Rubber-like PTFE Thin Coatings Deposited by Pulsed Electron Beam Deposition (PED) Method.

PTFE coatings were manufactured using the pulsed electron beam deposition (PED) technique and deposited on Si substrates. The deposition was carried out at constant parameters: temperature 24 °C, discharge voltages 12 kV, and 5000 electron pulses with a pulse frequency of 5 Hz. Nitrogen was used as the background gas. The gas pressure varied from 3 to 11 mTorr. The coating adhesion was evaluated using micro scratch testing and the residual scratch morphology was characterized by atomic force microscopy. Detailed studies of the chemical and physical structure were conducted using infrared spectroscopy and X-ray diffraction. These analyses were then correlated with the mechanical response of the coatings observed during the scratch tests. Drawing upon a review of the literature concerning energetic beam interactions with PTFE material, hypotheses were posed to explain why only specific conditions of the PED process yielded PTFE coatings with rubber-like properties.

Influence of Chemical Composition on Structure and Mechanical Properties of Vacuum-Carburized Low-Alloy Steels.

This study presents research results concerning the vacuum carburizing of four steel grades, specifically conforming to European standards 1.7243, 1.6587, 1.5920, and 1.3532. The experimental specimens exhibited variations primarily in nickel content, ranging from 0 to approximately 3.8 wt. %. As a comparative reference, gas carburizing was also conducted on the 1.3532 grade, which had the highest nickel content. Comprehensive structural analysis was carried out on the resultant carburized layers using a variety of techniques, such as optical and electron scanning, transmission microscopy, and X-ray diffraction. Additionally, mechanical properties such as hardness and fatigue strength were assessed. Fatigue strength evaluation was performed on un-notched samples having a circular cross-section with a diameter of 12 mm. Testing was executed via a three-point bending setup subjected to sinusoidally varying stresses ranging from 0 to maximum stress levels. The carburized layers produced had effective thicknesses from approximately 0.8 to 1.4 mm, surface hardness levels in the range of 600 to 700 HV, and estimated retained austenite contents from 10 to 20 vol%. The observed fatigue strength values for the layers varied within the range from 1000 to 1350 MPa. It was found that changing the processing method from gas carburizing, which induced internal oxidation phenomena, to vacuum carburizing improved the fatigue properties to a greater extent than increasing the nickel content of the steel.

Towards Understanding the Chemical Structure Modification of EVA Copolymer upon MAPLE Processing of Thin Films.

A series of coatings from poly(ethylene-co-vinyl acetate) (EVA) were obtained using the matrix-assisted pulsed laser evaporation (MAPLE) technique. By changing the process parameters, i.e., laser fluence and EVA co-polymer concentration in the target, coatings with various morphologies and topographies were produced. The evaluation of the film structure was based on an analysis of optical and atomic force microscopy and profilometry measurements. A detailed chemical structure investigation, conducted based on Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra, revealed that although the general structure was preserved, some alterations of ethylene (Et) and vinyl acetate (VAc) blocks took place. The most noticeable change was in the ester group that was transformed into ketone and carboxyl groups; nevertheless, some changes in the aliphatic main chain were also present. The chemical structure changes in EVA coatings took place regardless of the process parameters used. The use of chloroform as a solvent to dissolve the EVA copolymer was indicated as a possible reason of the changes as well as the tendency of EVA macromolecules to form clusters. Nevertheless, due to low level of structure alteration, it has been shown that the MAPLE technique can be successfully used to obtain coatings from polymers with more complex structures, which are soluble in a limited number of solvents.

Laser Direct Writing via Two-Photon Polymerization of 3D Hierarchical Structures with Cells-Antiadhesive Properties.

We report the design and fabrication by laser direct writing via two photons polymerization of innovative hierarchical structures with cell-repellency capability. The structures were designed in the shape of "mushrooms", consisting of an underside (mushroom's leg) acting as a support structure and a top side (mushroom's hat) decorated with micro- and nanostructures. A ripple-like pattern was created on top of the mushrooms, over length scales ranging from several µm (microstructured mushroom-like pillars, MMP) to tens of nm (nanostructured mushroom-like pillars, NMP). The MMP and NMP structures were hydrophobic, with contact angles of (127 ± 2)° and (128 ± 4)°, respectively, whereas flat polymer surfaces were hydrophilic, with a contact angle of (43 ± 1)°. The cell attachment on NMP structures was reduced by 55% as compared to the controls, whereas for the MMP, a reduction of only 21% was observed. Moreover, the MMP structures preserved the native spindle-like with phyllopodia cellular shape, whereas the cells from NMP structures showed a round shape and absence of phyllopodia. Overall, the NMP structures were more effective in impeding the cellular attachment and affected the cell shape to a greater extent than the MMP structures. The influence of the wettability on cell adhesion and shape was less important, the cellular behavior being mainly governed by structures' topography.

Hierarchical multi-layered scaffolds based on electrofluidodynamic processes for tissue engineering.

The aim of this study was to obtain hierarchical scaffolds combining 3D printing and two electrofluidodynamic methods. The multi-layered scaffold is composed by 3D printed struts, electrospun fibers obtained from poly(ϵ-caprolactone) and electrosprayed spheres produced from hydrophobically modified chitosan, namely chitosan grafted with linoleic acid (CHLA). Since CHLA has been used for the first time in the electrospraying (electro dynamic spraying, EDS) process, the formation of spheres needed an optimization process. The EDS process was strongly affected by the solvent mixture composition, concentration of acid used for CHLA dissolution and solution flow rate. By using the optimized electrospraying conditions, uniformly distributed spheres have been obtained, decorating struts and nanofibers. Preliminary biological tests with mouse preosteoblasts (MC3T3-E1) were performed to investigate the effect of the hierarchical scaffold on cell seeding efficacy. Results showed that the hierarchical structure enhances cell seeding efficacy, respect to the 3D printed struts alone, preventing that the cells passed through the struts during the seeding. Moreover, the addition of the electrosprayed nanoparticles does not affect the cell seeding efficiency. The versatility of the proposed structure, with the added value of CHLA nanoparticles decoration could be suitable for several applications in tissue engineering, mainly related to drug delivery systems.

Antibacterial Activity of N,O-Acylated Chitosan Derivative.

The antibacterial activity of N,O-acylated chitosan derivative with linoleic acid (CH_LA) was tested by disc and well diffusion, agar impregnation and microdilution methods against Staphylococcus aureus, Escherichia coli and Helicobacter pylori strains. Hydrophobically modified chitosan (HMC) was expected to exhibit enhanced antibacterial activity and specific mucin interactions. Although diffusion tests have not indicated the antibacterial potential of chitosan (CH) or CH_LA, the results of the microdilution method demonstrated that tested polymers significantly reduced the amount of living bacteria cells in different concentrations depending on the microorganism. Additionally, CH_LA was characterized by enhanced antibacterial activity compared to CH, which may suggest a different mechanism of interaction with S. aureus and H. pylori. Furthermore, the UV-VIS analysis revealed that the amphiphilic character of derivative led to strong CH_LA-mucin interactions. The study proved the high potential of CH_LA in antibacterial applications, especially for the gastrointestinal tract.

XPS and FTIR Studies of Polytetrafluoroethylene Thin Films Obtained by Physical Methods.

Two methods-attenuated total reflection Fourier infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)-have been used to analyze the chemical structure of polytetrafluorethylene (PTFE) thin coatings deposited by pulsed laser (PLD) and pulsed electron beam (PED) ablations. The volume of the analyzed materials is significantly different in these techniques which can be of great importance in the characterization of highly heterogeneous thin films. Optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been additionally used to examine the coating surface morphology. The studies have shown that in the case of thin polymer coatings deposited by physical methods, the application for chemical structure evaluation of complementary techniques, with different surface sensitivity, together with the use of surface topography imaging, provide unique insight into the film morphology. The results can provide information contributing to an in-depth understanding of the deposition mechanism of polymer coatings.

Biofunctional catheter coatings based on chitosan-fatty acids derivatives.

Multifunctional and biofunctional coatings for medical devices are an attractive strategy towards tailoring the interactions of the device with the body, thereby influencing the host response, and the susceptibility to microbial colonization. Here we describe the development of a coating process to yield amphiphilic, lubricious coatings, resistant to bacterial colonization, based on chitosan. Chitosan-fatty acid derivatives were obtained by simultaneous N,O-acylation of chitosan with either linoleic, α-linolenic, or dilinoleic acid. Chemical characterization of new materials was carried out using 1H NMR, FTIR, and XPS. Surface properties of coated polyester samples were studied using SEM and contact angle measurements, which indicated that the incorporation of hydrophobic constituents into chitosan macromolecules led to a decrease of both surface roughness and water contact angle. Importantly, tribological testing demonstrated that these new coatings decrease the coefficient of friction due to the self-organization of fatty acid (from 0.53 for the neat chitosan to 0.35 for chitosan-fatty acid derivative). Meanwhile, preliminary bacterial colonization tests indicated significant-over 80%-reduction in E. coli colonization following coating with chitosan-linoleic and chitosan-α-linolenic derivatives. Finally, cytotoxicity and hemocompatibility studies confirmed that all amphiphilic chitosan-fatty acid derivatives were non-toxic and non-hemolytic. Collectively, our results demonstrate the potential of the developed coating strategy, particularly the chitosan-linoleic and chitosan-α-linolenic acid derivatives, for applications as biofunctional catheter coatings.

Chemical Structure of EVA Films Obtained by Pulsed Electron Beam and Pulse Laser Ablation.

Poly(ethylene-co-vinyl acetate) (EVA) films were deposited for the first time using physical methods. The chemical structure of the films obtained using two techniques, pulsed electron beam deposition (PED) and pulsed laser deposition (PLD), was studied by attenuated total reflection Fourier infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Whilst significant molecular degradation of the EVA films was observed for the PLD method, the original macromolecular structure was only partially degraded when the PED technique was used, emphasizing the superiority of the PED method over PLD for structurally complex polymers such as EVA. Optical and scanning electron microscopic observations revealed compact and smooth EVA films deposited by pulsed electron beam ablation as opposed to heterogeneous films with many different sized particulates obtained by PLD.

The Importance of Reaction Conditions on the Chemical Structure of N,O-Acylated Chitosan Derivatives.

The structure of acylated chitosan derivatives strongly determines the properties of obtained products, influencing their hydrodynamic properties and thereby their solubility or self-assembly susceptibility. In the present work, the significance of slight changes in acylation conditions on the structure and properties of the products is discussed. A series of chitosan-acylated derivatives was synthesized by varying reaction conditions in a two-step process. As reaction media, two diluted acid solutions-i.e., acetic acid and hydrochloric acid)-and two coupling systems-i.e., 1-ethyl-3-(3-dimethyl-aminopropyl)-1-carbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (EDC/NHS)-were used. The chemical structure of the derivatives was studied in detail by means of two spectroscopic methods, namely infrared and nuclear magnetic resonance spectroscopy, in order to analyze the preference of the systems towards N- or O-acylation reactions, depending on the synthesis conditions used. The results obtained from advanced 1H-13C HMQC spectra emphasized the challenge of achieving a selective acylation reaction path. Additionally, the study of the molecular weight and solution behavior of the derivatives revealed that even slight changes in their chemical structure have an important influence on their final properties. Therefore, an exact knowledge of the obtained structure of derivatives is essential to achieve reaction reproducibility and to target the application.

Modification of bacterial cellulose through exposure to the rotating magnetic field.

The aim of the study was to assess the influence of rotating magnetic field (RMF) on production rate and quality parameters of bacterial cellulose synthetized by Glucanacetobacter xylinus. Bacterial cultures were exposed to RMF (frequency f=50Hz, magnetic induction B=34mT) for 72h at 28°C. The study revealed that cellulose obtained under RMF influence displayed higher water absorption, lower density and less interassociated microfibrils comparing to unexposed control. The application of RMF significantly increased the amount of obtained wet cellulose pellicles but decreased the weight and thickness of dry cellulose. Summarizing, the exposure of cellulose-synthesizing G. xylinus to RMF alters cellulose biogenesis and may offer a new biotechnological tool to control this process. As RMF-modified cellulose displays better absorbing properties comparing to non-modified cellulose, our finding, if developed, may find application in the production of dressings for highly exudative wounds.