Effect of cooling rate on properties of plasma nitrided AISI 1010 steel

In this work, AISI 1010 steel samples were plasma nitrided into 20% N 2 100 Pa and 400 Pa for N 2 and H 2 , respectively), temperatures of 500 and 580 °C, during 2 h. Three different procedures for cooling were accomplished after nitriding. In the first procedure the cooling occurred naturally, that is, the sample was kept on substrate holder. In the second one the sample was pulled off and cooling in a cold surface. Finally, in the third cooling process the sample was pulled off the substrate holder down into special reservoir filled with oil held at ambient temperature. The properties of the AISI 1010 steel samples were characterized by optical and electron microscopy, X-ray diffraction, Mössbauer spectroscopy and microhardness tests. Thermal gradient inside the sample kept on substrate holder during cooling process was measured by three inserted thermocouples at different depths. When samples were cooled rapidly the transformation of ϵ-Fe 2 − 3 N to γ′-Fe 4 N was inhibited. Such effect is indicated by the high concentration of ϵ-Fe compound zone. To get solid state solution of nitrogen in the diffusion zone, instead of precipitates of nitride phases, the cooling rate should be higher than a critical value of about 0.95 °C/s. When this value is reached at any depth of the diffusion zone, two distinct diffusion zones will appear. Temperature gradients were measured inside the samples as a consequence of the plasma treatment. It's suggested the need for standardization of the term “treatment temperature” for plasma treatment because different nitrided layer properties could be reported for the same “treatment temperature”.

Modificação de membranas de quitosana por plasma para uso biológico

Chitosan membranes have been modified by plasma, utilizing the following gases: nitrogen (N2), methane (CH4), argon (Ar), oxygen (O2) and hydrogen. The modified membranes by plasma were compared to the unmodified ones. The membranes were characterized by absorption assay, contact angle, atomic force microscopy (AFM). Also, permeability assay of sodium sulfamerazine from such membranes were carried out. Through the absorption assay and contact angle it was possible to obtain information of the wettability of the membranes and what changes the plasma treatment can promote in relation to it. The plasma treatment using oxygen promoted increase of the wetability and swelling while the samples treated with methane decrease of the wetability and swelling. Through the Optical Emission Spectroscopy (OES) it was possible to identify which species were present in the plasma during the treatment. And through the AFM analysis it was possible to observe the changes nanotopography occurred on the surface of the samples. Permeability assay were archived for all treated membranes and compared to no treated ones. Due to that assay it was possible verify which the plasma treatment increased the permeability spectrum of the membranes which has varied from 1,4548 *10-5cm2.min-1 to 2,7713*10-5cm2.min-1. Chitosan membranes with permeability varied are importance in systems drug delivery, to liberate a wide variety of drugs

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Influência dos parâmetros de processo na deposição de nitreto de titânio por plasma em gaiola catódica

Titanium nitride films were grown on glass using the Cathodic Cage Plasma Deposition technique in order to verify the influence of process parameters in optical and structural properties of the films. The plasma atmosphere used was a mixture of Ar, N2 and H2, setting the Ar and N2 gas flows at 4 and 3 sccm, respectively and H2 gas flow varied from 0, 1 to 2 sccm. The deposition process was monitored by Optical Emission Spectroscopy (OES) to investigate the influence of the active species in plasma. It was observed that increasing the H2 gas flow into the plasma the luminescent intensities associated to the species changed. In this case, the luminescence of N2 (391,4nm) species was not proportional to the increasing of the H2 gas into the reactor. Other parameters investigated were diameter and number of holes in the cage. The analysis by Grazing Incidence X-Ray Diffraction (GIXRD) confirmed that the obtained films are composed by TiN and they may have variations in the nitrogen amount into the crystal and in the crystallite size. The optical microscopy images provided information about the homogeneity of the films. The atomic force microscopy (AFM) results revealed some microstructural characteristics and surface roughness. The thickness was measured by ellipsometry. The optical properties such as transmittance and reflectance (they were measured by spectrophotometry) are very sensitive to changes in the crystal lattice of the material, chemical composition and film thicknesses. Therefore, such properties are appropriate tools for verification of this process control. In general, films obtained at 0 sccm of H2 gas flow present a higher transmittance. It can be attributed to the smaller crystalline size due to a higher amount of nitrogen in the TiN lattice. The films obtained at 1 and 2 sccm of H2 gas flow have a golden appearance and XRD pattern showed peaks characteristics of TiN with higher intensity and smaller FWHM (Full Width at Half Maximum) parameter. It suggests that the hydrogen presence in the plasma makes the films more stoichiometric and becomes it more crystalline. It was observed that with higher number of holes in the lid of the cage, close to the region between the lid and the sample and the smaller diameter of the hole, the deposited film is thicker, which is justified by the most probability of plasma species reach effectively the sample and it promotes the growth of the film

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Diagnóstico das espécies ativas do plasma usado em tratamentos termoquímicos do titânio

Plasma diagnostics by Optical Emission Spectroscopy were performed for electrical discharge in three gas mixture respecting the combinations z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, in which the indexes z and y systematically vary from 1 to 4 and x varies from 0 to 4, every one has dimension SCCM, resulting in 80 combinations. From the all obtained spectrums, the species CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) were analyzed because of their abundance and importance on the kinetic of reaction from the plasma to surface, besides their high dependences on the gases flows. Particularly interesting z, y and x combinations were chosen in order to study the influence of active species on the surface modification during the thermochemical treatment. From the mixtures N2 Ar O2 e N2 Ar CH4 were chosen three peculiar proportions which presented luminous intensity profile with unexpected maximum or minimum values, denominated as plasma anomaly. Those plasma concentrations were utilized as atmosphere of titanium treatment maintaining constant the control parameters pressure and temperature. It has been verified a relation among luminous intensity associated to N2+ and roughness, nanohardness and O atoms diffusion into the crystalline lattice of treated titanium and it has been seen which those properties becomes more intense precisely in the higher points found in the optical profile associated to the N2+ specie. Those parameters were verified for the mixture which involved O2 gas. For the mixture which involves CH4 gas, the relation was determinate by roughness, number of nitrogen and carbon atoms diffused into the titanium structure which presented direct proportionality with the luminous intensity referent to the N2+ and CH. It has been yet studied the formation of TiCN phases on the surface which presented to be essentially directly proportional to the increasing of the CH specie and inversely proportional to the increasing of the specie N2+

Modificação superficial de filmes de poliéster usando plasma a baixa temperatura

A polyester film has a vast application field, due some properties that are inherent of this kind of material such as, good mechanical resistance, chemical resistance to acids and bases and low production cost. However, this material has some limitations as low superficial tension, flat surface, low affinity to dyers, and poor adhesion which impede the use of the same ones for some finality as good wettability. Among the existent techniques to increase the superficial tension, plasma as energy source is the more promising technique, because of their versatility and for not polluting the environment. The plasma surface polymeric modification has been used for many researchers, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, polyester films were treated with oxygen plasma varying the treatment time from 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) varying the percentage of each gas the mixture from 0 to 100%, the treatment time remaining constant to all treatments (10 min). After plasma treatment the samples were characterized by contact angle, surface tension, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, with the aim to study the wettability increase of treated polyester films as its variables. In the (O2/N2) plasma treatment of polyester films can be observed an increase of superficial roughness superior to those treated by O2 plasma. By the other hand, the chemical modification through the implantation of polar groups at the surface is obtained more easily using O2 plasma treatment

Efeito do tratamento por plasma na proliferação de fibroblastos e esterilização de membranas de quitosana

Chitosan is being studied for use as dressing due their biological properties. Aiming to expand the use in biomedical applications, chitosan membranes were modified by plasma using the following gases: nitrogen (N2), methane (CH4), argon (Ar), oxygen (O2) and hydrogen (H2). The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle, surface energy and water absorption test. Biological Tests were also performed, such as: test sterilization and proliferation of fibroblasts (3T3 line). Through SEM we observed morphological changes occurring during the plasma treatment, the formation of micro and nano-sized valleys. MFA was used to analyze different roughness parameters (Ra, Rp, Rz) and surface topography. It was found that the treated samples had an increase in surface roughness and sharp peaks. Methane plasma treatment decreased the hydrophilicity of the membranes and also the rate of water absorption, while the other treatments turned the membranes hydrophilic. The sterilization was effective in all treatment times with the following gases: Ar, N2 and H2. With respect to proliferation, all treatments showed an improvement in cell proliferation increased in a range 150% to 250% compared to untreated membrane. The highlights were the treatments with Ar 60 min, O2 60 min, CH4 15 min. Observing the results of the analyzes performed in this study, it appears that there is no single parameter that influences cell proliferation, but rather a set of ideal conditions that favor cell proliferation

Superfícies de titânio modificadas termoquimicamente por plasma : avaliação da resposta biológica

This laboratory study involves the participation of a group with professionals from different areas that had contributed to the construction of a multidisciplinary knowledge, about biological response of titanium surfaces modified through thermochemical treatment by plasma. Thus, the crystalline phase was previously characterized in relation to the topography, roughness, molhability and nitrogen concentration in the samples surface. It s indispensable that materials implanted can influence in a good cellular response as well as promotes a bacteria action. Surfaces modified by plasma were exposed to different cultures such as: cellular (human osteoblastic) and bacteria (Staphylococcus epidermidis ATCC35984 and Pseudomonas aeruginosa ATCC 27853) in order to evaluate the biological response. It was evaluated the adhesion, proliferation, morphology and cellular preference of human ostheoblastic cells (HOST), as well as the formation of a biofilm and bacteria proliferation. It was still analyzed the bacteria selectivity ability in relation to the surfaces. The software Image Pro Plus was used to the counting of cells and bacteria adhered to the surface of disks. The results were submitted to the variance analysis (ANOVA), and then, by the Kruskal-Wallis test, using GraphPad Instat ® software, version 3.5 to Windows. The nitrided samples in spite of show a higher roughness and molhability showed a smaller bacteria growing and higher cellular proliferation, when compared to non treated samples, indicating that the treated material present a high efficiency to biomedical implants

Comparison of the quantification of caffeine in human plasma by gas chromatography and ELISA

In the present study we evaluated the precision of the ELISA method to quantify caffeine in human plasma and compared the results with those obtained by gas chromatography. A total of 58 samples were analyzed by gas chromatography using a nitrogen-phosphorus detector and routine techniques. For the ELISA test, the samples were diluted to obtain a concentration corresponding to 50% of the absorbance of the standard curve. To determine whether the proximity between the I50 of the standard curve and that of the sample would bring about a more precise result, the samples were divided into three blocks according to the criterion of difference, in modulus, of the I50 of the standard curve and of the I50 of the sample. The samples were classified into three groups. The first was composed of 20 samples with I50 up to 1.5 ng/ml, the second consisted of 21 samples with I50 ranging from 1.51 to 3 ng/ml, and the third of 17 samples with I50 ranging from 3.01 to 13 ng/ml. The determination coefficient (R² = 0.999) showed that the data obtained by gas chromatography represented a reliable basis. The results obtained by ELISA were also reliable, with an estimated Pearson correlation coefficient of 0.82 between the two methods. This coefficient for the different groups (0.88, 0.79 and 0.49 for groups 1, 2 and 3, respectively) showed greater reliability for the test with dilutions closer to I50.

Modificação superficial do tecido de malha de ácido polilatico (PLA) por tratamento plasma

Some fibrous materials, for having properties such as biocompatibility, strength and flexibility, are of great interest for medical and pharmaceutical applications. Among these materials, the fabric made from polylactic acid (PLA) has received special attention, and beside to present these features, is derived from biological source, antimicrobial and bioabsorbable. One of the limitations of PLA is its low wettability and capillarity. Due to this, it is necessary to perform surface modification of the knitted fabric, increasing its hydrophilicity. This work aims to realize the plasma treatment at low pressure in order to increase the surface energy of the polymer. The work was divided into three steps: i) Influence of the gas ratio (oxygen and nitrogen) in the surface modification of PLA fabric after the plasma treatment, ii) physical characterization and physicochemical surface tissue; iii) Evaluation of the effect from current and gas ratio in the capillary rise of tissues and iv) Study of capillarity in yarns and fabrics. The results showed that better gas ratios were the atmospheres: 100% oxygen; 100% nitrogen and 50% oxygen and 50% nitrogen. The surface characterization showed changes in topography and introduction of polar groups which increased the wettability of the fabric. In another part of this study, it was found that the atmosphere containing only nitrogen gas showed the most capillary rise to a current of 0.15 A. The results in capillary yarns and fabrics showed that the thread reached equilibrium in a time much less than the fabric to an atmosphere of 100% nitrogen and 0.15 A. Current Plasma technology was effective to increase the hydrophilicity of PLA fabric, providing surface characteristics favorable for future application in the biomedical field

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R-N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R-N. Water wettability decreased as the proportion of N in the gas phase increased while surface toughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment. (c) 2006 Elsevier B.V. All rights reserved.

Corrosion behavior of Ti-6Al-4V alloy treated by plasma immersion ion implantation process

Ti-6Al-4V alloy is one of the most frequently used Ti alloys with diverse applications in aerospace and biomedical areas due to its favorable mechanical properties, corrosion resistance and biocompatibility. Meanwhile, its surface can stiffer intense corrosion caused by wear processes due to its poor tribological properties. Thus in the present study, PIII processing of Ti-6Al-4V alloy was carried out to evaluate its corrosion resistance in 3.5% NaCl solution. Two different sets of Ti-6Al-4V samples were PIII treated, varying the plasma gases and the treatment time. The corrosion behavior is correlated with the surface morphology, and the nitrogen content. SEM micrographs of the untreated sample reveal a typical two-phase structure. PIII processing promotes surface sputtering and the surface morphology is completely different for samples treated with N-2/H-2 mixture and N-2 only. The highest penetration of nitrogen (similar to 88 nm), corresponding to 33% of N-2 was obtained for the sample treated with N-2/H-2 mixture for 1:30 h. The corrosion behavior of the samples was investigated by a potentiodynamic polarization method. A large passive region of the polarization curves (similar to 1.5 V), associated with the formation of a protective film, was observed for all samples. The passive current density (similar to 3 x 10(-6) A cm(-2)) of the PIII-treated Ti-6Al-4V samples is about 10 times higher than for the untreated sample. This current value is still rather low and maintains good corrosion resistance. The anodic branches of the polarization curves for all treated Ti-6Al-4V samples demonstrate also that the oxide films break down at approximately 1.6 V, forming an active region. Although the sample treated by N-2/H-2 mixture for 1.30 It has thicker nitrogen enriched layer, better corrosion resistance is obtained for the PIII process performed with N, gas only. (c) 2007 Elsevier B.V. All rights reserved.

Nanohardness and contact angle of Si wafers implanted with N and C and Al alloy with N by plasma ion implantation

Surfaces of silicon wafers implanted with N and C, respectively, and aluminum 5052 implanted with N alone by plasma immersion ion implantation WHO were probed by a nanoindentor and analyzed by the contact-angle method to provide information on surface nanohardness and wettability. Silicon nitride and silicon carbide are important ceramic materials for microelectronics, especially for high-temperature applications. These compounds can be synthesized by high-dose ion implantation. The nanohardness of a silicon sample implanted with 12-keV nitrogen PIII (with 3 X 10(17) cm(-2) dose) increased by 10% compared to the unimplanted sample, in layers deeper than the regions where the formation of the Si,N, compound occurred. A factor of 2.5 increase in hardness was obtained for C-implanted Si wafer at 35 keV (with 6 X 10(17) cm(-2) dose), again deeper than the SiC-rich layer, Both compounds are in the amorphous state and their hardness is much lower than that of the crystalline compounds, which require an annealing process after ion implantation. In the same targets, the contact angle increased by 65% and 35% for N- and C-implanted samples, respectively. Compared to the Si target, the nitrogen PIII-irradiated Al 5052 (wish 15 keV) showed negligible change in its hydrophobic character after ion implantation. Its near-surface nanohardness measurement showed a slight increase for doses of 1 X 10(17) cm(-2). We have been searching for an AlN layer of the order of 1000 A thick, using such a low-energy PIII process, but oxide formation during processing has precluded its synthesis. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Treatment of PET and PU polymers by atmospheric pressure plasma generated in dielectric barrier discharge in air

Plasma treatments are frequently employed to modify surface properties of materials such as adhesivity, hydrophobicity, oleophobicity etc. Present work deals with surface modification of common commercial polymers such as polyethylene terephthalate (PET) and polyurethane (PU) by an air dielectric barrier discharge (DBD) at atmospheric pressure. The DBD treatment was performed in a plain reactor in wire-duct geometry (non-uniform field reactor), which was driven by a 60 Hz power supply. Material characterization was carried out by water contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The plasma-induced modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. The AFM analysis reveals that the plasma treatment roughens the material surface. Due to these structural and morphological changes the surface of DBD-treated polymers becomes more hydrophilic resulting in enhanced adhesion properties. (C) 2010 Elsevier B.V. All rights reserved.