Structural Parameters and Behavior in Simulated Body Fluid of High Entropy Alloy Thin Films.

The structure, composition and corrosion properties of thin films synthesized using the Pulsed Laser Deposition (PLD) technique starting from a three high entropy alloy (HEA) AlCoCrFeNix produced by vacuum arc remelting (VAR) method were investigated. The depositions were performed at room temperature on Si and mirror-like polished Ti substrates either under residual vacuum (low 10-7 mbar, films denoted HEA2, HEA6, and HEA10, which were grown from targets with Ni concentration molar ratio, x, equal to 0.4, 1.2, and 2.0, respectively) or under N2 (10-4 mbar, films denoted HEN2, HEN6, and HEN10 for the same Ni concentration molar ratios). The deposited films' structures, investigated using Grazing Incidence X-ray Diffraction, showed the presence of face-centered cubic and body-centered cubic phases, while their surface morphology, investigated using scanning electron microscopy, exhibited a smooth surface with micrometer size droplets. The mass density and thickness were obtained from simulations of acquired X-ray reflectivity curves. The films' elemental composition, estimated using the energy dispersion X-ray spectroscopy, was quite close to that of the targets used. X-ray Photoelectron Spectroscopy investigation showed that films deposited under a N2 atmosphere contained several percentages of N atoms in metallic nitride compounds. The electrochemical behavior of films under simulated body fluid (SBF) conditions was investigated by Open Circuit Potential (OCP) and Electrochemical Impedance Spectroscopy measurements. The measured OCP values increased over time, implying that a passive layer was formed on the surface of the films. It was observed that all films started to passivate in SBF solution, with the HEN6 film exhibiting the highest increase. The highest repassivation potential was exhibited by the same film, implying that it had the highest stability range of all analyzed films. Impedance measurements indicated high corrosion resistance values for HEA2, HEA6, and HEN6 samples. Much lower resistances were found for HEN10 and HEN2. Overall, HEN6 films exhibited the best corrosion behavior among the investigated films. It was noticed that for 24 h of immersion in SBF solution, this film was also a physical barrier to the corrosion process, not only a chemical one.

A New Method for Tungsten Oxide Nanopowder Deposition on Carbon-Fiber-Reinforced Polymer Composites for X-ray Attenuation.

A new method for the synthesis and deposition of tungsten oxide nanopowders directly on the surface of a carbon-fiber-reinforced polymer composite (CFRP) is presented. The CFRP was chosen because this material has very good thermal and mechanical properties and chemical resistance. Also, CFRPs have low melting points and are transparent under ionized radiation. The synthesis is based on the direct interaction between high-power-density microwaves and metallic wires to generate a high-temperature plasma in an oxygen-containing atmosphere, which afterward condenses as metallic oxide nanoparticles on the CFRP. During microwave discharge, the value of the electronic temperature of the plasma, estimated from Boltzmann plots, reached up to 4 eV, and tungsten oxide crystals with a size between 5 nm and 100 nm were obtained. Transmission electron microscopy (TEM) analysis of the tungsten oxide nanoparticles showed they were single crystals without any extended defects. Scanning electron microscopy (SEM) analysis showed that the surface of the CFRP sample does not degrade during microwave plasma deposition. The X-ray attenuation of CFRP samples covered with tungsten oxide nanopowder layers of 2 µm and 21 µm thickness was measured. The X-ray attenuation analysis indicated that the thin film with 2 µm thickness attenuated 10% of the photon flux with 20 to 29 KeV of energy, while the sample with 21 µm thickness attenuated 60% of the photon flux.

Enhancing the Hydrophobicity and Antibacterial Properties of SiCN-Coated Surfaces with Quaternization to Address Peri-Implantitis.

Peri-implantitis is a major cause of dental implant failure. This disease is an inflammation of the tissues surrounding the implant, and, while the cause is multi-factorial, bacteria is the main culprit in initiating an inflammatory reaction. Dental implants with silicon carbonitride (SiCN) coatings have several potential advantages over traditional titanium implants, but their antibacterial efficiency has not yet been evaluated. The purpose of this study was to determine the anti-bacterial potential of SiCN by modifying the surface of SiCN-coated implants to have a positive charge on the nitrogen atoms through the quaternization of the surface atoms. The changes in surface chemistry were confirmed using contact angle measurement and XPS analysis. The modified SiCN surfaces were inoculated with Streptococcus mutans (S. mutans) and compared with a silicon control. The cultured bacterial colonies for the experimental group were 80% less than the control silicon surface. Fluorescent microscopy with live bacteria staining demonstrated significantly reduced bacterial coverage after 3 and 7 days of incubation. Scanning electron microscopy (SEM) was used to visualize the coated surfaces after bacterial inoculation, and the mechanism for the antibacterial properties of the quaternized SiCN was confirmed by observing ruptured bacteria membrane along the surface.

Band-gap engineering of zirconia by nitrogen doping in reactive HiPIMS: a step forward in developing innovative technologies for photocatalysts synthesis.

In the global context of climate change and carbon neutrality, this work proposes a strategy to improve the light absorption of photocatalytic water-splitting materials into the visible spectrum by anion doping. In this framework, reactive high power impulse magnetron sputtering (HiPIMS) of a pure Zr target in Ar/N2/O2 gas mixture was used for the deposition of crystalline zirconium oxynitride (ZrO2-xNx) thin films with variable nitrogen doping concentration and energy band-gap. The nitrogen content into these films was controlled by the discharge pulsing frequency, which controls the target surface poisoning and peak discharge current. The role of the nitrogen doping on the optical, structural, and photocatalytic properties of ZrO2-xNx films was investigated. UV-Vis-NIR spectroscopy was employed to investigate the optical properties and to assess the energy band-gap. Surface chemical analysis was performed using X-ray photoelectron spectroscopy, while structural analysis was carried out by X-ray diffraction. The increase in the pulse repetition frequency determined a build-up in the nitrogen content of the deposited ZrO2-xNx thin films from ∼10 to ∼25 at.%. This leads to a narrowing of the optical band-gap energy from 3.43 to 2.20 eV and endorses efficient absorption of visible light. Owing to its narrow bandgap, ZrO2-xNx thin films obtained by reactive HiPIMS can be used as visible light-driven photocatalyst. For the selected processing conditions (pulsing configuration and gas composition), it was found that reactive HiPIMS can suppress the hysteresis effect for a wide range of frequencies, leading to a stable deposition process with a smooth transition from compound to metal-sputtering mode.

Hydroxyapatite Thin Films of Marine Origin as Sustainable Candidates for Dental Implants.

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical-chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15-18°. The inferred bonding strength adherence values were superior (i.e., ~49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

Modulation of Structural, Electronic, and Optical Properties of Titanium Nitride Thin Films by Regulated In Situ Oxidation.

Epitaxial titanium nitride (TiN) and titanium oxynitride (TiON) thin films have been grown on sapphire substrates using a pulsed laser deposition (PLD) method in high-vacuum conditions (base pressure <3 × 10-6 T). This vacuum contains enough residual oxygen to allow a time-independent gas phase oxidation of the ablated species as well as a time-dependent regulated surface oxidation of TiN to TiON films. The time-dependent surface oxidation is controlled by means of film deposition time that, in turn, is controlled by changing the number of laser pulses impinging on the polycrystalline TiN target at a constant repetition rate. By changing the number of laser pulses from 150 to 5000, unoxidized (or negligibly oxidized) and oxidized TiN films have been obtained with the thickness in the range of four unit cells to 70 unit cells of TiN/TiON. X-ray photoelectron spectroscopy (XPS) investigations reveal higher oxygen content in TiON films prepared with a larger number of laser pulses. The oxidation of TiN films is achieved by precisely controlling the time of deposition, which affects the surface diffusion of oxygen to the TiN film lattice. The lattice constants of the TiON films obtained by x-ray diffraction (XRD) increase with the oxygen content in the film, as predicted by molecular dynamics (MD) simulations. The lattice constant increase is explained based on a larger electrostatic repulsive force due to unbalanced local charges in the vicinity of Ti vacancies and substitutional O. The bandgap of TiN and TiON films, measured using UV-visible spectroscopy, has an asymmetric V-shaped variation as a function of the number of pulses. The bandgap variation following the lower number of laser pulses (150-750) of the V-shaped curve is explained using the quantum confinement effect, while the bandgap variation following the higher number of laser pulses (1000-5000) is associated with the modification in the band structure due to hybridization of O2p and N2p energy levels.

Subthreshold Laser Ablation Measurements by Langmuir Probe Method for ns Irradiation of HfO2 and ZrO2.

The unbiased Langmuir probe (LP) method was used to perform measurements on HfO2 and ZrO2 samples around the laser ablation threshold on a wide range of irradiation conditions. Important changes in the lifetime (from ms to µs) and the shape of the charge particle current were seen with the increase of the laser fluence. The ablation threshold was estimated by evaluating the overall average ablated charge as a function of the laser fluence. Above the ablation threshold, the generation of high kinetic species is seen, which can reach several keV. An important jump in ion acceleration potential is observed for values above 1 J/cm2, which coincides with the dominant presence of negative ions in the plasma. The evolution of several plasma parameters (ion density, expansion velocity, electron temperature, Debye length) was investigated and correlated with the fundamental ablation mechanism involved in various irradiation regimes. The LP data were correlated with COMSOL simulations on the maximum surface temperature reached during irradiation. Important correlations between the evaporation and melting processes and ablation threshold fluence and ion acceleration phenomena are also reported.

Langmuir Probe Perturbations during In Situ Monitoring of Pulsed Laser Deposition Plasmas.

The recent advancements in pulsed laser deposition (PLD) control via plasma diagnostics techniques have been positive and raised questions on the limitation of some techniques, such as the Langmuir probe (LP). The particularities of laser-produced plasma can lead to incorrect interpretation of collected electrical signal. In this paper, we explored the limitations of LP as a technique for in situ PLD control by performing investigations on several metallic plasmas, expanding in various Ar atmosphere conditions. Sub-microsecond modulation was seen in the reconstructed IV characteristics attributed to non-equilibrium dynamics of the ejected charges. A perturbative regime was recorded for Ar pressures higher than 2 Pa, where ionic bursts were observed in the electron saturation region. This perturbation was identified as a plasma fireball. A non-linear multifractal model was developed here to explore these new regimes of the LP. The strange attractors characterizing each fireball were reconstructed, and their evolution with the Ar pressure is discussed. Both short- and long-time non-linear behavior were correlated via probe bias, and the pressure effect on the strange attractor's defining the fireball-like behavior was investigated. A good correlation was noticed between the simulated data and experimental findings.

On the Dynamics of Transient Plasmas Generated by Nanosecond Laser Ablation of Several Metals.

The dynamics of transient plasma generated by UV ns-laser ablation of selected metals (Co, Cu, Ag, Bi) were investigated by the Langmuir Probe method in angle- and time-resolved modes. Multiple ionic and electronic structures were seen for all plasmas with some corresponding to anions or nanoparticle-dominated structures. The addition of an Ar atmosphere energetically confined the plasma and increased the charge density by several orders of magnitude. For pressure ranges exceeding 0.5 Pa fast ions were generated in the plasma as a result of Ar ionization and acceleration in the double layer defining the front of the plasma plume. Several correlations between the target nature plasma properties were attempted. The individual plasma structure expansion velocity increases with the melting point and decreases with the atomic mass while the corresponding charged particle densities decrease with the melting point, evidencing the relationship between the volatility of the sample and the overall abated mass.

Measurement error due to self-absorption in calibration-free laser-induced breakdown spectroscopy.

Self-absorption of spectral lines is known to lower the performance of analytical measurements via calibration-free laser-induced breakdown spectroscopy. However, the error growth due to this effect is not clearly assessed. Here we propose a method to quantify the measurement error due to self-absorption based on the calculation of the spectral radiance of a plasma in local thermodynamic equilibrium. Validated through spectroscopic measurements for a binary alloy thin film of compositional gradient, the method evidences that measurement performance lowering due to self-absorption depends on the spectral shape of the analytical transition and on the intensity measurement method. Thus, line-integrated intensity measurements of Stark broadened lines enable accurate analysis, even at large optical thickness, if line width and plasma size are precisely known. The error growth due to self-absorption is significantly larger for line shapes dominated by Doppler broadening and for line-center intensity measurements. The findings present a significant advance in compositional measurements via calibration-free laser-induced breakdown spectroscopy, as they enable straightforward selection of most appropriate analytical lines.

Qualitative Analysis of Remineralization Capabilities of Bioactive Glass (NovaMin) and Fluoride on Hydroxyapatite (HA) Discs: An In Vitro Study.

Tooth decay is a prevalent disease that initiates when the oral pH becomes acidic. Fluoride and/or bioactive glass (NovaMin) were used to regenerate/repair teeth that had been decalcified. In this present study, we investigated the effect of fluoride and/or bioactive glass (NovaMin) on remineralization of hydroxyapatite (HA) discs, which mimic the enamel surface of natural teeth. HA discs were etched with phosphoric acid and treated with one of the following toothpastes: (1) Sensodyne toothpaste with fluoride; (2) Sensodyne toothpaste with fluoride and bioactive glass (NovaMin); (3) Tom's toothpaste without fluoride or bioactive glass (NovaMin); and (4) Tom's toothpaste with bioactive glass (NovaMin). The toothpastes were applied on the etched discs for two minutes, once a day for 15 days. Scanning electron microscopy (SEM) was used to analyze surface morphologies and X-ray photoelectron spectroscopy (XPS) was used to analyze surface compositions. Tom's toothpaste with only NovaMin demonstrated the most remineralization potential compared with the other groups. In conclusion, incorporating bioactive glass (NovaMin) into toothpastes could benefit the repair and remineralization of teeth.

Structural and optical characteristics determined by the sputtering deposition conditions of oxide thin films.

The influence of film thickness on the structural and optical properties of silicon dioxide (SiO2) and zinc oxide (ZnO) thin films deposited by radio frequency magnetron sputtering on quartz substrates was investigated. The deposition conditions were optimized to achieve stoichiometric thin films. The orientation of crystallites, structure, and composition were investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), while the surface topography of the samples was analyzed using scanning electron microscopy (SEM). The optical characteristics were measured for samples with the same composition but obtained with different deposition parameters, such as increasing thickness. The optical constants (i.e., the refractive index n, the extinction coefficient k, and the absorption coefficient α) of the SiO2 and ZnO oxide films were determined from the transmission spectra recorded in the range of 190-2500 nm by using the Swanepoel method, while the energy bandgap was calculated from the absorption spectra. The influence of thickness on the structural and optical properties of the oxide films was investigated. Good optical quality and performance were noticed, which makes these thin films worthy of integration into metamaterial structures.

The Effects Induced by Microwave Field upon Tungsten Wires of Different Diameters.

The effects induced by microwave field upon tungsten wires of different diameters were investigated. Tungsten wires with 0.5 and 1.0 mm diameters were placed in the focal point of a single-mode cylindrical cavity linked to a microwave generator and exposed to microwave field in ambient air. The experimental results showed that the 0.5 mm diameter wire was completely vaporized due to microwaves strong absorption, while the wire with 1 mm diameter was not ignited. During the interaction between microwaves and tungsten wire with 0.5 mm diameter, a plasma with a high electronic excitation temperature was obtained. The theoretical analysis of the experiment showed that the voltage generated by metallic wires in interaction with microwaves depended on their electric resistance in AC and the power of the microwave field. The physical parameters and dimension of the metallic wire play a crucial role in the ignition process of the plasma by the microwave field. This new and simple method to generate a high-temperature plasma from a metallic wire could have many applications, especially in metal oxides synthesis, metal coatings, or thin film deposition.

Cutting Behavior of Al0.6CoCrFeNi High Entropy Alloy.

There is an increased interest in high entropy alloys as a result of the special possibilities of improving the mechanical, physical or chemical characteristics resulting from metallic matrices made of different chemical elements added in equimolar proportions. The next step in developing new alloys is to determine the cutting conditions to optimize manufacturing prescriptions. This article presents a series of tests performed to estimate the machining behavior of the Al0.6CoCrFeNi high entropy alloy. The effects of temperature during machining, wear effects on the cutting tool, evolution of the hardness on the processed areas, cutting force components and resultant cutting force for high entropy alloy (HEA) in comparison with 304 stainless steel, scrap aspect and machined surface quality were analyzed to have an image of the HEA machinability. In terms of cutting forces, the behavior of the HEA was found to be about 59% better than that of stainless steel. XRD analysis demonstrated that the patterns are very similar for as-cast and machined surfaces. The wear effects that appear on the cutting edge faces for the tool made of rapid steel compared to carbide during HEA machining led to the conclusion that physical vapor deposition (PVD)-coated carbide inserts are suitable for the cutting of HEAs.

Annealing and N2 Plasma Treatment to Minimize Corrosion of SiC-Coated Glass-Ceramics.

To improve the chemical durability of SiC-based coatings on glass-ceramics, the effects of annealing and N2 plasma treatment were investigated. Fluorapatite glass-ceramic disks were coated with SiC via plasma-enhanced chemical vapor deposition (PECVD), treated with N2 plasma followed by an annealing step, characterized, and then immersed in a pH 10 buffer solution for 30 days to study coating delamination. Post-deposition annealing was found to densify the deposited SiC and lessen SiC delamination during the pH 10 immersion. When the SiC was treated with a N2 plasma for 10 min, the bulk properties of the SiC coating were not affected but surface pores were sealed, slightly improving the SiC's chemical durability. By combining N2 plasma-treatment with a post-deposition annealing step, film delamination was reduced from 94% to 2.9% after immersion in a pH 10 solution for 30 days. X-ray Photoelectron spectroscopy (XPS) detected a higher concentration of oxygen on the surface of the plasma treated films, indicating a thin SiO2 layer was formed and could have assisted in pore sealing. In conclusion, post-deposition annealing and N2 plasma treatment where shown to significantly improve the chemical durability of PECVD deposited SiC films used as a coating for glass-ceramics.

Rapid thermal annealing for high-quality ITO thin films deposited by radio-frequency magnetron sputtering.

In this work, rapid thermal annealing (RTA) was applied to indium tin oxide (ITO) films in ambient atmosphere, resulting in significant improvements of the quality of the ITO films that are commonly used as conductive transparent electrodes for photovoltaic structures. Starting from a single sintered target (purity 99.95%), ITO thin films of predefined thickness (230 nm, 300 nm and 370 nm) were deposited at room temperature by radio-frequency magnetron sputtering (rfMS). After deposition, the films were subjected to a RTA process at 575 °C (heating rate 20 °C/s), maintained at this temperature for 10 minutes, then cooled down to room temperature at a rate of 20 °C/s. The film structure was modified by changing the deposition thickness or the RTA process. X-ray diffraction investigations revealed a cubic nanocrystalline structure for the as-deposited ITO films. After RTA, polycrystalline compounds with a textured (222) plane were observed. X-ray photon spectroscopy was used to confirm the beneficial effect of the RTA treatment on the ITO chemical composition. Using a Tauc plot, values of the optical band gap ranging from 3.17 to 3.67 eV were estimated. These values depend on the heat treatment and the thickness of the sample. Highly conductive indium tin oxide thin films (ρ = 7.4 × 10-5 Ω cm) were obtained after RTA treatment in an open atmosphere. Such films could be used to manufacture transparent contact electrodes for solar cells.

Growth of WOx from Tungsten(VI) Oxo-Fluoroalkoxide Complexes with Partially Fluorinated ß-Diketonate/ß-Ketoesterate Ligands: Comparison of Chemical Vapor Deposition to Aerosol-Assisted CVD.

Tungsten(VI) oxo complexes of the type WO(OR)3L [R = C(CH3)2CF3, C(CF3)2CH3, CH(CF3)2, L = hexafluoroacetylacetonate (hfac), ethyl trifluoroacetoacetonate (etfac), acetylacetonate (acac)] bearing partially fluorinated alkoxide and/or chelating ligands were synthesized. Thermal decomposition behavior and mass spectrometry (MS) fragmentation patterns of selected examples were studied. The thermolysis products of WO(OC(CF3)2CH3)3(hfac) were characterized by nuclear magnetic resonance and gas chromatography-MS. Studies of the sublimation behavior of the complexes demonstrated that their volatility depends on the degree of fluorination. Comparative studies of the deposition of tungsten oxide by chemical vapor deposition (CVD) and aerosol-assisted CVD were carried out using WO(OC(CF3)2CH3)3(hfac) as a single-source precursor. WOx materials were successfully deposited by both deposition methods, but the deposits differed in morphology, structure, and crystallinity.

Influence of Ag, Au and Pd noble metals doping on structural, optical and antimicrobial properties of zinc oxide and titanium dioxide nanomaterials.

Oxide materials (ZnO, TiO2) doped with noble metals were synthesized using the combustion technique. The results of the addition of Ag, Au, and Pd up to a concentration of 2 mol% on the structural, optical, morphological and antimicrobial properties was considered. X-ray diffraction experiments revealed that the crystal structure of the host materials remained unaltered despite doping with noble metals. From the scanning electron microscopy results, it was evident that the doped nanoparticles aggregated in clusters of different sizes in the host matrix. The plasmonic effect was also observed in the absorbance spectra of the different doped materials. The obtained materials have shown promising antimicrobial features. All ZnO materials exhibited a high antimicrobial activity, with very low minimum inhibitory concentration values, against the planktonic growth of all tested Gram-positive and Gram-negative bacterial strains. All doped materials exhibited very good anti-biofilm activity, the lowest minimal biofilm eradication concentration values being registered for ZnO doped with Au and Pd toward Escherichia coli and for ZnO doped with Ag against Candida albicans. These results indicate the potential that these materials have for antimicrobial applications in the fields of biomedicine and environmental protection.

Analysis of Multi-elemental Thin Films via Calibration-Free Laser-Induced Breakdown Spectroscopy.

Elemental analyses of thin films with complex composition are challenging as the standard analytical techniques based on measurement calibration are difficult to apply. We show that calibration-free laser-induced breakdown spectroscopy (LIBS) presents a powerful solution, enabling quantitative analyses of multielemental thin films with analytical performances better than those obtained with other techniques. The demonstration is given for a nickel-chromium-molybdenum alloy film of 150 nm thickness that was produced by pulsed laser deposition. The LIBS spectra were recorded under experimental conditions that enable simple and accurate modeling of plasma emission. Thus, a calibration-free approach based on the calculation of the spectral radiance of a uniform plasma in local thermodynamic equilibrium was applied to deduce the elemental composition. Supported by analyses via Rutherford backscattering spectrometry and energy-dispersive X-ray spectroscopy, the LIBS measurements evidence nonstoichiometric mass transfer of the alloy during the thin-film deposition process. This technique could be used even for thinner films, provided that the film-composing elements are not present in the substrate.

Antibacterial Properties of Charged TiN Surfaces for Dental Implant Application.

The formation and characterization of positively surface charged TiN surfaces were investigated for improving dental implant survival. Surface nitrogen atoms of a traditional TiN implant were converted to a positive charge by a quaternization reaction which greatly increased the antibacterial efficiency. Ti, TiN, and quaternized TiN samples were incubated with human patient subgingival bacteria for 4 hours at 37°C in an anaerobic environment with an approximate 40% reduction in counts on the quaternized surface over traditional Ti and TiN. The samples were challenged with Streptococcus Mutans and fluorescent imaging confirmed significant reduction in the quaternized TiN over the traditional Ti and TiN. Contact angle measurement and X-Ray Photoelectron Spectroscopy (XPS) were utilized to confirm the surface chemistry changes. The XPS results found the charged quaternized nitrogen peak at 399.75 eV that is unique to the quaternized sample.