-spraying technique for hydroxyapatite. Biomaterials, vol.13(7): 471–477.

Choi J M, Kim H E and Lee I S, 2000, Ion-beam-assisted deposition (IBAD) of hydroxyapatite coating layer on Ti-based metal substrate. Biomaterials, vol.21(5): 469–473.

Moskalewicz T, Kot M, Seuss S, et al., 2015, Electrophoretic deposition and characterization of HA/chitosan nanocomposite coatings on Ti6Al7Nb alloy. Metals and Materials International, vol.21(1): 96–103.

Yang Y, Kim K H and Ong J L, 2005, A review on calcium phosphate coatings produced using a sputtering process — an alternative to plasma spraying. Biomate-rials, vol.26(3): 327–337.

Deplaine H, Lebourg M, Ripalda P, et al., 2013, Bio-mimetic hydroxyapatite coating on pore walls improves osteointegration of poly(Llactic acid) scaffolds. Journal of Biomedical Materials Research Part B: Applied Biomaterials, vol.101B(1): 173–186.

Socol G, Torricelli P, Bracci B, et al., 2004, Biocompatible nanocrystalline octacalcium phosphate thin films obtained by pulsed laser deposition. Biomaterials, vol.25(13): 2539–2545.

Tang P H, Song R G, Chai G Z, et al., 2012, Microstructure and nanoindentation hardness of TiN/AlN multilayer films prepared by pulsed laser deposition. Surface Engineering, vol.28(3): 165–170.

Lo W J, Grant D M, Ball M D, et al., 2000, Physical, chemical, and biological characterization of pulsed laser deposited and plasma sputtered hydroxyapatite thin films on titanium alloy. Journal of Biomedical Materials Research, vol.50(4): 536–545.<536::AID-JBM9>3.0.CO;2-U

Junker R, Dimakis A, Thoneick M, et al., 2009, Effects of implant surface coatings and composition on bone integration: A systematic review. Clinical Oral Implants Research, vol.20(S4): 185–206.

McBeath R, Pirone D M, Nelson C M, et al., 2004, Cell shape, cytoskeletal tension, and RhoA regulate stem cell lineage commitment. Developmental Cell, vol.6(4): 483– 495.

Engler A J, Sen S, Sweeney H L, et al., 2006, Matrix elasticity directs stem cell lineage specification. Cell, vol.126(4): 677–689.

Dalby M J, Gadegaard N, Tare R, et al., 2007, The control of human mesenchymal cell differentiation using nanoscale symmetry and disorder, Nature Materials, vol.6(12): 997–1003.

Schmidt D R, Waldeck H and Kao W J, 2009, Protein adsorption to biomaterials, in Puleo D A and Bizios R (eds), Biological Interactions on Materials Surfaces, Springer, New York, 1–18.

Riss T L, Moravec R A, Niles A L, et al., 2004, Cell viability assays, in Sittampalam G S, Coussens N P, Nelson H, et al. (eds), Assay Guidance Manual, Bethesda (MD): Eli Lilly & Company and the National Center for Advancing Translational Sciences, viewed April 3, 2016,

Buehler M J, 2006, Nature designs tough collagen: Explaining the nanostructure of collagen fibrils. Proceedings of the National Academy of Sciences of the United States of America, vol.103(33): 12285–12290.

EOSINT, Plastic laser-sintering for direct manufacturing. EOS GmbH, Technical Data. Birmingham — UK, 2002. Fine Polyamide PA 2200 for EOSINT P, Material Data Sheet.

Wong K V and Hernandez A, 2012, A review of additive manufacturing. ISRN Mechanical Engineering, vol.2012(208760): 1–10.

Salmoria G V, Leite J L and Paggi R A, 2009, The microstructural characterization of PA6/PA12 blend specimens fabricated by selective laser sintering. Polymer Testing, vol.28(7): 746–751.

Liu Y, Hou D and Wang G, 2004, A simple wet chemical synthesis and characterization of hydroxyapatite nano-rods. Materials Chemistry and Physics, vol.86(1): 69–73.

Khandelwal H, Singh G, Agrawal K, et al., 2013, Characterization of hydroxyapatite coating by pulse laser deposition technique on stainless steel 316 L by varying laser energy. Applied Surface Science, vol.265: 30–35.

Rajesh P, Muraleedharan C V, Komath M, et al., 2011, Laser surface modification of titanium substrate for pulsed laser deposition of highly adherent hydroxyapa-tite. Journal of Materials Science: Materials in Medi-cine, vol.22(7): 1671–1679.

Gittens R A, McLachlan T, Olivares-Navarrete R, et al., 2011, The effects of combined micron-submicron-scale surface roughness and nanoscale features on cell proli-feration and differentiation. Biomaterials, vol.32(13): 3395–3403.

Wang G and Zreiqat H, 2010, Functional coatings or films for hard-tissue applications. Materials, vol.3(7): 3994–4050.

Guerrini L M, Branciforti M C, Canova T, et al., 2009, Electrospinning and characterization of polyamide 66 nanofibers with different molecular weights. Materials Research, vol.12(2): 181–190.



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