Competitividade de diferentes atmosferas de plasma sobre as propriedades hidrofílicas em tecidos de polilático

Os polímeros biodegradáveis, como o poliácido láctico (PLA) apesar de consolidado nos campos farmacêuticos, médico e biomédico como biomateriais úteis para aplicações variadas, porém, depende da necessidade de funcionalizar a sua superfície estudando suas propriedades tais como hidrofilidade e hidrofobicidade favorecendo a interação do polímero com os materiais de aplicação farmacêutica, médica e biomédica. Este trabalho tem como objetivo produzir um material com características diferentes em cada um de seus lados, sendo um lado hidrofílico e o outro hidrofóbico. O substrato têxtil utilizado neste estudo foi um tecido de malha de composição 100% PLA que é biodegradável e biocompatível, o que possibilita sua aplicação na área biomédica. Para modificação superficial foi utilizado o tratamento a plasma de baixa pressão. A técnica de modificação de superfície por plasma foi escolhida por ser uma tecnologia limpa, anticorrosiva e não tóxica ao contrario de muitos processos químicos convencionais utilizados na indústria têxtil, além disso, não afeta as propriedades de massa do substrato. Neste estudo, um lado da superfície do substrato foi tratado com plasma oxigênio, argônio e nitrogênio, para o trabalho de melhoria da hidrofilidade da superfície e metano para a hidrofobicidade da amostra. A espectroscopia de emissão ótica (OEE) foi utilizada para fazer o diagnóstico das espécies do plasma durante o tratamento. Após o tratamento a plasma as amostras foram caracterizadas por medidas de ângulo de contato, microscopia eletrônica de varredura (MEV), Espectroscopia de fotoelétrons de raios-X (XPS), Infravermelho com Transformada de Fourier (FTIR) de reflexão total atenuada (ATR), medidas da área de espalhamento do líquido e arraste vertical. Onde foi caracterizado o aumento e diminuição da molhabilidade das amostras tratadas por plasma bem como as variáveis que contribuíram para tal efeito. O tratamento das amostras de PLA com O2 + CH4 apresenta comportamento hidrofílico no lado tratado com O2, apresentando aumento de rugosidade e grupos funcionais e no lado tratado com CH4, apresentando a formação de um filme polimérico formado sobre a superfície da amostra. O tratamento com N2 + CH4 apresenta comportamento hidrofóbico, porém com variações no fluxo do CH4 tem-se um controle da molhabilidade na superfície das amostras, podendo ir de hidrofóbico a hidrofílico, neste tratamento as amostras apresentaram pequenas diferenças de molhabilidade entre os lados tratados com plasma de N2 e com plasma de CH4

Medida indireta de temperatura de corpos imersos em plasma

O gradiente térmico da superfície para o interior do sólido depende da taxa de colisões das partículas e da condutividade térmica do material utilizado. Quando um sólido é imerso em plasma, a transferência de energia ocorre por radiação e colisões das partículas sobre a superfície do material. Dependendo da taxa de colisões das particulas e da condutividade térmica do sólido existirão gradientes térmicos da superfície para o interior das amostras, ocorrendo picos térmicos na superficie, ou seja, o aquecimento pontual nas regiões de colisões. A fim de estudar esse efeito, amostras de aço rápido AISI M35 cujos valores de dureza são fortemente sensíveis à temperatura de revenimento, foram utilizadas como micro sensores térmicos. Amostras foram temperadas em forno resistivo e, em seguida, parte das mesmas foram revenidas em forno resistivo e a outra parte em plasma. A partir do gráfico da dureza (Hv) em função da temperatura (T) das amostras revenidas em forno resistivo foi possível obter uma função Hv(T) para determinação indireta do perfil térmico das amostras tratadas em plasma. As amostras foram revenidas em plasma utilizando temperatura de referência igual a 550 oC. Em seguida foi obtido o perfil de dureza dessas amostras ao longo da seção transversal e, subsequentemente, o perfil de temperatura. Verificou-se que amostras tratadas em plasma, ao contrário daquelas tratadas em forno resistivo, apresentaram gradiente de temperatura da superfície para o núcleo. Além disso, verificou-se que as amostras tratadas em configuração planar apresentaram gradientes térmicos inferiores àquelas tratadas em configuração cátodo oco, variando de 20 a 120 °C, respectivamente

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

Desenho e Construção de um protótipo gerador de jato de plasma frio a pressão atmosférica para aplicações biomédicas

Research for better performance materials in biomedical applications are constants. Thus recent studies aimed at the development of new techniques for modification of surfaces. The low pressure plasma has been highlighted for its versatility and for being environmentally friendly, achieving good results in the modification of physic chemical properties of materials. However, it is requires an expensive vacuum system and cannot able to generate superficial changes in specific regions. Furthermore, it is limits their use in polymeric materials and sensitive terms due to high process temperatures. Therefore, new techniques capable of generating cold plasma at atmospheric pressure (APPJ) were created. In order to perform surface treatments on biomaterials in specific regions was built a prototype capable of generating a cold plasma jet. The prototype plasma generator consists of a high voltage source, a support arm, sample port and a nozzle through which the ionized argon. The device was formed to a dielectric tube and two electrodes. This work was varied some parameters such as position between electrodes, voltage and electrical frequency to verify the behavior of glow discharges. The disc of titanium was polished and there was a surface modification. The power consumed, length, intensity and surface modifications of titanium were analyzed. The energy consumed during the discharges was observed by the Lissajous figure method. To check the length of the jets was realized with Image Pro Plus software. The modifications of the titanium surfaces were observed by optical microscopy (OM ) and atomic force microscopy (AFM ). The study showed that variations of the parameters such as voltage, frequency and geometric position between the electrodes influence the formation of the plasma jet. It was concluded that the plasma jet near room temperature and atmospheric pressure was able to cause modifications in titanium surface

Estudo das ligas titânio-zircônio resultantes do processo de fundição plasma-skull para aplicações como biomateriais

The aim of this work was to study a series of 11 different compositions of Ti-Zr binary alloys resistance to aggressive environment, i. e., their ability to keep their surface properties and mass when exposed to them as a way to evaluate their performance as biomaterials. The first stage was devoted to the fabrication of tablets from these alloys by Plasma-Skull casting method using a Discovery Plasma machine from EDG Equipamentos, Brazil. In a second stage, the chemical composition of each produced tablet was verified. In a third stage, the specimen were submitted to: as-cast microstructure analysis via optical and scanning electron microscopy (OM and SEM), x-ray dispersive system (EDS) chemical analysis via SEM, Vickers hardness tests for mechanical evaluation and corrosion resistence tests in a 0.9% NaCl solution to simulate exposition to human saliva monitored by open circuit potential and polarization curves. From the obtained results, it was possible to infer that specimens A1 (94,07 wt% Ti and 5,93% wt% Zr), A4 (77,81 wt % Ti and 22,19 wt % Zr) and A8 (27,83 wt% Ti and 72,17 wt% Zr), presented best performance regarding to corrosion resistance, homogeneity and hardness which are necessary issues for biomaterials to be applied as orthopedic and odontological prosthesis

Confecção e caracterização físico-química de filmes compósitos autossustentáveis NaAlg-TiO2-WO3

A new self-sustainable film was prepared through the sol-gel modified method, previously employed in our research group; sodium alginate was used as the polymer matrix, along with plasticizer glycerol, doped with titanium dioxide (TiO2) and tungsten trioxide (WO3). By varying WO3 concentration (0,8, 1,6, 2,4 and 3,2 μmol) and keeping TiO2 concentration constant (059 mmol), it was possible to study the contribution of these oxides on the obtained films morphological and electrical properties. Self-sustainable films have analyzed by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XDR), Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and Electrochemical Impedance Spectroscopy (EIS). By the IR specters, it was possible identify the TiO2, and posteriorly WO3, addition has provided dislocation of alginate characteristics bands to smaller vibrations frequencies indicating an electrostatic interaction between the oxides and the polymer matrix. Diffractograms show predominance of the amorphous phase in the films. SEM, along with EDX, analysis revealed self-sustainable films showed surface with no cracks and relative dispersion of the oxides throughout the polymer matrix. From Impedance analysis, it was observe increasing WO3 concentration to 2,4 μmol provided a reduction of films resistive properties and consequent improvement of conductive properties

Obtenção e caracterização de filmes SnO2 depositados em vidro borosilicato por silk-screen modificado: SnCl2.2H2O como precursor

O presente trabalho tem como objetivo investigar as características de filmes de SnO2 depositados em substrato de vidro borosilicato por um processo de silk-screen modificado para obtenção de espessura fina compatível com a aplicação em células solares policristalinas de baixo custo. O filme de SnO2 é um dos mais apropriados para obtenção de vidro TCO (transparent conductive oxide) para uso em células solares devido a sua baixa resistividade elétrica e alta transmitância, sendo quimicamente inerte, mecanicamente duro e tem resistência a altas temperaturas, o que facilita então a calcinação das amostras entre 500º C a 550º C. Os filmes foram obtidos a partir de uma solução precursora básica, preparada pela dissolução de SnCl2.2H2O em Etanol (99,5 %). Foi realizado um planejamento fatorial 2(3-1) para analisar a influência dos parâmetros concentração da solução precursora (CETN), temperatura de calcinação (TC) e taxa de aquecimento (tX) na calcinação, sendo a concentração CETN o parâmetro que apresentou maior efeito sobre os parâmetros de respostas investigados: espessura do filme (ω), resistividade de superfície (ρ) e a transmitância relativa (θ). Foi possível obter com a metodologia utilizada, filmes com espessuras da ordem de 1 Nm com resistividade de superfície de 10 / e transmitância relativa entre 70 e 80 %.

Modificação de superfícies de titânio tratadas por plasma de Ar + N2 + O2 visando aplicações biomédicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES

Processing of highly porous titanium parts by metal injection moulding in combination with innovative plasma treatment

A combinação da Moldagem por Injeção de pós Metálicos (Metal Injection Moulding MIM) e o Método do Retentor Espacial (Space Holder Method - SHM) é uma técnica promissora para fabricação de peças porosas de titânio com porosidade bem definida como implantes biomédicos, uma vez que permite um alto grau de automatização e redução dos custos de produção em larga escala quando comparado a técnica tradicional (SHM e usinagem a verde). Contudo a aplicação desta técnica é limitada pelo fato que há o fechamento parcial da porosidade na superfície das amostras, levando ao deterioramento da fixação do implante ao osso. E além disso, até o presente momento não foi possível atingir condições de processamento estáveis quando a quantidade de retentor espacial excede 50 vol. %. Entretanto, a literatura descreve que a melhor faixa de porosidade para implantes de titânio para coluna vertebral está entre 60 - 65 vol. %. Portanto, no presente estudo, duas abordagens foram conduzidas visando a produção de amostras altamente porosas através da combinação de MIM e SHM com o valor constante de retentor espacial de 70 vol. % e uma porosidade aberta na superfície. Na primeira abordagem, a quantidade ótima de retentor espacial foi investigada, para tal foram melhorados a homogeneização do feedstock e os parâmetros de processo com o propósito de permitir a injeção do feedstock. Na segunda abordagem, tratamento por plasma foi aplicado nas amostras antes da etapa final de sinterização. Ambas rotas resultaram na melhoria da estabilidade dimensional das amostras durante a extração térmica do ligante e sinterização, permitindo a sinterização de amostras de titânio altamente porosas sem deformação da estrutura.

Estudo da adesão de pinos endodônticos modificados superficialmente por plasma de oxigênio

The work presents the effect of plasma treatment when applied in fibers or carbon/glass posts in the adhesion fiber/resin and posts/cement. This has for objective the modification of the surface of the fibers, as well as the wettability of the posts, seeking the improvement of the adhesion and of the connection fiber/resin in the processing of polymeric composites reinforced with the same ones. 120 posts (Reforpost) were used and 30 meters of fibers of carbon and of glass (Fibrex), of the company Angelus. The samples were divided in three groups of 40 specimens: GROUP I - 20 posts of glass fiber and 20 of carbon without treatment to it shapes, GROUP II -20 posts of glass fiber and 20 of carbon treated to it shapes in the surface and GROUP III - 20 posts of glass fiber and 20 of carbon make with fibers in natura after plasma treatment. The plasma treatment was accomplished with oxygen and with temperature in the camera fixed at 200°C, for one hour of exhibition. The posts and the fibers were characterized before and after the treatment. The wettability was measure by pendent drop method, and interface fiber/resin and posts/cement were observed by optical and electronic microscopy. It was observed that both wettability and texture were increased with plasma treatment

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

Tratamento termoquímico do titânio auxiliado por plasma de ar - N2 - O2

Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension

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.

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+

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