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Surface Modification of Medical Implants

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A special issue of Coatings (ISSN 2079-6412). This special issue belongs to the section "Bioactive Coatings and Biointerfaces".

Deadline for manuscript submissions: closed (30 November 2022) | Viewed by 25729

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Dr. Alina Vladescu

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National Institute of Research and Development for Optoelectronics-INOE 2000, 077125 Magurele, Romania
Interests: biomaterials; coatings; deposition PVD techniques; bioactivity; corrosion; degradation
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Dear Colleagues,

The mechanism of implant failure is nowadays the target of intensive research, aiming to increase implant’s service life, since bone fixation devices and artificial joints comprise 44% of all medical devices. The results obtained world-wide in the last 15 years have demonstrated that the most important causes of artificial joint loosening are due to implant infection, osseointegration, degradation, friction, and abrasive wear. Thus, many efforts have been directed towards finding a solution to obtain a new implant with good mechanical, osseoconductive, and antibacterial properties, and good resistance to wear and corrosion (low friction coefficient and wear rate in the solution specific to the human body). One of prospective ways is to induce the surface modification of common medical implants in order to obtain the desired properties for clinical applications. Currently, several techniques have been developed for preparing biocompatible coatings, such as plasma spray, sol–gel, micro-arc oxidation, electrodeposition, anodization, plasma electrolytic oxidation, magnetron sputtering, and pulsed laser deposition, etc. The main goal of this Special Issue is to present the latest developments in the field of the surface modification of medical implants for enhancing the specific functionality in human aggressive media.

In particular, the topics of interest include, but are not limited to:

Surface science of bioactive coatings
Deposition and growth of biocompatible coatings
Coatings-based polymers
Surface modification by directed energy deposition (lasers, ion, or electron beams) or other techniques such as plasmas
Friction performance, corrosion, and wear resistance of coated load-bearing implants and/or dental implants

Dr. Alina Vladescu
Guest Editor

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Published Papers (10 papers)

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25 pages, 12875 KiB

Open AccessArticle

Influence of Magnesium Content on the Physico-Chemical Properties of Hydroxyapatite Electrochemically Deposited on a Nanostructured Titanium Surface

by Cosmin Mihai Cotrut, Elena Ungureanu, Ionut Cornel Ionescu, Raluca Ioana Zamfir, Adrian Emil Kiss, Anca Constantina Parau, Alina Vladescu, Diana Maria Vranceanu and Adriana Saceleanu

Coatings 2022, 12(8), 1097; https://doi.org/10.3390/coatings12081097 - 2 Aug 2022

Cited by 9 | Viewed by 2919

Abstract

The aim of this research was to obtain hydroxyapatite (HAp)-based coatings doped with different concentrations of Mg on a Ti nanostructured surface through electrochemical techniques and to evaluate the influence of Mg content on the properties of HAp. The undoped and doped HAp-based coatings were electrochemically deposited in galvanostatic pulsed mode on titania nanotubes with a diameter of ~72 nm, being designed to enhance the adhesion of the HAp coatings to the Ti substrate. The obtained materials were investigated by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD), and Fourier-Transform Infra-Red spectroscopy (FTIR). The adhesion of the coatings to the substrate was also evaluated with the help of the “tape-test” and the micro-scratch test. The morphology (SEM) of all the coatings is made of very thin and narrow ribbon-like crystals, with some alterations with respect to the Mg amount in the coatings. Thus, a concentration of 1 mM of Mg in the electrolyte leads to wider and thicker ribbon-like crystals, while a concentration of 1.5 mM in the electrolyte generated a morphology that resembles the undoped HAp. Both phase composition (XRD) and chemical bonds (FTIR) analysis proved the formation of HAp in all coatings. Moreover, according to XRD, all coatings have a strong orientation toward the (002) plane. Irrespective of the Mg content, all coatings registered an average roughness between approx. 500 and 600 nm, while the coating thickness increased after addition of Mg, from a value of 9.6 μm, for the undoped HAp, to 11.3 μm and ~13.7 μm for H/Mg1 and H/Mg2, respectively. In terms of adhesion, it was shown that the coatings a H/Mg2 had a poorer adhesion when compared to H/Mg1 and the undoped HAp (H), which registered similar adhesion, indicating that a concentration of 1.5 mM of Mg in the electrolyte reduces the adhesion of the Hap-based coatings to the nanostructured surface. The obtained results indicated that Mg concentrations up to 1 mM in the electrolyte can enhance the properties of HAp-based coatings electrochemically deposited on a nanostructured surface, while even a slightly higher concentration of 1.5 mM can negatively impact the characteristics of HAp coatings. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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16 pages, 6534 KiB

Open AccessArticle

Electrochemical Surface Biofunctionalization of Titanium through Growth of TiO₂ Nanotubes and Deposition of Zn Doped Hydroxyapatite

by Diana Maria Vranceanu, Elena Ungureanu, Ionut Cornel Ionescu, Anca Constantina Parau, Adrian Emil Kiss, Alina Vladescu and Cosmin Mihai Cotrut

Coatings 2022, 12(1), 69; https://doi.org/10.3390/coatings12010069 - 7 Jan 2022

Cited by 21 | Viewed by 3384

Abstract

The current research aim is to biofunctionalize pure titanium (Ti, grade IV) substrate with titania nanotubes and Zn doped hydroxyapatite-based coatings by applying a duplex electrochemical treatment, and to evaluate the influence of Zn content on the physico-chemical properties of hydroxyapatite (HAp). The obtained nanostructured surfaces were covered with HAp-based coatings doped with Zn in different concentrations by electrochemical deposition in pulsed galvanostatic mode. The obtained surfaces were characterized in terms of morphology, elemental and phasic composition, chemical bonds, roughness, and adhesion. The nanostructured surface consisted of titania nanotubes (NT), aligned, vertically oriented, and hollow, with an inner diameter of ~70 nm. X-ray Diffraction (XRD) analysis showed that the nanostructured surface consists of an anatase phase and some rutile peaks as a secondary phase. The morphology of all coatings consisted of ribbon like-crystals, and by increasing the Zn content the coating became denser due to the decrement of the crystals’ dimensions. The elemental and phase compositions evidenced that HAp was successfully doped with Zn through the pulsed galvanostatic method on the Ti nanostructured surfaces. Fourier Transform Infrared spectroscopy (FTIR) and XRD analysis confirmed the presence of HAp in all coatings, while the adhesion test showed that the addition of a high quantity leads to some delamination. Based on the obtained results, it can be said that the addition of Zn enhances the properties of HAp, and through proper experimental design, the concentration of Zn can be modulated to achieve coatings with tunable features. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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25 pages, 42494 KiB

Open AccessArticle

Improved Adsorption of the Antimicrobial Agent Poly (Hexamethylene) Biguanide on Ti-Al-V Alloys by NaOH Treatment and Impact of Mass Coverage and Contamination on Cytocompatibility

by Paula Zwicker, Norman Geist, Elisabeth Göbler, Martin Kulke, Thomas Schmidt, Melanie Hornschuh, Ulrich Lembke, Cornelia Prinz, Mihaela Delcea, Axel Kramer and Gerald Müller

Coatings 2021, 11(9), 1118; https://doi.org/10.3390/coatings11091118 - 15 Sep 2021

Cited by 3 | Viewed by 2978

Abstract

Unlike the native surface of the implant material (Ti6Al4V), oxidation with H₂O₂ leads to increased binding of the effective antimicrobial agent poly(hexamethylene) biguanide [PHMB]. However, treating with NaOH instead results in an even higher PHMB mass coverage. After oxidation with H₂O₂, strong differences in the PHMB adsorption capability between polished and corundum-blasted surfaces appear, indicating a roughness dependence. After NaOH treatment, no such effect was observed. The wetting properties of specimens treated with either H₂O₂ or NaOH prior to PHMB exposure clearly varied. To unravel the nature of this interaction, widespread in silico and in vitro experiments were performed. Methods: By X-ray photoelectron spectroscopy, scanning electron microscopy, water contact angle measurements and MD simulations, we characterized the interplay between the polycationic antimicrobial agent and the implant surface. A theoretical model for PHMB micelles is tested for its wetting properties and compared to carbon contaminated TiO₂. In addition, quantitation of anionic functional group equivalents, the binding properties of PHMB with blocked amino end-group, and the ability to bind chlorhexidine digluconate (CHG) were investigated. Ultimately, the capability of osteoblasts to build calcium apatite, and the activity of alkaline phosphatase on PHMB coated specimens, were determined. Results: Simulated water contact angles on carbon contaminated TiO₂ surfaces and PHMB micelle models reveal little influence of PHMB on the wetting properties and point out the major influence of remaining and recovering contamination from ambient air. Testing PHMB adsorption beyond the critical micelle concentration and subsequent staining reveals an island-like pattern with H₂O₂ as compared to an evenly modified surface with NaOH. Both CHG and PHMB, with blocked amino end groups, were adsorbed on the treated surfaces, thus negating the significant influence of PHMB’s terminal groups. The ability of osteoblasts to produce calcium apatite and alkaline phosphatase is not negatively impaired for PHMB mass coverages up to 8 μg/specimen. Conclusion: Differences in PHMB adsorption are triggered by the number of anionic groups and carbon contaminants, both of which depend on the specimen pre-treatment. With more PHMB covering, the implant surface is protected against the capture of new contamination from the ambient air, thus building a robust antimicrobial and biocompatible surface coating. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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23 pages, 6708 KiB

Open AccessArticle

Zn-Doped CaP-Based Coatings on Ti–6Al–4V and Ti–6Al–7Nb Alloys Prepared by Magnetron Sputtering: Controllable Biodegradation, Bacteriostatic, and Osteogenic Activities

by Konstantin A. Prosolov, Dmitrii V. Mitrichenko, Aleksandr B. Prosolov, Olga O. Nikolaeva, Vladimir V. Lastovka, Olga A. Belyavskaya, Valentina A. Chebodaeva, Ivan A. Glukhov, Larisa S. Litvinova, Valeria V. Shupletsova, Olga G. Khaziakhmatova, Vladimir V. Malashchenko, Kristina A. Yurova, Egor O. Shunkin, Maxim A. Fedorov, Andrei R. Komkov, Vladimir V. Pavlenko, Ilya I. Anisenya, Yurii P. Sharkeev, Alina Vladescu and Igor A. Khlusov Show full author list Hide full author list

Coatings 2021, 11(7), 809; https://doi.org/10.3390/coatings11070809 - 3 Jul 2021

Cited by 20 | Viewed by 4174

Abstract

New TiNb-based alloys, such as Ti–6Al–7Nb, are currently being studied around the world as an alternative to other Ti alloys, e.g., instead of Ti–6Al–4V. We conducted a pilot study where thin (approximately 1.2 micron) CaP coatings containing low doses of Zn²⁺ (0.4–0.8 wt.%) were prepared by the radio frequency magnetron sputtering (RFMS) of Zn-hydroxyapatite (HA) target on Ti–6Al–4V and Ti–6Al–7Nb substrates and investigated their physicochemical properties, in vitro solubility, cytotoxicity, and antibacterial and osteogenic activities. The thickness of the obtained coatings was approximately 1.2–1.3 microns. Zn substitution did not result in roughness or structural or surface changes in the amorphous CaP coatings. The distributions of Ca, P, and Zn were homogeneous across the film thickness as shown by the EDX mapping of these elements. Zn doping of CaP coatings on both types of Ti-based alloys statistically influenced the results of the scratch-test. However, obtained values are satisfactory to use Zn-CaP coatings on biomedical implants. Increased Zn²⁺ release vs. tapered output of Ca and phosphate ions occurred during 5 weeks of an in vitro immersion test in 0.9% NaCl solution. Ti–6Al–7Nb alloy, unlike Ti–6Al–4V, promoted more linear biodegradation of CaP coatings in vitro. As a result, CaP-based surfaces on Ti–6Al–7Nb, compared with on Ti–6Al–4V alloy, augmented the total areas of Alizarin red staining in a 21-day culture of human adipose-derived mesenchymal stem cells in a statistically significant manner. Moreover, Zn–CaP coatings statistically reduced leukemic Jurkat T cell survival within 48 h of in vitro culture. Along with the higher solubility of the Zn–CaP surface, a greater reduction (4- to 5.5-fold) in Staphylococcus aureus growth was observed in vitro when 7-day extracts of the coatings were added into the microbial culture. Hence, Zn–CaP-coated Ti–6Al–7Nb alloy with controllable biodegradation as prepared by RFMS is a prospective material suitable for bone applications in cases where there is a risk of bacterial contamination with severe consequences, for example, in leukemic patients. Further research is needed to closely investigate the mechanical features and pathways of their solubility and antimicrobial, antitumor, and osteogenic activities. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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15 pages, 5025 KiB

Open AccessArticle

Tunable Microstructure and Morphology of the Self-Assembly Hydroxyapatite Coatings on ZK60 Magnesium Alloy Substrates Using Hydrothermal Methods

by Taolei Wang, Chao Lin, Dan Batalu, Jingzhou Hu and Wei Lu

Coatings 2021, 11(1), 8; https://doi.org/10.3390/coatings11010008 - 24 Dec 2020

Cited by 9 | Viewed by 2639

Abstract

Hydroxyapatite coatings have been widely used to improve the corrosion resistance of biodegradable magnesium alloys. In this paper, in order to manufacture the ideal hydroxyapatite (HA) coating on the ZK60 magnesium substrate by hydrothermal method, formation mechanism of enhanced hydroxyapatite (HA) coatings, influence of pH values of the precursor solution on the HA morphology, corrosion resistance and cytotoxicity of HA coatings have been investigated. Results show that the growth pattern of the HA is influenced by the local pH value. HA has a preferential c-axis and higher crystallinity in the alkaline environment developing a nanorod-like structure, while in acid and neutral environments it has a preferential growth along the a(b)-plane with a lower crystallinity, developing a nanosheet-like structure. The different morphology and microstructure lead to different degradation behavior and performance of HA coatings. Immersion and electrochemical tests show that the neutral environment promote formation of HA coatings with high corrosion resistance. The cell culture experiments confirm that the enhanced corrosion resistance assure the biocompatibility of the substrate-coating system. In general, the HA coating prepared in neutral environment shows great potential in surface modification of magnesium alloys. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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18 pages, 3289 KiB

Open AccessArticle

In Vitro Corrosion of Titanium Nitride and Oxynitride-Based Biocompatible Coatings Deposited on Stainless Steel

by Iulian Pana, Viorel Braic, Mihaela Dinu, Emile S. Massima Mouele, Anca C. Parau, Leslie F. Petrik and Mariana Braic

Coatings 2020, 10(8), 710; https://doi.org/10.3390/coatings10080710 - 22 Jul 2020

Cited by 33 | Viewed by 5865

Abstract

The reactive cathodic arc deposition technique was used to produce Ti nitride and oxynitride coatings on 304 stainless steel substrates (SS). Both mono (SS/TiN, SS/TiNO) and bilayer coatings (SS/TiN/TiNO and SS/TiNO/TiN) were investigated in terms of elemental and phase composition, microstructure, grain size, morphology, and roughness. The corrosion behavior in a solution consisting of 0.10 M NaCl + 1.96 M H₂O₂ was evaluated, aiming for biomedical applications. The results showed that the coatings were compact, homogeneously deposited on the substrate, and displaying rough surfaces. The XRD analysis indicated that both mono and bilayer coatings showed only cubic phases with (111) and (222) preferred orientations. The highest crystallinity was shown by the SS/TiN coating, as indicated also by the largest grain size of 23.8 nm, which progressively decreased to 16.3 nm for the SS/TiNO monolayer. The oxynitride layers exhibited the best in vitro corrosion resistance either as a monolayer or as a top layer in the bilayer structure, making them a good candidate for implant applications. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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16 pages, 4106 KiB

Open AccessEditor’s ChoiceArticle

In Vitro Corrosion and Tribocorrosion Performance of Biocompatible Carbide Coatings

by Iulian Pana, Alina Vladescu, Lidia R. Constantin, Ioan G. Sandu, Mihaela Dinu and Cosmin M. Cotrut

Coatings 2020, 10(7), 654; https://doi.org/10.3390/coatings10070654 - 7 Jul 2020

Cited by 14 | Viewed by 3658

Abstract

The present study aims to explain the corrosion and the tribocorrosion performance in simulated conditions of the human body by the level of stress, adhesion of coating to substrate, roughness, and hardness. The coatings were synthesized by the cathodic arc evaporation method on 316L stainless steel substrates to be used for load bearing implants. Structure, elemental, and phase compositions were studied by means of energy dispersive spectrometry and X-ray diffraction, respectively. The grain size and strain of the coatings were determined by the Williamson–Hall plot method. Tests on hardness, adhesion, roughness, and electrochemical behavior in 0.9% NaCl solution at 37 ± 0.5 °C were carried out. Tribocorrosion performances, evaluated by measuring the friction coefficient and wear rate, were conducted in 0.9% NaCl solution using the pin on disc method at 37 ± 0.5 °C. TiC and ZrC exhibited a (111) preferred orientation, while TiNbC had a (200) orientation and the smallest crystallite size (8.1 nm). TiC was rougher than ZrC and TiNbC; the lowest roughness was found for TiNbC coatings. The highest hardness and adhesion values were found for TiNbC, followed by TiC and the ZrC. All coatings improved the corrosion resistance of 316L steels, but TiNbC showed the best corrosion behavior. TiNbC had the lowest friction coefficient (1.6) and wear rate (0.99 × 10⁻⁵ mm³·N⁻¹∙m⁻¹) values, indicating the best tribocorrosive performance in 0.9% NaCl at 37 ± 0.5 °C. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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10 pages, 1913 KiB

Open AccessArticle

Comparison of the Clinical Results of Identically Designed Total Knee Prostheses with Different Surface Roughnesses

by Sang Hyun Ko and Kyoung Ho Moon

Coatings 2020, 10(5), 486; https://doi.org/10.3390/coatings10050486 - 19 May 2020

Cited by 1 | Viewed by 3395

Abstract

The purpose of this study was to investigate the effects of the undersurface roughness of total knee prosthesis on clinical outcomes. We compared the clinical and radiological outcomes and prosthesis survivals in patients who underwent total knee arthroplasty using prosthesis with identical designs but different surface roughness (average surface roughnesses (R_a), 5.0 μm vs. 11.6 μm). The results showed that the knee prostheses with a more roughened undersurface (R_a = 11.6 μm) produced significantly better functional results and enhanced prosthesis survival. The difference in surface roughness was associated with incidence of osteolysis and loosening at the tibial baseplate, but not at the femoral component. Overall, our results provided significant evidence that the use of roughened undersurface of tibial baseplate would be a way to prevent aseptic loosening. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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17 pages, 5224 KiB

Open AccessArticle

In Vitro Activity Assays of Sputtered HAp Coatings with SiC Addition in Various Simulated Biological Fluids

by Alina Vlădescu, Anca Pârâu, Iulian Pană, Cosmin M. Cotruț, Lidia R. Constantin, Viorel Braic and Diana M. Vrânceanu

Coatings 2019, 9(6), 389; https://doi.org/10.3390/coatings9060389 - 15 Jun 2019

Cited by 27 | Viewed by 4810

Abstract

Considering the requirements of medical implantable devices, it is pointed out that biomaterials should play a more sophisticated, longer-term role in the customization and optimization of the material–tissue interface in order to ensure the best long-term clinical outcomes. The aim of this contribution was to assess the performance of silicon carbide–hydroxyapatite in various simulated biological fluids (Dulbecco’s modified Eagle’s medium (DMEM), simulated body fluid (SBF), and phosphate buffer solution (PBS)) through immersion assays for 21 days at 37 ± 0.5 °C and to evaluate the electrochemical behavior. The coatings were prepared on Ti6Al4V alloy substrates by magnetron sputtering method using two cathodes made of hydroxyapatite and silicon carbide (SiC). After immersion assays the coating’s surface was analyzed in terms of morphology, chemical and phase composition, and chemical bonds. According to the electrochemical behavior in the media investigated at 37 ± 0.5 °C, SiC addition inhibits the dissolution of the hydroxyapatite in DMEM acellular media. Furthermore, after adding SiC, the slow degradation of hydroxyapatite in PBS and SBF media as well as biomineralization in DMEM were observed. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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13 pages, 2850 KiB

Open AccessSystematic Review

Role of Stem Cells in Augmenting Dental Implant Osseointegration: A Systematic Review

by Mohammed E. Sayed, Maryam H. Mugri, Mazen A. Almasri, Manea Musa Al-Ahmari, Shilpa Bhandi, Thodur Balaji Madapusi, Saranya Varadarajan, A. Thirumal Raj, Rodolfo Reda, Luca Testarelli and Shankargouda Patil

Coatings 2021, 11(9), 1035; https://doi.org/10.3390/coatings11091035 - 27 Aug 2021

Cited by 16 | Viewed by 5732

Abstract

Dental implants are a widely used treatment modality for oral rehabilitation. Implant failures can be a result of many factors, with poor osseointegration being the main culprit. The present systematic review aimed to assess the effect of stem cells on the osseointegration of dental implants. An electronic search of the MEDLINE, LILACS, and EMBASE databases was conducted. We examined quantitative preclinical studies that reported on the effect of mesenchymal stem cells on bone healing after implant insertion. Eighteen studies that fulfilled the inclusion criteria were included. Various surface modification strategies, sites of placement, and cell origins were analyzed. The majority of the selected studies showed a high risk of bias, indicating that caution must be exercised in their interpretation. All the included studies reported that the stem cells used with graft material and scaffolds promoted osseointegration with higher levels of new bone formation. The mesenchymal cells attached to the implant surface facilitated the expression of bio-functionalized biomaterial surfaces, to boost bone formation and osseointegration at the bone–implant interfaces. There was a promotion of osteogenic differentiation of human mesenchymal cells and osseointegration of biomaterial implants, both in vitro and in vivo. These results highlight the significance of biomodified implant surfaces that can enhance osseointegration. These innovations can improve the stability and success rate of the implants used for oral rehabilitation. Full article

(This article belongs to the Special Issue Surface Modification of Medical Implants)

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