Properties of biodegradable polymer coatings with hydroxyapatite on a titanium alloy substrate.

Purpose: Titanium alloys are among the most widely used materials in medicine, especially in orthopedics. However, their use requires the application of an appropriate surface modification method to improve their properties. Such methods include anodic oxidation and the application of polymer coatings, which limit the release of alloying element ions. In addition, biodegradable polymer coatings can serve as a carrier for drugs and other substances. The paper presents the results of research on the physical properties of biodegradable polymer coatings containing nanoparticle hydroxyapatite on a titanium alloy substrate. Methods: A PLGA coating was used in the tests. The coatings on the substrate of the anodized Ti6Al7Nb alloy were applied by ultrasonic spray coating. The tests were carried out for coatings with various hydroxyapatite content (5, 10, 15, 20%) and thickness resulting from the number of layers applied (5, 10, 15 layers). The scope of the research included microscopic observations using scanning electron microscopy, topography tests with optical profilometry, structural studies using X-ray diffraction, as well as wettability and adhesion tests. Results: The results shows that with the use of ultrasonic spray coating system is possible to obtain the continuous coatings containing hydroxyapaptite. Conclusions: The properties of the coating can be controlled by changing the percentage of hydroxyapatite and the number of layers of which the coating is composed.

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.

Comparison of the Visibility of Canine Menisci before and after Tibial Plateau Leveling Osteotomy: 3D-Printed Model Study.

The aim of this study was to compare the degree of visibility of the lateral and medial menisci before and after tibial plateau leveling osteotomy (TPLO) on 3D-printed models created after laser scanning of the right tibia with menisci derived from a fresh cadaver of a 4-year-old adult male golden retriever. The models were produced of white polylactic acid, and the menisci were filled with light-curing red resin. The models showed a similar conformation as the natural specimen harvested from the cadaver, maintaining the same length and width, in addition to reproducing the anatomical structures. From the pre- and post-TPLO radiographs, it was possible to identify the anatomical structures corresponding to the tibial plateau. The preoperative tibial plateau angle was 26.2°, and the postoperative one ranged between 4.0° and 5.3° (4.6 ± 0.4°). In the bird's-eye photo, the total number of red pixels in the lateral and the medial meniscus was 2,053,995 and 2,140,939, respectively. Before TPLO, only between 14% and 19% of the entire area of the menisci was visible, and the unhidden part of the entire area of the meniscus before TPLO did not differ significantly between the lateral (16.2 ± 1.6%) and the medial (16.4 ± 1.6%) meniscus (p = 0.351). The visible part of the entire meniscus area increased significantly after TPLO both in the lateral and medial menisci (p < 0.001)-mean difference ± SD of 30.3 ± 4.3% (CI 95%: 27.9%, 32.6%) and 36.4 ± 6.4% (CI 95%: 32.9%, 40.0%), respectively. In conclusion, the intraoperative examination and treatment of dog menisci are easier after TPLO.

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.

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.

Effect of Nitrided and Nitrocarburised Austenite on Pitting and Crevice Corrosion Resistance of 316LVM Steel Implants.

Harmful lesions occur in the body around multielement stabilisers made of AISI 316 LVM (Low Vacuum Melted) steel, caused by products of pitting, fretting or crevice corrosion. Preventing the effect is possible by modifying the surface of the steel implants. Therefore, the goal of the paper is the comparison of the mechanical and physiochemical properties of plates for treating deformations of the anterior chest wall made of AISI 316 LVM steel, subjected to diffusion and sterilisation processes and exposed to Ringer's solution. The surface of the implants was subjected to electrochemical polishing, chemical passivation and, in order to modify their properties, nitrocarburised and nitrided diffusion layers were created on selected stabilisers under glow discharge conditions with the use of an active screen at a temperature of 420 °C, over 60 min. The conducted studies involved the examination of the microstructure of the formed layers, surface roughness testing, analysis of contact angles and surface free energy, examination of resistance to pitting and crevice corrosion and examination of nanohardness. On the basis of the results of the conducted studies, it was established that the most advantageous set of properties after sterilisation and exposure to Ringer's solution was displayed by implants with a formed diffusion nitrocarburised layer.

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.

Properties of Ti-6Al-7Nb titanium alloy nitrocarburized under glow discharge conditions.

PURPOSE: The paper presents the results of physicochemical and mechanical properties of the Ti-6Al-7Nb alloy with surface modified by formation of a diffusive nitrocarburized layer deposited in a low-temperature plasma process. The main aim of the study was to evaluate the influence of steam sterilization and exposure to Ringer's solution on the utility properties of the alloy. METHODS: Based on the study of the microstructure, roughness, wettability, resistance to pitting corrosion, ion infiltration and mechanical properties, the usefulness of the proposed method of surface treatment for clinical application was proven. RESULTS: Deposition of the nitrocarburized layer increased the surface roughness and surface hardness, but also reduced the contact angle, and corrosion resistance with respect to the polished surfaces. The nitrocarburized layer is a barrier against the infiltration of ions to the solution and sterilization and exposure to Ringer solution have greater effect on the physicochemical properties rather than on the mechanical ones. CONCLUSION: It was found that sterilization, and exposure to Ringer's solution greatly affect the change of physicochemical properties rather than mechanical properties for both nitrocarburized layers and the Ti-6Al-7Nb alloy of mechanically polished surface.

Evaluation of physicochemical properties of surface modified Ti6Al4V and Ti6Al7Nb alloys used for orthopedic implants.

The paper presents the results of selected functional properties of TiO2 layers deposited by ALD method on the surface of Ti6Al4V and Ti6Al7Nb alloys intended for implants in bone surgery. TiO2 layer was applied at the constant temperature of the ALD process at T=200°C at a variable number of cycles, which resulted in a different layer thickness. Different process cycles of 500, 1250, and 2500 were analyzed. The application of experimental methods (AFM, SEM, wettability, potentiodynamic test, EIS, scratch test, nanohardness and layer thickness) enabled to select the optimal number of cycles, and thus the thickness of the TiO2 layer of the most favorable functional properties. The obtained results clearly showed that regardless of the type of titanium substrate, the TiO2 layer applied in a 2500cycle ALD process has the best physicochemical and electrochemical properties. These properties have major impact on biocompatibility, and therefore the quality of the final product. The information obtained can be useful for manufacturers of medical devices involved in the production of implants used in reconstructive surgery of skeletal system.

The study of physicochemical properties of stabilizing plates removed from the body after treatment of pectus excavatum.

This paper presents the results of a physicochemical surface study and clinical observation of a new generation of plates for the treatment of pectus excavatum. Analysis of the data allowed us to investigate the effect of implant design and condition of their surface on the results of treatment of pectus excavatum. In the study, we performed an analysis of clinical data, obtained after a suitable period of treatment with the use of implants, as well as a study of physicochemical properties of stabilizing plates after their removal from the body. Surface roughness, the surface wettability and corrosion resistance were measured, and the results were compared with clinical observations. When removing the plates we found only slight inflammatory-periosteal reactions around the wire fixing transverse stabilizing plates to the ribs and locking the base plate correcting the distortion. The corrective plates did not shift or rotate during the entire treatment period, giving an optimal, oval and natural shape of the chest. The obtained values of the parameters investigated indicate that the reduction in resistance to pitting corrosion occurred in the areas where laser marking was made to identify the plate. The remaining plates, in spite of mechanical damage of the surface, were characterized by good corrosion resistance, a fact which is confirmed by the results of clinical evaluation.

Total hip arthroplasty using cementless avantage cup in patients with risk of hip prosthesis instability.

BACKGROUND: The aim of the study was to assess total hip arthroplasty procedures using the cementless Avantage cup in women with additional risk factors for postoperative hip instability. MATERIAL AND METHODS: A total of 280 cementless Avantage and Avantage Reload cups were implanted in 260 women aged between 29 and 79 years (60.9 years on average) in the years 2004-2010. In 217 women, there was at least one additional risk factor for prosthesis dislocation. The survival of the cup was assessed by using the necessity of cup replacement as an endpoint of the study. The statistical analyses used the Fisher test to assess the difference in the necessity of revision surgery between the Avantage and Avantage Reload cups, and the Kaplan Meier method was used to evaluate the effective functioning time of the prosthesis. Additionally, tests were conducted on the surface layer of 2 not used and 4 removed cups. RESULTS: 239 patients (259 arthroplasties) were subjected to the final examination. The follow-up period ranged from 2.7 to 9.7 years, 7.0 years on average. None of the patients demonstrated postoperative prosthesis instability. Aseptic loosening was observed in 19 cups in 18 women (7.3%). Intra-prosthetic dislocation occurred 4 times, and in two cases it was combined with loosening of the cup. Revision surgery was required more often in patients with the Avantage cup (9.5%, 17 out of 179) in comparison to the Avantage Reload (2.5%, 2 out of 80). However, the observed differences did not reach the level of statistical significance. The cumulative survival rate of the Avantage cup was 0.94 at 5 years and 0.86 at 8 years. CONCLUSIONS: 1. Avantage cups reduce the risk of postoperative hip instability. 2. Patients with cementless Avantage cups should be closely monitored for signs of aseptic loosening.

Experimental biomechanical assessment of plate stabilizers for treatment of pectus excavatum.

The paper discusses results of experimental research involving new generation of plate stabilizers used for the treatment of deformation of the front chest wall. Previous clinical monitoring revealed instances of minimal rotation, which caused destabilization of the anastomosis and pain in patients. In order to prevent this, transverse stabilizing plates were introduced to the structure of the stabilizer. The new structure of stabilizers was tested using two specially prepared research posts: 1 - which enables fastening of the plate stabilizers to a platform simulating human ribs, 2 - using a pig chest, to which plates were fastened according to the stabilization conditions in the stabilizer-chest structure. The tests recorded displacement values in selected areas of the plates in response to applied loading forces.