Enhanced Corrosion Resistance and Mechanical Durability of the Composite PLGA/CaP/Ti Scaffolds for Orthopedic Implants.

In addressing the challenge of enhancing orthopedic implants, 3D porous calcium phosphate (CaP) coatings on titanium (Ti) substrates modified with poly(lactic-co-glycolic acid) (PLGA) were proposed. CaP coatings on Ti were deposited using the ultrasonic-assisted micro-arc oxidation (UMAO) method, followed by modification with PLGA through a dip coating process at concentrations of 5%, 8%, and 10%. The addition of PLGA significantly improved adhesive-cohesive strength according to the scratch test, while PLGA to CaP adhesion was found to be not less than 8.1 ± 2.2 MPa according to the peel test. Tensile testing showed a typical fracture of CaP coatings and mechanisms of brittle fracture. Corrosion resistance, assessed via gravimetric and electrochemical methods in 0.9% NaCl and PBS solutions, revealed PLGA's substantial reduction in corrosion rates, with the corrosion current decreasing by two orders of magnitude even for the 5% PLGA/CaP/Ti sample. Also, the PLGA layer significantly enhanced the impedance modulus by two orders of magnitude, indicating a robust barrier against corrosion at all PLGA concentrations. Higher PLGA concentrations offered even greater corrosion resistance and improved mechanical properties. This research underscores the potential of using CaP- and PLGA-modified coatings to extend the life and functionality of orthopedic implants, addressing a significant challenge in biomedical engineering.

RF Magnetron Sputtering of Substituted Hydroxyapatite for Deposition of Biocoatings.

Functionalization of titanium (Ti)-based alloy implant surfaces by deposition of calcium phosphates (CaP) has been widely recognized. Substituted hydroxyapatites (HA) allow the coating properties to be tailored based on the use of different Ca substitutes. The formation of antibacterial CaP coatings with the incorporation of Zn or Cu by an RF magnetron sputtering is proposed. The influence of RF magnetron targets elemental composition and structure in the case of Zn-HA and Cu-HA, and the influence of substrate's grain size, the substrate's temperature during the deposition, and post-deposition heat treatment (HT) on the resulting coatings are represented. Sintering the targets at 1150 °C resulted in a noticeable structural change with an increase in cell volume and lattice parameters for substituted HA. The deposition rate of Cu-HA and Zn-HA was notably higher compared to stochiometric HA (10.5 and 10) nm/min vs. 9 ± 0.5 nm/min, respectively. At the substrate temperature below 100 °C, all deposited coatings were found to be amorphous with an atomic short-range order corresponding to the {300} plane of crystalline HA. All deposited coatings were found to be hyper-stochiometric with Ca/P ratios varying from 1.9 to 2.5. An increase in the substrate temperature to 200 °C resulted in the formation of equiaxed grain structure on both coarse-grained (CG) and nanostructured (NS) Ti. The use of NS Ti notably increased the scratch resistance of the deposited coatings from18 ± 1 N to 22 ± 2 N. Influence of HT in air or Ar atmosphere is also discussed. Thus, the deposition of Zn- or Cu-containing CaP is a complex process that could be fine-tuned using the obtained research results.

UMAOH Calcium Phosphate Coatings Designed for Drug Delivery: Vancomycin, 5-Fluorouracil, Interferon α-2b Case.

Drug delivery systems based on calcium phosphate (CaP) coatings have been recently recognized as beneficial drug delivery systems in complex cases of bone diseases for admission of drugs in the localized area, simultaneously inducing osteoinduction because of the bioavailable Ca and P ions. However, micro-arc oxidation (MAO) deposition of CaP does not allow for the formation of a coating with sufficient interconnected porosity for drug delivery purposes. Here, we report on the method to deposit CaP-based coatings using a new hybrid ultrasound-assisted MAO (UMAOH) method for deposition of coatings for drug delivery that could carry various types of drugs, such as cytostatic, antibacterial, or immunomodulatory compositions. Application of UMAOH resulted in coatings with an Ra roughness equal to 3.5 µm, a thickness of 50-55 µm, and a combination of high values of internal and surface porosity, 39 and 28%, respectively. The coating is represented by the monetite phase that is distributed in the matrix of amorphous CaP. Optimal conditions of coating deposition have been determined and used for drug delivery by impregnation with Vancomycin, 5-Fluorouracil, and Interferon-α-2b. Cytotoxicity and antimicrobial activity of the manufactured drug-carrying coatings have been studied using the three different cell lines and methicillin-resistant S. aureus.

Advances in Laser Additive Manufacturing of Ti-Nb Alloys: From Nanostructured Powders to Bulk Objects.

The additive manufacturing of low elastic modulus alloys that have a certain level of porosity for biomedical needs is a growing area of research. Here, we show the results of manufacturing of porous and dense samples by a laser powder bed fusion (LPBF) of Ti-Nb alloy, using two distinctive fusion strategies. The nanostructured Ti-Nb alloy powders were produced by mechanical alloying and have a nanostructured state with nanosized grains up to 90 nm. The manufactured porous samples have pronounced open porosity and advanced roughness, contrary to dense samples with a relatively smooth surface profile. The structure of both types of samples after LPBF is formed by uniaxial grains having micro- and nanosized features. The inner structure of the porous samples is comprised of an open interconnected system of pores. The volume fraction of isolated porosity is 2 vol. % and the total porosity is 20 vol. %. Cell viability was assessed in vitro for 3 and 7 days using the MG63 cell line. With longer culture periods, cells showed an increased cell density over the entire surface of a porous Ti-Nb sample. Both types of samples are not cytotoxic and could be used for further in vivo studies.

Zn- or Cu-Containing CaP-Based Coatings Formed by Micro-arc Oxidation on Titanium and Ti-40Nb Alloy: Part I-Microstructure, Composition and Properties.

Zn- and Cu-containing CaP­based coatings, obtained by micro-arc oxidation process, were deposited on substrates made of pure titanium (Ti) and novel Ti-40Nb alloy. The microstructure, phase, and elemental composition, as well as physicochemical and mechanical properties, were examined for unmodified CaP and Zn- or Cu-containing CaP coatings, in relation to the applied voltage that was varied in the range from 200 to 350 V. The unmodified CaP coatings on both types of substrates had mainly an amorphous microstructure with a minimal content of the CaHPO4 phase for all applied voltages. The CaP coatings modified with Zn or Cu had a range from amorphous to nano- and microcrystalline structure that contained micro-sized CaHPO4 and Ca(H2PO4)2·H2O phases, as well as nano­sized ß­Ca2P2O7, CaHPO4, TiO2, and Nb2O5 phases. The crystallinity of the formed coatings increased in the following order: CaP/TiNb < Zn-CaP/TiNb < Cu-CaP/TiNb < CaP/Ti < Zn-CaP/Ti < Cu-CaP/Ti. The increase in the applied voltage led to a linear increase in thickness, roughness, and porosity of all types of coatings, unlike adhesive strength that was inversely proportional to an increase in the applied voltage. The increase in the applied voltage did not affect the Zn or Cu concentration (~0.4 at%), but led to an increase in the Ca/P atomic ratio from 0.3 to 0.7.

Investigation of the adhesion properties of calcium-phosphate coating to titanium substrate with regards to the parameters of high-frequency magnetron sputtering.

PURPOSE: The main goal of the work was to find the interconnection between the high-frequency magnetron sputtering parameters and the adhesion properties of CaP coatings formed on the surface of titanium substrate. METHODS: Calcium-phosphate coatings, similar in composition to hydroxyapatite, were generated by high-frequency magnetron sputtering on titanium substrate at different values of high-frequency specific power over times of one and two hours. Afterwards, the generated coatings were studied using the method of X-ray phase analysis, and sclerometric tests (scratch test) were carried out. The adhesion strength of the deposited coatings was tested for different coating thicknesses from 0.45 to 1.1 × 10⁻³ mm. RESULTS: According to the results of sclerometry, it was found that with an increase in the high-frequency specific power of plasma to 3.15 W/cm², the adhesion strength of the calcium-phosphate coating also increases. For all the coatings, the critical loads at which the coating completely exfoliated from the substrate were determined. CONCLUSIONS: According to the research results, the most optimal conditions for obtaining high-adhesive calcium-phosphate coatings were determined.

Tailoring the Surface Morphology and the Crystallinity State of Cu- and Zn-Substituted Hydroxyapatites on Ti and Mg-Based Alloys.

Titanium-based alloys are known as a "gold standard" in the field of implantable devices. Mg-based alloys, in turn, are very promising biocompatible material for biodegradable, temporary implants. However, the clinical application of Mg-based alloys is currently limited due to the rapid resorption rate in the human body. The deposition of a barrier layer in the form of bioactive calcium phosphate coating is proposed to decelerate Mg-based alloys resorption. The dissolution rate of calcium phosphates is strongly affected by their crystallinity and structure. The structure of antibacterial Cu- and Zn-substituted hydroxyapatite deposited by an radiofrequency (RF) magnetron sputtering on Ti and Mg-Ca substrates is tailored by post-deposition heat treatment and deposition at increased substrate temperatures. It is established that upon an increase in heat treatment temperature mean crystallite size decreases from 47 ± 17 to 13 ± 9 nm. The character of the crystalline structure is not only governed by the temperature itself but relies on the condition such as either post-deposition treatment, where an amorphous calcium phosphate undergoes crystallization or instantaneous crystalline coating growth during deposition on the hot substrate. A higher treatment temperature at 700 °C results in local coating micro-cracking and induced defects, while the temperature of 400-450 °C resulted in the formation of dense, void-free structure.

Nanoscale Electrical Potential and Roughness of a Calcium Phosphate Surface Promotes the Osteogenic Phenotype of Stromal Cells.

Mesenchymal stem cells (MSCs) and osteoblasts respond to the surface electrical charge and topography of biomaterials. This work focuses on the connection between the roughness of calcium phosphate (CP) surfaces and their electrical potential (EP) at the micro- and nanoscales and the possible role of these parameters in jointly affecting human MSC osteogenic differentiation and maturation in vitro. A microarc CP coating was deposited on titanium substrates and characterized at the micro- and nanoscale. Human adult adipose-derived MSCs (hAMSCs) or prenatal stromal cells from the human lung (HLPSCs) were cultured on the CP surface to estimate MSC behavior. The roughness, nonuniform charge polarity, and EP of CP microarc coatings on a titanium substrate were shown to affect the osteogenic differentiation and maturation of hAMSCs and HLPSCs in vitro. The surface EP induced by the negative charge increased with increasing surface roughness at the microscale. The surface relief at the nanoscale had an impact on the sign of the EP. Negative electrical charges were mainly located within the micro- and nanosockets of the coating surface, whereas positive charges were detected predominantly at the nanorelief peaks. HLPSCs located in the sockets of the CP surface expressed the osteoblastic markers osteocalcin and alkaline phosphatase. The CP multilevel topography induced charge polarity and an EP and overall promoted the osteoblast phenotype of HLPSCs. The negative sign of the EP and its magnitude at the micro- and nanosockets might be sensitive factors that can trigger osteoblastic differentiation and maturation of human stromal cells.