ABSTRACT This work aimed to analyze the influence of treatment pressure on the interaction between stearic acid and an Argon-Oxygen plasma. The fixed variables were the applied RF plasma power (50 W), treatment time (30 min), and treatment starting temperature (273 K). The pressure was varied as follows: 0.2, 0.6, and 1.0 Torr. For all treatment conditions, the etching of the samples was observed, as evidenced by the mass loss of the specimens and by following the gaseous by-products of reactions employing a mass spectrometer coupled to the reaction chamber. Optical emission spectroscopy followed the emission lines of oxygen active species. Functionalization of the specimens was also observed, as shown by the results obtained by Fourier-transform infrared spectroscopy (FTIR) and through XRD analysis. A liquid phase was formed for samples treated at 0.6 and 1.0 Torr, which favored the functionalization process and broadened the band present in the region from 1750 to 1700 cm–1, resulting in amorphous phases. An increase in the intensity of the characteristic peaks of esters was also observed. It can be concluded that the higher pressure favors the formation of a liquid phase and reaction kinetics, resulting in higher functionalization and lower etching.

ABSTRACT Surface treatments such as heat treatments, paints, plasma treatments and galvanizing are important in metal working industry. In those treatments, the required adhesion characteristics can be limited if contaminants are present, so there is a need to clean these surfaces. Conventional processes can be costly, some generated waste may be environmentally hazardous and, in some cases, due to part geometry, they are not effective. Alternatively, plasma treatments which are considered to be environmentally clean, more efficient and with lower operating costs can overcome those difficulties. Due to the reactional complexity of these treatments, there are many fields to be researched, such as which reactions are due to impacts of (neutral) chemical species and which are due to excited species and radiation. The present work aims to verify the interactions between Ar-10%O2 plasma using amino acid L-proline in an inductively coupled radiofrequency plasma. This study showed that oxidative plasma promotes high degradation of the sample. A gas analyzer (quadrupole mass spectrometer) coupled to the gas outlet was used and many gaseous products are detected during treatment, such: H2, H2O, CO, NO (Nitric Oxide) and CO2 while L-proline undergoes intense degradation. The conclusions allow to state that the interaction between the Ar/O2 plasma and L-proline promotes intense degradation through the breakdown of the heterocyclic ring of the molecule.

The aim of this work was to study the influence of varying nitrogen potential during plasma nitriding of stainless steel ISO 5832-1. The control of nitrogen potential was achieved by pulsing the nitrogen flow for different times (01/19, 02/18, and 05/15), where the numbers represent the time (in minutes) of nitrogen flow on/off, thus creating an intermittent flow of nitrogen during the treatment. For all tested conditions - continuous and pulsed flow of nitrogen - the treatment temperature was kept at 425ºC during 2 and 8 hours. Specimens were characterized by means of X-ray diffraction, scanning electron microscopy, optical microscopy, energy-dispersive X-ray spectroscopy, and nanohardness. Results showed that the layer thickness increases with the increase of total treatment time, and decreased for shorter times of pulsed nitrogen flow. Smaller expansion of the austenite phase, as well as less precipitation of chromium nitrides, were also observed for shorter times of pulsed nitrogen flow. Hence, the use of intermittent nitrogen flow appears to be an efficient approach in order to control the nitrogen concentration within the layer, reducing its brittleness.

Abstract ISO 5832-1 stainless steel specimens were plasma nitrided at different nitrogen potentials. The main goal was to obtain the S-phase with different nitrogen concentrations and free of chromium-based precipitates. The control of nitrogen potential was made by pulsing the gas at predetermined times: 10/10, 05/15, 02/18, and 01/19, where the numbers represent the time in minutes that the nitrogen flow was kept on/off, respectively. For all pulsing conditions, the nitriding was carried out at 450 °C for 2 hours. After nitriding, specimens were characterized by means of optical (OM) and electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and microhardness. Results show that the nitrided layer thickness decreases with decreasing times of nitrogen pulse, and that lower times of nitrogen flow lead to lower precipitation of chromium nitrides. It can be thus concluded that the use of intermittent nitrogen flow is an alternative to control the nitrided layer in terms of thickness, hardness, and the amount of nitrogen present in phase ɣN (S-phase).

The reactions that can occur on organic materials treated in plasma enviorement are strongly affected by surface temperature, thus the sharp determination of this variable is extremely important to process control. In situ temperature measurements are often employed; however, the measured point is generally under the treated surface. If in metallic materials the high thermal conductivity minimizes this problem, in non-metallic materials processing it becomes important, because its thermal resistivity besides a high sensibility to small temperature variations. The present work uses a simulation tool to extract thermal data on Ar+O2 RF plasma processing of Stearic Acid. Experimental data were obtained by thermocouples placed inside the samples. The extrapolation of surface temperature was performed by numerical simulation with Autodesk CFD software v.15.1. Results show that the temperature of the surface reaches values higher than the ones measured inside the sample holder. This difference of temperature is in good agreement with the visual observation of the phase transformations in the treated material, showing a simple and valuable tool to better control of plasma treatments.

ABSTRACT Plasma surface cleaning is an alternative process that aims at the fully removal of organic contaminants on several kinds of materials. Despite its advantages, there are still lacks on the comprehension of the complex relations between plasma-generated species and organic molecules during plasma cleaning. In the present work, a linear alkane (hexatriacontane - C36H74), used as a contaminant model, was exposed to an Argon radiofrequency (RF) inductively coupled plasma (ICP). The by-products from degradation were monitored by optical emission spectroscopy (OES) and residual gas analysis (RGA), to identify the influence of sample positioning on E and H discharge modes regions. The exposition to H-mode discharge resulted in more intense and profuse emissions of C-H and C2 systems. RGA results show similar byproducts from degradation in both modes; however, the intensity from treatment in H-mode is largely greater. It was also observed that plasma etching in H-mode is enough to melt the sample, while E-type discharge leaves the surface of the sample apparently unchanged.

In this work, plasma carburizing of sintered pure iron at low temperature was investigated. Samples were carburized under a dc abnormal glow discharge in two mixed atmospheres (5%CH4 + 95%H2 and 20%CH4 + 80%H2) at 500 °C and 700 °C for 3 and 6 hours. The influence of these parameters was investigated by Scan Electron Microscopy (SEM), X-ray Diffraction (DRX), Raman spectroscopy and microhardness measurements. There is a correlation between temperature and layer morphology, and a layer of polycrystalline cementite was obtained at 500 °C and 700 °C on a ferrite substrate. Furthermore, the carburized layer thickness increased with an increase in the treatment time and the methane percentage. The topography is very dependent on the treatment temperature.

Plasma cleaning is a promising technology in surface treatments, despite technological interest its use is limited because its mechanisms still are not entirely understood. This work aims to evaluate how the applied power of an inductively coupled RF discharge at 13,56 MHz, with Ar and Ar+10%O2 atmospheres, affects its capabilities to etch an organic molecule. Mass variation rate was used as direct characterization of degradation process and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) was performed to search for residual molecular modifications. Additionally, optical emission spectroscopy (OES) measurements were performed to monitor the offer of active species in the gaseous volume. In experimental conditions was possible attain mass reduction from sample, with higher mass loss rate when applied power is increased. Material characterization shows the possibility of attain a high etch rate, while no structural modifications were detected, if the temperature is controlled.

In this work, stearic acid (SA) was degraded in an Ar-O2and Ar-H2post-discharge environment created by a plasma reactor with a microwave source and in an Ar, Ar-H2and Ar-O2DC (Direct Current) discharge environment created in a cathode-anode confined system. The afterglow region is useful for understanding the role of the chemically active species (O, O2, H and H2). In contrast, the discharge region allows the observation of the effects of chemically active species, charged species (ions and electrons) and photons. The influence of these species on the grafting and etching of SA was evaluated by measuring the mass variation, mass variation rate and chemical composition. The results showed that when only chemically active oxygen species are present, the SA is preferentially grafted. However, when both photons and charged species are present, the SA is more efficiently etched. When the Ar-H2and Ar environments are utilized; the SA is not efficiently degraded.

Stearic acid (CH3(CH2)16COOH) was treated with Ar and Ar-O2 (10%) pulsed DC discharges created by a cathode-anode confined system to elucidate the role of oxygen in plasma cleaning. The treatment time (5 to 120 minutes) and plasma gas mixture (Ar and Ar-O2) were varied, and the results showed that the mass variation of stearic acid after Ar-O2 plasma exposure was greater than that of pure Ar plasma treatment. Thus, compared to Ar*, active oxygen species (O and O2, in all states) enhance the etching process, regardless of their concentration. During the treatments, a liquid phase developed at the melting temperature of stearic acid, and differential thermal analyses showed that the formation of a liquid phase was associated with the breakage of bonds due to treatment with an Ar or Ar-O2 plasma. After treatment with Ar and Ar-O2 plasmas, the sample surface was significantly modified, especially when Ar-O2 was utilized. The role of oxygen in the treatment process is to break carbonaceous chains by forming oxidized products and/or to act as a barrier again ramification, which accelerates the etching of stearic acid.