917 resultados para Fourier transfer infrared spectroscopy
Resumo:
A indústria de alimentos está constantemente desenvolvendo produtos que fornecem, além de nutrientes, benefícios adicionais à saúde, tais como os enriquecidos com vitaminas. A vitamina D3 (colecalciferol) é sintetizada na pele durante a exposição da luz solar, controla a homeostase de cálcio e fósforo, metabolismo ósseo, pressão arterial e reabsorção renal de cálcio. O processo de microencapsulação vem sendo bastante aplicado em alimentos e um dos objetivos principais é o controle da liberação do agente ativo no momento e local desejado. A tecnologia de spray chilling é interessante para a microencapsulação de vitaminas lipossolúveis. O objetivo deste trabalho foi microencapsular vitamina D3, utilizando o método de spray chilling para a produção das micropartículas lipídicas sólidas (MLS). Para produção das MLS utilizou-se gordura vegetal com ponto de fusão em torno de 48 °C como carreador. Três tratamentos foram estabelecidos: sem aditivos (T1), com adição de 1% de cera de abelha (T2) e com 1% de lecitina de soja (T3). As micropartículas foram caracterizadas quanto à morfologia por microscopia eletrônica de varredura, tamanho médio por difração a laser, espectroscopia no infravermelho por transformada de Fourier (FTIR) e foi analisada a estabilidade da vitamina D3 durante o armazenamento a 10 e 25 °C, por meio de quantificações periódicas em cromatografia líquida de alta eficiência (CLAE). As micropartículas obtidas foram esféricas, semelhantes morfologicamente e com distribuição monocaudal de partículas. O tamanho médio das partículas variou em função dos seus ingredientes, sendo que as micropartículas produzidas apenas com vitamina e gordura foram menores em relação às demais (83,0% < 100 µm). A espectroscopia na região do infravermelho (FTIR) demonstrou que não ocorreu interação entre os ingredientes. A estabilidade da vitamina D3 encapsulada foi satisfatória ao longo de 65 dias com valores superiores a 87% para os três tratamentos e a temperatura apresentou influência na estabilidade. As MLS produzidas com cera apresentaram melhores resultados de estabilidade de vitamina D3 com valores de 90,18 ± 2,23 % após 65 dias de estocagem. Esses resultados são promissores e demostram a viabilidade da técnica de spray chilling na produção de MLS carregadas de vitamina D3, possibilitando uma futura aplicação em alimentos.
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Este trabalho concentra-se na preparação e caracterizações estrutural e espectroscópica de materiais nanoestruturados à base de SiO2-Nb2O5 dopados e codopados com íons Er3+, Yb3+ e Eu3+ na forma de pós e guias de onda planares. Os nanocompósitos foram preparados através de uma nova rota sol-gel utilizando óxido de nióbio como precursor em substituição ao alcóxido de nióbio. A correlação estrutura propriedades luminescentes foi estudada por difração de raios X, microscopia eletrônica de transmissão, espectroscopia vibracional de absorção no infravermelho, espectroscopia vibracional de espalhamento Raman, análise térmica, reflectância difusa e especular, espectroscopia de fotoluminescência e acoplamento M-line. Inicialmente foi avaliado a influência da concentração de nióbio nas propriedades estruturais e luminescentes de nanocompósitos (100-x)Si-xNb dopados e codopados com íons Er3+, Yb3+ e Eu3+ tratados termicamente a 900 °C por 3h. A cristalização do Nb2O5 foi dependente da concentração de Nb na matriz, com a distribuição dos íons lantanídeos preferencialmente no Nb2O5, afetando as propriedades luminescentes. Para os nanocompósitos codopados com íons Er3+ e Yb3+ foram obtidos valores de largura de banda a meia altura (FWHM) da ordem de 70 nm na região de 1550 nm e tempos de vida de até 5,2 ms. A emissão na região do visível, decorrente de processos de conversão ascendente, revelou-se dependente da concentração de nióbio. Foi verificada emissão preferencial na região do verde para menores concentrações de Nb. Enquanto que, para as maiores concentrações, processos de relaxação cruzada levaram a um aumento relativo na intensidade de emissão na região do vermelho. A eficiência quântica de emissão dos nanocompósitos (100-x)Si-xNb dopados com Eu3+ variou com o comprimento de onda de excitação, refletindo os diferentes sítios de simetria ocupados por este íons nesta estrutura complexa. A influência da temperatura de tratamento térmico no processo de cristalização do Nb2O5 em nanocompósitos 70Si:30Nb codopados com íons Er3+ e Yb3+ foi avaliada. Material amorfo foi obtido a 700 °C enquanto que a 900 e 1100 °C foram identificas as fases ortorrômbica (fase T) e monoclínica (fase M) do Nb2O5. Intensa emissão na região de 1550 nm com valores de FWHM de 52 e 67 nm e tempos de vida de 5,6 e 5,4 ms foram verificados a 700 e 900 °C sob excitação em 977 nm, respectivamente. Por fim, foram obtidos guias de onda planares com excelentes propriedades ópticas e com grande potencial de aplicação em dispositivos de amplificação óptica. Especificamente, materiais fotônicos com banda larga de emissão na região do infravermelho foram preparados, indicando fortemente a potencialidade para a aplicação em telecomunicações envolvendo não somente a banda C como também as bandas L e S em materiais contendo somente íons Er3+ como centros emissores.
Resumo:
Filmes à base de biopolímeros podem ser utilizados para produção de embalagens ativas, que além de proteger os alimentos, podem interagir com o produto. No caso de embalagens ativas com atividade antioxidante, tem-se privilegiado o uso de agentes antioxidantes naturais, considerando-se que o uso de antioxidantes sintéticos tem sido questionado, sobretudo em relação à sua inocuidade. Existem muitos extratos de plantas já conhecidos por sua atividade antioxidante, que têm sido utilizados com frequência em estudos de filmes à base de biopolímeros, não somente por serem ricos em polifenóis, mas principalmente por sua boa interação com a matriz polimérica. O extrato de boldo-do-Chile (Peumus boldus) possui atividade antioxidante comprovada, entretanto, não existem relatos sobre sua adição em filmes. Dessa forma, o objetivo geral desta tese foi o desenvolvimento de filmes à base de colágeno ou gelatina adicionados de extrato de boldo-do-Chile, com propriedades físicas e funcionais para seu emprego como embalagens bioativas. Foram realizadas as caracterizações (fenólicos totais, ABTS, DPPH, cor, °Brix e pH) do extrato aquoso de boldo-do-Chile, preparado em quatro diferentes temperaturas. Além disso, foram avaliadas as propriedades reológicas e térmicas da solução de gelatina, e também foram elaborados filmes com as soluções de gelatina e colágeno a partir de soluções filmogênicas com diferentes concentrações de macromoléculas e extrato de boldo. Esses filmes foram caracterizados para conhecimento de suas propriedades mecânicas (tração e perfuração), propriedades óticas (cor e opacidade), espessura, umidade e solubilidade em água. Uma concentração de macromoléculas foi escolhida para a realização de análises complementares, a saber: análises térmicas (DSC), cristalinidade por difração de raio X (DRX), permeabilidade ao vapor de água (PVA), microscopia eletrônica de varredura (MEV), brilho, espectroscopia de infravermelho com transformada de Fourier (FTIR), ângulo de contato, propriedades de barreira UV/Visível e atividade antioxidante. A adição do extrato de boldo-do-Chile nos filmes de gelatina e colágeno produziu filmes com atividade antioxidante, sem prejuízo às demais propriedades estudadas. Observou-se que o extrato aquoso de boldo-do-Chile apresentou propriedades antioxidantes, mas que foram dependentes da temperatura de extração. O extrato de boldo-do-Chile foi capaz de modificar as propriedades térmicas das soluções filmogênicas de gelatina, não sendo observado efeito nas análises reológicas. Por outro lado, o extrato aquoso de boldo-do-Chile não influenciou as propriedades mecânicas, solubilidade, umidade, cristalinidade e a permeabilidade ao vapor de água dos filmes de gelatina ou colágeno. Algumas propriedades térmicas sofreram efeito dos extratos, mas as análises de FTIR não mostraram a formação de novas interações. As propriedades óticas e de barreira UV/Visível foram influenciadas pelo extrato de boldo-do-Chile, sendo que os filmes se apresentaram mais amarelados com o aumento da concentração do extrato de boldo-do-Chile. As micrografias mostraram filmes de gelatina bastante homogêneos e filmes de colágeno com superfícies mais rugosas. Os resultados de brilho e ângulo de contato corroboraram com estas respostas. Em conclusão, os filmes de ambas macromoléculas apresentaram atividade antioxidante, podendo dessa forma, serem considerados como filmes ativos.
Resumo:
The electrochemical behaviour of o-cresol in acidic medium on platinum electrode has been studied by cyclic voltammetry and in situ Fourier transform infrared spectroscopy. The o-cresol suffers hydrolysis during oxidation giving rise to the formation of methyl-p-benzoquinone. In situ FTIR spectroscopic studies also reveal the presence of CO2, formed as a consequence of the rupture of the aromatic ring. Moreover, the oxidation of o-cresol in acidic medium produces a polymeric film on the platinum surface that precludes further oxidation of o-cresol. The reduction of o-cresol at potentials below 0 V produces in the first step the partial reduction of the aromatic ring and when the potential goes to values below 0 V, methyl-cyclohexanone.
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Edible active films based on sodium caseinate (SC) and calcium caseinate (CC) plasticized with glycerol (G) at three different concentrations and carvacrol (CRV) as active agent were prepared by solvent casting. Transparent films were obtained and their surfaces were analysed by optical microscopy and scanning electron microscopy (SEM). The influence of the addition of three different plasticizer concentrations was studied by determining tensile properties, while Fourier transformed infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were used to evaluate the structural and thermal behavior of such films. The addition of glycerol resulted in a reduction in the elastic modulus and tensile strength, while some increase in the elongation at break was observed. In general terms, SC films showed flexibility higher than the corresponding CC counterparts. In addition, the presence of carvacrol caused further improvements in ductile properties suggesting the presence of stronger interactions between the protein matrix and glycerol, as it was also observed in thermal degradation studies. FTIR spectra of all films showed the characteristic bands and peaks corresponding to proteins as well as to primary and secondary alcohols. In summary, the best results regarding mechanical and structural properties for caseinates-based films containing carvacrol were found for the formulations with high glycerol concentrations.
Resumo:
The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L-lactide by ring-opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long-term stability of a suspension of poly(lactic acid)-grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X-ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy.
Resumo:
The disintegration under composting conditions of films based on poly(lactic acid)–poly(hydroxybutyrate) (PLA–PHB) blends and intended for food packaging was studied. Two different plasticizers, poly(ethylene glycol) (PEG) and acetyl-tri-n-butyl citrate (ATBC), were used to limit the inherent brittleness of both biopolymers. Neat PLA, plasticized PLA and PLA–PHB films were processed by melt-blending and compression molding and they were further treated under composting conditions in a laboratory-scale test at 58 ± 2 °C. Disintegration levels were evaluated by monitoring their weight loss at different times: 0, 7, 14, 21 and 28 days. Morphological changes in all formulations were followed by optical and scanning electron microscopy (SEM). The influence of plasticizers on the disintegration of PLA and PLA–PHB blends was studied by evaluating their thermal and nanomechanical properties by thermogravimetric analysis (TGA) and the nanoindentation technique, respectively. Meanwhile, structural changes were followed by Fourier transformed infrared spectroscopy (FTIR). The ability of PHB to act as nucleating agent in PLA–PHB blends slowed down the PLA disintegration, while plasticizers speeded it up. The relationship between the mesolactide to lactide forms of PLA was calculated with a Pyrolysis–Gas Chromatography–Mass Spectrometry device (Py–GC/MS), revealing that the mesolactide form increased during composting.
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Tourmaline from a gem-quality deposit in the Grenville province has been studied with X-ray diffraction, visible-near infrared spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, electron microprobe and optical measurements. The tourmaline is found within tremolite-rich calc-silicate pods hosted in marble of the Central Metasedimentary Belt. The crystals are greenish-greyish-brown and have yielded facetable material up to 2.09 carats in size. Using the classification of Henry et al. 2011 the tourmaline is classified as a dravite, with a representative formula shown to be (Na0.73Ca0.2380.032)(Mg2+2.913Fe2+0.057Ti4+0.030) (Al3+5.787Fe3+0.017Mg2+0.14)(Si6.013O18)(BO3)3(OH)3((OH,O)0.907F0.093). Rietveld analysis of powder diffraction data gives a = 15.9436(8) Å, c = 7.2126(7) Å and a unit cell volume of 1587.8 Å3. A polished thin section was cut perpendicular to the c-axis of one tourmaline crystal, which showed zoning from a dark brown core into a lighter rim into a thin darker rim and back into lighter zonation. Through the geochemical data, three key stages of crystal growth can be seen within this thin section. The first is the core stage which occurs from the dark core to the first colourless zone; the second is from this colourless zone increasing in brown colour to the outer limit before a sudden absence of colour is noted; the third is a sharp change from the end of the second and is entirely colourless. These events are the result of metamorphism and hydrothermal fluids resulting from nearby felsic intrusive plutons. Scanning electron microscope, and electron microprobe traverses across this cross-section revealed that the green colour is the result of iron present throughout the system while the brown colour is correlated with titanium content. Crystal inclusions in the tourmaline of chlorapatite, and zircon were identified by petrographic analysis and confirmed using scanning electron microscope data and occur within the third stage of formation.
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As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.
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Here we present a detailed multi-proxy record of the climate and environmental evolution at Lake El'gygytgyn, Far East Russian Arctic during the period 430-395 ka covering the marine isotope stage (MIS) 12/11 transition and the thermal maximum of super interglacial MIS 11c. The MIS 12/11 transition at Lake El'gygytgyn is characterized by initial warming followed by a cold reversal implying similarities to the last deglaciation. The thermal maximum of MIS 11c is characterized by full and remarkably stable interglacial conditions with mean temperatures of the warmest month (MTWM) ranging between ca. 10-15 °C; annual precipitation (PANN) ranging between ca. 300-600 mm; strong in-lake productivity coinciding with dark coniferous forests in the catchment; annual disintegration of the lake ice cover; and full mixis of the water column. Such conditions persisted, according to our age model, for ca. 27 ± 8 kyr between ca. 425-398 ka. The Lake El'gygytgyn record closely resembles the climate pattern recorded in Lake Baikal (SE Siberia) sediments and Antarctic ice cores, implying interhemispheric climate connectivity during MIS 11c.
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We present biogenic opal flux records from two deep-sea sites in the Scotia Sea (MD07-3133 and MD07-3134) at decadal-scale resolution, covering the last glacial cycle. Besides conventional and time-consuming biogenic opal measuring methods, we introduce new biogenic opal estimation methods derived from sediment colour b*, wet bulk density, Si/Ti-count ratio, and Fourier transform infrared spectroscopy (FTIRS). All methods capture the biogenic opal amplitude, however, FTIRS - a novel method for marine sediment - yields the most reliable results. 230Th normalization data show strong differences in sediment focusing with intensified sediment focusing during glacial times. At MD07-3134 230Th normalized biogenic opal fluxes vary between 0.2 and 2.5 g/cm2/kyr. Our biogenic opal flux records indicate bioproductivity changes in the Southern Ocean, strongly influenced by sea ice distribution and also summer sea surface temperature changes. South of the Antarctic Polar Front, lowest bioproductivity occurred during the Last Glacial Maximum when upwelling of mid-depth water was reduced and sea ice cover intensified. Around 17 ka, bioproductivity increased abruptly, corresponding to rising atmospheric CO2 contents and decreasing seasonal sea ice coverage.
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The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon(TM) 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane(R) 2363-80A, Pellethane(R) 2363-55D and Bionate(R) 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane(R) 80A, and as good as or better than both of the harder commercially available negative control polyurethanes. Pellethane(R) 55D and Bionate(R) 55D. Changes observed in the surface of the Pellethane(R) materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane(R) 80A significantly more severe than that observed in Pellethane(R) 55D. Very minor changes were seen on the surfaces of the Elast-Eon(TM) 2 80A and Bionate(R) 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, M-w/M-n, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon(TM) 2 80A and Bionate(R) 55D following implantation under strained conditions. However, ultimate strain decreased and elastic modulus increased in the explanted specimens of all three materials when compared with their unimplanted unstrained counterparts. The results indicate that a soft, flexible PDMS-based polyurethane synthesized using 20% PHMO and 80% PDMS macrodiols has excellent long-term biostability compared with commercially available polyurethanes. (C) 2004 Elsevier Ltd. All rights reserved.
Resumo:
Polybenzoxazine (PBA-a)/poly(epsilon-caprolactone) (PCL) blends were prepared by an in situ curing reaction of benzoxazine (BA-a) in the presence of PCL. Before curing, the benzoxazine (BA-a)/PCL blends are miscible, which was evidenced by the behaviors of single and composition-dependant glass transition temperature and equilibrium melting point depression. However, the phase separation induced by polymerization was observed after curing at elevated temperature. It was expected that after curing, the PBA-a/PCL blends would be miscible since the phenolic hydroxyls in the PBA-a molecular backbone have the potential to form inter- molecular hydrogen-bonding interactions with the carbonyls of PCL and thus would fulfil the miscibility of the blends. The resulting morphology of the blends prompted an investigation of the status of association between PBA-a and PCL under the curing conditions. Although Fourier-transform infrared spectroscopy (FT-IR) showed that there were intermolecular hydrogen-bonding interactions between PBA-a and PCL at room temperature, especially for the PCL-rich blends, the results of variable temperature FT-IR spectroscopy by the model compound indicate that the phenolic hydroxyl groups could not form efficient intermolecular hydrogen-bonding interactions at elevated temperatures, i.e., the phenolic hydroxyl groups existed mainly in the non-associated form in the system during curing. The results are valuable to understand the effect of curing temperature on the resulting morphology of the thermosetting blends. SEM micrograph of the dichloromethane-etched fracture surface of a 90:10 PBA-a PCL blend showing a heterogeneous morphology.
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Ordered mesoporous bioactive glasses (MBGs) with different compositions were prepared by using nonionic block copolymer surfactants as structure-directing agents through an evaporation-induced self-assembly process. Their in-vitro bioactivities were studied in detail by electron microscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma (ICP) atomic emission spectroscopy. The ICP element analysis results were further calculated in terms of the total consumption of Ca and P, Delta[Ca]/Delta[P] ratios, and ionic activity product (IP) of hydroxyapatite. Through the above analysis, it is clear that MBGs show a different structure-bioactivity correlation compared to conventional sol-gel-derivcd BGs. The in vitro bioactivity of MBGs is dependent on the Si/Ca ratio in the network when the other material parameters such as the mesostructure and texture properties (pore size, pore volume) are controlled. MBG 80S15C with relatively lower calcium content exhibits the best in vitro bioactivity, in contrast to conventional sol-gel-derived BGs where usually higher calcium percentage BGs (e.g. 60S35C) show better bioactivity. Calcination temperature is another important factor that influences the in vitro bioactivity. According to our results, MBGs calcined at 973 K may possess the best in vitro bioactivity. The influences of the composition and calcination temperature upon bioactivity are explained in terms of the unique structures of MBGs. (c) 2006 Elsevier Ltd. All rights reserved.
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Ultem 1000 polyetherimide films prepared by cast-evaporating technique were covered with a 1H,1H,2H-tridecafluoro-oct-1-ene (PFO) plasma-polymerized layer. The effects of the plasma exposure time on the surface composition were studied by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and surface energy analysis. The surface topography of the plasma layer was deduced from scanning electron microscopy. The F/C ratio for plasma-polymerized PFO under the input RF power of 50 W can be as high as 1.30 for 480 s and similar to 0.4-2 at % of oxygen was detected, resulting from the reaction of long-lived radicals in the plasma polymer with atmospheric oxygen. The plasma deposition of fluorocarbon coating from plasma PFO reduces the surface energy from 46 to 18.3 mJ m(-2). (c) 2006 Wiley Periodicals, Inc.