Influence of Hybrid Surface Modification on Biocompatibility and Physicochemical Properties of Ti-6Al-4V ELI Titanium.

Titanium-based materials are the most widely used materials in biomedical applications. However, according to literature findings, the degradation products of titanium have been associated with potential allergic reactions, inflammation, and bone resorption. The corrosion process of Ti-6Al-4V in the human body environment may be exacerbated by factors such as reduced pH levels and elevated concentrations of chloride compounds. Coatings made of biopolymers are gaining attention as they offer numerous advantages for enhancing implant functionality, including improved biocompatibility, bioactivity, wettability, drug release, and antibacterial activity. This study analyzes the physicochemical and electrochemical behavior of the Ti-6Al-4V ELI alloy subjected to PCL and PCL/TiO2 deposition by the electrospinning method. To characterize the polymer-based layer, tests of chemical and phase composition, as well as surface morphology investigations, were performed. Wetting angle tests were conducted as part of assessing the physicochemical properties. The samples were subjected to corrosion behavior analysis, which included open circuit potential measurements, potentiodynamic tests, and the electrochemical impedance spectroscopy method. Additionally, the quantification of released ions post the potentiodynamic test was carried out using the inductively coupled plasma atomic emission spectrometry (ICP-AES) method. Cytotoxicity tests were also performed. It was found that surface modification by depositing a polymer-based layer on the titanium substrate material using the electrospinning method provides improved corrosion behavior, and the samples exhibit non-toxic properties.

Study of the Effect of Anodic Oxidation on the Corrosion Properties of the Ti6Al4V Implant Produced from SLM.

Additive technologies allowed for the development of medicine and implantology, enabling the production of personalized and highly porous implants. Although implants of this type are used clinically, they are usually only heat treated. Surface modification using electrochemical methods can significantly improve the biocompatibility of biomaterials used for implants, including printed ones. The study examined the effect of anodizing oxidation on the biocompatibility of a porous implant made of Ti6Al4V by the SLM method. The study used a proprietary spinal implant intended for the treatment of discopathy in the c4-c5 section. As part of the work, the manufactured implant was assessed in terms of compliance with the requirements for implants (structure testing-metallography) and the accuracy of the pores produced (pore size and porosity). The samples were subjected to surface modification using anodic oxidation. The research was carried out for 6 weeks in in vitro conditions. Surface topographies and corrosion properties (corrosion potential, ion release) were compared for unmodified and anodically oxidized samples. The tests showed no effect of anodic oxidation on the surface topography and improved corrosion properties. Anodic oxidation stabilized the corrosion potential and limited the release of ions to the environment.

Assessment of encrustation and physicochemical properties of poly(lactide-glycolide) - Papaverine hydrochloride coating on ureteral double-J stents after long-term flow of artificial urine.

Implantation of ureteral stents is associated with inconvenience for the patient, which is related to the natural ability of the ureter to contract. The most frequently used solution is the systemic administration of a diastolic drug, which has a relaxing effect on smooth muscle cells and decreases inconvenience. Current interdisciplinary research aimed at reducing the complications after the implantation of ureteral stents used in the treatment of upper urinary tracts with regard to infection, initiation of encrustation, and fragmentation of stents, and patient pain has not been resolved. This study presents the results of research regarding the impact of a biodegradable coating with the active substance on the physical and chemical properties of ureteral stents used in the treatment of the upper urinary tract. The surface of polyurethane double-J stents was coated with poly(lactide-glycolide) (PLGA) 85/15 loaded with papaverine hydrochloride (PAP) with diastolic properties. The coating for ureteral stents has been designed for short-term implantation. The effect of the coating on the process of encrustation and PAP release by the dynamic in vitro model with artificial urine (AU) up to 30 days was evaluated. The influence of AU on the physical and chemical properties of ureteral stents was determined. As part of the study, surface structure and topography researches; chemical composition analyses using X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and wetting; and surface roughness studies of both PUR stents and coated stents were carried out. The proposed biodegradable PLGA+PAP coating is characterized by controlled drug release, while optimal physicochemical properties does not increase the encrustation process.

Functional Properties of Polyurethane Ureteral Stents with PLGA and Papaverine Hydrochloride Coating.

Despite the obvious benefits of using ureteral stents to drain the ureters, there is also a risk of complications from 80-90%. The presence of a foreign body in the human body causes disturbances in its proper functioning. It can lead to biofilm formation on the stent surface, which may favor the development of urinary tract infections or the formation of encrustation, as well as stent fragmentation, complicating its subsequent removal. In this work, the effect of the polymeric coating containing the active substance-papaverine hydrochloride on the functional properties of ureteral stents significant for clinical practice were assessed. Methods: The most commonly clinically used polyurethane ureteral Double-J stent was selected for the study. Using the dip-coating method, the surface of the stent was coated with a poly(D,L-lactide-glycolide) (PLGA) coating containing the papaverine hydrochloride (PAP). In particular, strength properties, retention strength of the stent ends, dynamic frictional force, and the fluoroscopic visibility of the stent during X-ray imaging were determined. Results: The analysis of the test results indicates the usefulness of a biodegradable polymer coating containing the active substance for the modification of the surface of polyurethane ureteral stents. The stents coated with PLGA+PAP coating compared to polyurethane stents are characterized by more favorable strength properties, the smaller value of the dynamic frictional force, without reducing the fluoroscopic visibility.

Physical Properties of Electropolished CoCrMo Alloy Coated with Biodegradable Polymeric Coatings Releasing Heparin after Prolonged Exposure to Artificial Urine.

In this study, we aimed to determine the effect of long-term exposure to artificial urine on the physical properties of CoCrMo alloy with biodegradable heparin-releasing polymeric coatings. Variants of polymer coatings of poly(L,L-lactide-ɛ-caprolactone) (P(L,L-L/CL)) and poly(D,L-lactide-ɛ-caprolactone) (P(D,L-L/CL)) constituting the base for heparin-releasing (HEP) polyvinyl alcohol (PVA) coatings were analyzed. The coatings were applied by the dip-coating method. Heparin was used to counteract the incrustation process in the artificial urine. The study included tests of wettability, resistance to pitting and crevice corrosion, determination of the mass density of metal ions penetrating into the artificial urine, and the kinetics of heparin release. In addition, microscopic observations of surface roughness and adhesion to the metal substrate were performed. Electrolytically polished CoCrMo samples (as a reference level) and samples with polymer coatings were used for the tests. The tests were conducted on samples in the initial state and after 30, 60, and 90 days of exposure to artificial urine. The analysis of the test results shows that the polymer coatings contribute by improving the resistance of the metal substrate to pitting and crevice corrosion in the initial state and reducing (as compared with the metal substrate) the mass density of metal ion release into the artificial urine. Moreover, the PVA + HEP coating, regardless of the base polymer coatings used, contributes to a reduction in the incrustation process in the first 30 days of exposure to the artificial urine.

Impact of Surface Treatment on the Functional Properties Stainless Steel for Biomedical Applications.

The main goal of the carried out tests was to analyze the influence of the surface modification of a substrate by depositing composite ZnO layers by the Atomic Layer Deposition (ALD) method. The samples were subjected to preliminary surface modification consisting of being sandblasted and electropolished. A ZnO layer was applied to the prepared substrates by the ALD method. As a precursor of ZnO, diethylzinc (DEZ) was used, which reacted with water, enabling the deposition of the thin films. The chamber temperature was as follows: T = 100-300 °C. The number of cycles was 500 and 1500. As part of the assessment of the physicochemical properties of the resulting surface layers, the tests of chemical composition of the layer, pitting corrosion, impedance corrosion, adhesion to the metal substrate, morphology surface, and wettability were carried out. On the basis of the obtained research, it was found that a composite ZnO layer deposited onto a substrate previously subjected to the electrochemical polishing process has more favorable physicochemical properties. Moreover, an influence of temperature and the number of cycles of the deposition process on the obtained properties was observed, where the ZnO layer was characterized by more favorable properties at a temperature of 200-300 °C at 1500 cycles of the deposition process.

Electrochemical and Biological Performance of Biodegradable Polymer Coatings on Ti6Al7Nb Alloy.

The inhibition of the corrosion of metal implants is still a challenge. This study aimed to increase the corrosion resistance of Ti6Al7Nb alloy implants through surface modification, including grinding, sandblasting, and anodic oxidation followed by the deposition of a polymer coating. The aim of the work was to determine the influence of biodegradable polymer coatings on the physico-chemical properties of a Ti6Al7Nb alloy used for short-term implants. Biodegradable coatings prepared from poly(glycolide-caprolactone) (P(GCap)), poly(glycolide ε-caprolactone-lactide) (P(GCapL)), and poly(lactide-glycolide) (PLGA) were applied in the studies. The dip-coating method with three cycles of dipping was applied. Corrosion resistance was assessed on the basis of potentiodynamic studies. The studies were carried out on samples after 30, 60, and 90 days of exposure to Ringer's solution. Surface topography, wettability, and cytotoxicity studies were also carried out. The degradation process of the base material was evaluated on the basis of the mass density of the metal ions released to the solution. The results indicated the influence of the coating type on corrosion resistance. In addition, a beneficial effect of the polymer coating on the reduction of the density of the released metal ions was found, as compared to the samples without polymer coatings. The obtained results provide basic knowledge for the development of polymer coatings enriched with an active substance. The presence of ciprofloxacin in the coating did not reduce the corrosion resistance of the metal substrate. Moreover, the cytotoxicity test using the extract dilution method demonstrated that the implants' coatings are promising for further in vitro and in vivo studies.

Development of antibacterial, ciprofloxacin-eluting biodegradable coatings on Ti6Al7Nb implants to prevent peri-implant infections.

Various types of biodegradable polymers containing lactide, glycolide, caprolactone, and trimethylene carbonate units have been used to obtain ciprofloxacin (CFX)-enriched coatings developed on the Ti6Al7Nb alloy, intended for short-term therapy. In the first step, the surface of the Ti6Al7Nb alloy was modified, mostly according to sandblasting and anodic oxidation to obtain the TiO2 layer. Anodizing can be an effective method for preparing TiO2 coatings with osteoconductive properties. The polymer containing CFX molecules was deposited on the modified alloy, and Polymer + CFX/TiO 2 /Ti6Al7Nb systems were developed. CFX-enriched coatings adhered well to the surface of the previously modified alloy. Polymer layers maintain the topography of the alloy due to the development of the surface during the sandblasting method. As polymers intended for the study possess degradation ability, they are capable of releasing the incorporated drug. Antibacterial activity of CFX-enriched coatings was examined to verify the functionality of designed Polymer + CFX/TiO 2 /Ti6Al7Nb systems, and the bactericidal effect was confirmed for all cases. The presented study is an extension of previous, initial research and creates an overview of polyester or polyestercarbonate CFX-eluting coatings.

Biodegradable polymer coatings on Ti6Al7Nb alloy.

The aim of the study was to determine the influence of long term exposure to Ringer's solution of biodegradable polymer coatings containing an active substance on the Ti6Al7Nb alloy substrate on the physical and chemical properties of the coatings and the degradation process of the metal substrate. The studies used poly(L-lactide-co-trimethylene carbonate) P(L/TMC), poly(L-lactide-co-trimethylene carbonate-glycolide) P(L/TMC/G) and poly(D,L-lactide-glycolide) (PLGA) coatings applied to the anodically oxidized Ti6Al7Nb alloy by means of dipping method (1, 2 and 3 dips). The polymer coatings contained ciprofloxacin. Roughness and wettability tests were carried out on the substrate and polymer coatings, the pitting corrosion resistance of the substrate and samples with polymer coating was determined, the number of metallic ions released to the solution from the coated and uncoated samples was determined as well as the adhesion of polymer coatings. The research was supplemented by microscopic observations. The results of the research indicate different influence of exposure to Ringer's solution on the physical and chemical properties of biodegradable polymer coatings containing ciprofloxacin and the course of the degradation process of the metal substrate.

Corrosion resistance of PLGA-coated biomaterials.

The aim of the study was to determine the influence of PLGA bioresorbable polymer coating on corrosion resistance of metal biomaterial. Polymer coating deposited by immersion method was applied. Corrosion resistance of metal biomaterials (stainless steel, Ti6Al4V, Ti6Al7Nb) coated with PLGA polymer, after 90 days exposure to Ringer's solution was tested. The amount of metal ions released to the solution was also investigated (inductively coupled plasma-atomic emission spectrometry (ICP-AES) method). The surface of the samples was observed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Degradation of PLGA was monitored with the use of the 1H NMR spectroscopy and GPC (Gel Permeation Chromatography). The studies were carried out for non-sterilized (NS) and sterilized (S) samples. Application of the polymer coating causes a reduction of release of metal ions to the solution. Depending on metal substrate different course of destruction of polymer layer was observed. After 90 days of incubation in Ringer's solution polymer layer was highly degraded, however, the composition of copolymer (ratio of the comonomeric units in the chain) remained unchanged during the whole process, which suggests even degradation. The polymer layer reduced degradation kinetics of the metal substrate. Moreover, degradation process did not change surface morphology of metal substrate and did not disturb its integrity. The results obtained indicate that the applied polymer layer improves corrosion resistance of the alloys being investigated. Thus, the developed implants with bioresorbable coatings could be advantageous for medical applications.

Technological capabilities of surface layers formation on implant made of Ti-6Al-4V ELI alloy.

PURPOSE: The aim of the presented research was to find a combination of surface modification methods of implants made of the Ti-6Al-4V ELI alloy, that lead to formation of effective barrier for metallic ions that may infiltrate into solution. METHODS: To this end, the following tests were carried out: roughness measurement, the voltamperometric tests (potentiodynamic and potentiostatic), and the ion infiltration test. RESULTS: The electropolishing process resulted in the lowering of surface roughness in comparison with mechanical treatment of the surface layer. The anodization process and steam sterilization increased corrosion resistance regardless of the mechanical treatment or electropolishing. The crevice corrosion tests revealed that independent of the modification method applied, the Ti-6Al-4V ELI alloy has excellent crevice corrosion resistance. The smallest quantity of ions infiltrated to the solution was observed for surface modification consisting in the mechanical treatment and anodization with the potential of 97 V. CONCLUSIONS: Electric parameters deter- mined during studies were the basis for effectiveness estimation of particular surface treatment methods. The research has shown that the anodization process significantly influences the pitting corrosion resistance of the Ti-6Al-4V ELI alloy independent of the previous surface treatment methods (mechanical and electrochemical). The surface layer after such modification is a protective barrier for metallic ions infiltrated to solution and protects titanium alloy against corrosive environment influence.

The effects of a SiO2 coating on the corrosion parameters cpTi and Ti-6Al-7Nb alloy.

The aim of this paper was to evaluate the usefulness of the sol-gel method application, to modificate the surface of the Ti6Al7Nb alloy and the cpTi titanium (Grade 4) with SiO2 oxide, applied on the vascular implants to improve their hemocompatibility. Mechanical treatment was followed by film deposition on surface of the titanium samples. An appropriate selection of the process parameters was verified in the studies of corrosion, using potentiodynamic and impedance method. A test was conducted in the solution simulating blood vessels environment, in simulated body fluid at t = 37.0 ± 1 °C and pH = 7.0 ± 0.2. Results showed varied electrochemical properties of the SiO2 film, depending on its deposition parameters. Correlations between corrosion resistance and layer adhesion to the substrate were observed, depending on annealing temperature.

Influence of surgical drills wear on thermal process generated in bones.

The influence of the wear rate of drills used in bone surgery on the temperature distribution in the femur models (Sawbones) is presented in the paper. Surgical drills of diameter d = 4.5 mm and diverse edge geometry (90° and 120°) were selected for the study. In order to carry out thermal analysis with the use of finite element, experimental studies of wear process were necessary. These studies, among others, consisted in determination of average values of axial forces and cutting torques as a function of the number of drilled holes. The study showed an impact of the drill geometry on values that describe cutting process. It was found that the greatest values of torques and axial cutting forces occur in drills of point angle of 120°. Next, in order to determine the effect of wear rate on the generation of temperature in the cutting zone, thermal analysis of the drilling process using the finite element method was carried out. It was found that higher temperatures in the bone are observed for drilling with the use of the drill of point angle equal to 120°, as in the experimental study. For the tools of such edge geometry the wear of cutting edge is more intensive and the generated temperature in femur for the wear land VBB = 0.32 mm has reached the critical value associated with the process of thermal necrosis.

Numerical and experimental analyses of drills used in osteosynthesis.

This paper presents the results of numerical analysis and experimental studies of the process of bone drilling using drills applied in osteosynthesis procedures. In the studies, two surgical drills with a diameter d = 4.5 mm and varying in drill point geometry 2κ were used. Thermal analysis based on FEM allowed determining the distribution of temperatures generated in the bone as a function of rotational speed of the drill. The results indicate that both drill point geometry and rotational speed of the drill have influence on temperatures generated in bone tissue. Additionally, the range was determined for possible values of rotational speed, which does not initiate the process of thermal necrosis of bone. The experimental studies of the process of drilling in a femur model showed the impact of drill point geometry on the values describing the cutting process. It was concluded that the highest values of torques and axial forces during cutting occur in the tools with angle 2κ2 = 120°.