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Poly(methyl methacrylate)-silica-calcium phosphate coatings for the protection of Ti6Al4V alloy

  • Invited Paper: Sol-gel and hybrid materials with surface modification for applications
  • Published:
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Abstract

Poly(methyl methacrylate) (PMMA)-silica coatings modified with calcium phosphates (CaPs) in the form of hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) have been developed to improve the corrosion resistance and bioactivity of Ti6Al4V titanium alloys, applied in medical and dental implants. PMMA-silica hybrids containing 1000 ppm HA or β-TCP were prepared by combining the sol-gel reactions of tetraethylorthosilicate (TEOS) with the radical polymerization of methyl methacrylate (MMA) and 3-methacryloxypropyl trimethoxysilane (MPTS), used as molecular coupling agent. Bi-layer coatings about 15 μm thick, deposited by immersion on Ti6Al4V, are homogeneous, defect-free, and exhibit strong adhesion to the substrate (>14 MPa). The addition of HA and β-TCP led to a slight increase in thermal stability, without affecting the structural integrity of the highly crosslinked PMMA-silica matrix. The greater hydrophilicity and surface roughness of coatings containing HA and β-TCP are associated with the size and chemical composition of CaPs, necessary for effective osteointegration. The modified coatings showed high anti-corrosion efficiency with low-frequency impedance modulus values of up to 73 GΩ cm2, remaining stable after 150 days of exposure to simulated body fluid (SBF) solution.

Graphical Abstract

To protect the Ti6Al4V alloy used for orthopedic and orthodontic implants, poly(methyl methacrylate) (PMMA)-silica-calcium phosphates coatings were obtained by the addition of bioactive additives such as β-tricalcium phosphate (β-TCP) and hydroxyapatite (HA). Bi-layer coatings of about 15 µm thickness formed by a calcium phosphate-modified surface layer and an unmodified barrier base layer, were deposited by immersion on the Ti6Al4V substrates. The high corrosion resistance and long durability of the coatings in simulated body fluid (SBF) solution are related to a highly reticulated nanostructure of uniformly distributed silica nanodomains covalently conjugated with the polymer matrix.

Highlights

  • Biocompatible PMMA-silica/PMMA-silica-calcium phosphate coatings for protection of Ti6Al4V alloy.

  • Calcium phosphate addition preserves the integrity of the highly cross-linked PMMA-silica hybrid.

  • Adherent bilayer coating provides efficient and durable corrosion protection for the Ti6Al4V alloy.

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Acknowledgements

We are thankful to the Brazilian funding agencies: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) [grant numbers 309419/2020-4, 142305/2020-0, 304410/2022-5] and Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) [grant number: 2019/13871-6].

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  1. São Paulo State University (UNESP), Institute of Chemistry, 14800-060, Araraquara/SP, Brazil

    Mayara Carla Uvida, Sandra Helena Pulcinelli, Celso Valentim Santilli & Peter Hammer

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Correspondence to Mayara Carla Uvida.

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Uvida, M.C., Pulcinelli, S.H., Santilli, C.V. et al. Poly(methyl methacrylate)-silica-calcium phosphate coatings for the protection of Ti6Al4V alloy. J Sol-Gel Sci Technol 106, 627–638 (2023). https://doi.org/10.1007/s10971-023-06111-z

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