P. Piszczek

CVD of AgI complexes with tertiary phosphines and perfluorinated carboxylates : A new class of silver precursors

C 2 F 5 COOAgPMe 3 (1) and C 2 F 5 COOAg (2) have been used as precursors for the CVD of silver layers in the temperature range 493-623 K. The thin films obtained were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning tunneling electrochemical microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and temperature variable infrared (IR) measurements. The SEM images of Ag films grown from 2 exhibited a surface with a grain size in the range 0.4-1.5 μm, whereas from 1 the size was ∼0.1 μm. This was confirmed by the STEM studies. The better stability of 1 in the vapor phase was proved by temperature variable IR spectra (373-523 K). Mass spectrometry (MS) images confirmed the presence of the monomeric and dimeric species, and the recombination ions transported in vapors. The XPS image analysis of the silver layers revealed the presence of some carbon impurities. The films demonstrated good adhesion to silicon substrates.

Studies of thermal decomposition process of Ag(I) perfluorinated carboxylates with temperature variable IR and MS

Abstract The thermal decomposition process of C2F5COOAg (1) and C3F7COOAg (2) was characterised with temperature variable infrared (IR) and mass spectra (MS). Thermal decomposition of 1 and 2 proceeds in two stages: endothermic and exothermic. Analysis of IR and MS spectra revealed C2F5COOAg monomeric silver species in the gas phase between 473 and 573 K. The volatility of 2 is lower then that of 1, which can be explained as being due to the formation of stable dimeric forms during thermal decomposition of 2 between 373 and 523 K. Both salts decompose to metallic silver, as is evident from the analysis of the X-ray diffractogram.

Optimization of the Silver Nanoparticles PEALD Process on the Surface of 1-D Titania Coatings

Plasma enhanced atomic layer deposition (PEALD) of silver nanoparticles on the surface of 1-D titania coatings, such as nanotubes (TNT) and nanoneedles (TNN), has been carried out. The formation of TNT and TNN layers enriched with dispersed silver particles of strictly defined sizes and the estimation of their bioactivity was the aim of our investigations. The structure and the morphology of produced materials were determined using X-ray photoelectron spectroscopy (XPS) and scanning electron miscroscopy (SEM). Their bioactivity and potential usefulness in the modification of implants surface have been estimated on the basis of the fibroblasts adhesion and proliferation assays, and on the basis of the determination of their antibacterial activity. The cumulative silver release profiles have been checked with the use of inductively coupled plasma-mass spectrometry (ICPMS), in order to exclude potential cytotoxicity of silver decorated systems. Among the studied nanocomposite samples, TNT coatings, prepared at 3, 10, 12 V and enriched with silver nanoparticles produced during 25 cycles of PEALD, revealed suitable biointegration properties and may actively counteract the formation of bacterial biofilm.

The Bioactivity and Photocatalytic Properties of Titania Nanotube Coatings Produced with the Use of the Low-Potential Anodization of Ti6Al4V Alloy Surface

Titania nanotube (TNT) coatings were produced using low-potential anodic oxidation of Ti6Al4V substrates in the potential range 3–20 V. They were analysed by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The wettability was estimated by measuring the contact angle when applying water droplets. The bioactivity of the TNT coatings was established on the basis of the biointegration assay (L929 murine fibroblasts adhesion and proliferation) and antibacterial tests against Staphylococcus aureus (ATCC 29213). The photocatalytic efficiency of the TNT films was studied by the degradation of methylene blue under UV irradiation. Among the studied coatings, the TiO2 nanotubes obtained with the use of 5 V potential (TNT5) were found to be the most appropriate for medical applications. The TNT5 sample possessed antibiofilm properties without enriching it by additional antimicrobial agent. Furthermore, it was characterized by optimal biocompatibility, performing better than pure Ti6Al4V alloy. Moreover, the same sample was the most photocatalytically active and exhibited the potential for the sterilization of implants with the use of UV light and for other environmental applications.

Biocompatibility of Titania Nanotube Coatings Enriched with Silver Nanograins by Chemical Vapor Deposition

Bioactivity investigations of titania nanotube (TNT) coatings enriched with silver nanograins (TNT/Ag) have been carried out. TNT/Ag nanocomposite materials were produced by combining the electrochemical anodization and chemical vapor deposition methods. Fabricated coatings were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The release effect of silver ions from TNT/Ag composites immersed in bodily fluids, has been studied using inductively coupled plasma mass spectrometry (ICP-MS). The metabolic activity assay (MTT) was applied to determine the L929 murine fibroblasts adhesion and proliferation on the surface of TNT/Ag coatings. Moreover, the results of immunoassays (using peripheral blood mononuclear cells—PBMCs isolated from rats) allowed the estimation of the immunological activity of TNT/Ag surface materials. Antibacterial activity of TNT/Ag coatings with different morphological and structural features was estimated against two Staphylococcus aureus strains (ATCC 29213 and H9). The TNT/Ag nanocomposite layers produced revealed a good biocompatibility promoting the fibroblast adhesion and proliferation. A desirable anti-biofilm activity against the S. aureus reference strain was mainly noticed for these TiO2 nanotube coatings, which contain dispersed Ag nanograins deposited on their surface.

Bioactivity Studies on Titania Coatings and the Estimation of Their Usefulness in the Modification of Implant Surfaces

Morphologically different titania coatings (nanofibers (TNFs), nanoneedles (TNNs), and nanowires (TNWs)) were studied as potential biomedical materials. The abovementioned systems were produced in situ on Ti6Al4V substrates via direct oxidation processes using H2O2 and H2O2/CaCl2 agents, and via thermal oxidation in the presence of Ar and Ar/H2O2. X-ray diffraction and Raman spectroscopy have been used to structurally characterize the produced materials. The morphology changes on the titanium alloy surface were investigated using scanning electron microscopy. The bioactivity of the samples has been estimated by the analysis of the produced titania coatings’ biocompatibility, and by the determination of their ability to reduce bacterial biofilm formation. The photoactivity of the produced nanocoatings was also analyzed, in order to determine the possibility of using titania coated implant surfaces in the sterilization process of implants. Photocatalytic activity was estimated using the methylene blue photodegradation kinetics, in the presence of UV light.

Tetranuclear Oxo-Titanium Clusters with Different Carboxylate Aromatic Ligands: Optical Properties, DFT Calculations, and Photoactivity

Titanium(IV) oxo-clusters of the general formula (Ti4O2(OiBu)10(O2CR’)2) (R’ = C13H9 (1), PhCl (2), PhNO2 (3)) were studied in order to estimate their potential photoactivity. The structure of the resulting tetranuclear Ti(IV) oxo-complexes was then determined via single crystal X-ray diffraction, infrared and Raman spectroscopy, and electron spin resonance (ESR). An analysis of diffuse reflectance spectra (DRS) allowed for the assessment of band gap values of (1)–(3) microcrystalline samples complexes. The use of different carboxylate ligands allowed the band gap of tetranuclear Ti(IV) oxo-clusters to be modulated in the range of 3.6 eV–2.5 eV. Density functional theory (DFT) methods were used to explain the influence of substitutes on band gap and optical activity. Dispersion of (1)–(3) microcrystals in the poly(methyl methacrylate) (PMMA) matrixes enabled the formation of composite materials for which the potential photocatalytic activity was estimated through the study on methylene blue (MB) photodegradation processes in the presence of UV light. The results obtained revealed a significant influence of carboxylate ligands functionalization on the photoactivity of synthesized tetranuclear Ti(IV) oxo-complexes.