Effect of current density on the microstructure and corrosion properties of plasma electrolytic oxidation (PEO) coatings on AM50 Mg alloy produced in an electrolyte containing clay additives

Plasma electrolytic oxidation coatings were produced on AM50 Mg alloy in alkaline phosphate based electrolyte with montmorillonite clay additives employing current densities of 30, 60, and 120 mA/cm(2). The effect of current density on the microstructure and corrosion properties of the coating was investigated. The clay additives got melted and reactively incorporated into the coating forming an amorphous phase, at all the current densities. However, the coating was predominantly amorphous only at 30 mA/cm(2) and with increasing current density, increasing fractions of crystalline phases were formed. Higher current densities resulted in increased thickness of the coating, but reduced the compactness of the coatings. Electrochemical impedance spectroscopy tests in 0.5 wt.% (0.08 M) and 3.5 wt.% (0.6 M) NaCl solution revealed that the coatings processed at 30 mA/cm(2) exhibited a relatively better initial corrosion resistance owing to its relatively defect-free barrier layer and compactness of the coating. However, the presence of amorphous phases in significant amounts and lack of MgO in the coating resulted in increased rate of dissolution of the coatings and degradation of corrosion resistance. Coatings produced at higher current densities exhibited initial inferior corrosion resistance due to a more defective barrier layer and increased porosity in pore band and outer porous layer. However, the increased amount of crystalline phases and an increased amount of MgO, which resisted dissolution, counterbalanced the negative effects of defective barrier and increased porosity resulting in a relatively lower rate of the degradation of the corrosion resistance. Thus, the corrosion resistance of all the coatings continuously decreased with time and became similar after prolonged immersion in NaCl solution. Increasing current density, therefore, did not prove to be beneficial for the improvement of the corrosion performance of the PEO coatings. (C) 2016 Elsevier B.V. All rights reserved.

Avaliação das propriedades de barreira a gases de membranas obtidas a partir de dispersões aquosas à base de poliuretanos e argila

Materiais nanoestruturados têm recebido destaque na comunidade científica, destacando-se, dentre eles, os nanocompósitos à base de polímeros e argila. Quando esses materiais são obtidos no estado líquido, ressalta-se também o uso de água em substituição a solventes orgânicos, devido a questões ambientais. Neste trabalho foram sintetizadas dispersões aquosas à base de poliuretanos (WPUs) e argila hidrofílica do tipo montimorilonita (MMT) de natureza sódica, com o objetivo de avaliar as propriedades de barreira a gases conferidas pela presença de argila e pela variação nas proporções entre os segmentos flexíveis poli(glicol propilênico) (PPG) e o copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG). Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e etilenodiamina (EDA), como extensor de cadeia. Foram sintetizadas dispersões aquosas com e sem a presença de argila, fixando-se a razão entre o número de equivalentes-grama de grupos diisocianato e hidroxila (razão NCO/OH) em 1,5. Nas formulações foi variado também o teor de argila em relação à massa de prepolímero em 0,5% e 1%. Foi adicionada uma etapa de agitação adicional com dispersor Turrax em algumas formulações. A argila foi previamente deslaminada em água deionizada e incorporada à formulação na etapa da dispersão do prepolímero. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade aparente. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR) e permeabilidade ao CO2. A resistência térmica dos filmes foi determinada por termogravimetria (TG). Foram observadas modificações nas propriedades dos filmes obtidos com a inserção da argila e com a variação no teor de segmentos à base de poli(glicol etilênico). A inserção da argila promoveu uma melhoria na resistência térmica das membranas bem como uma redução na permeabilidade das mesmas. Foi observado um aumento na permeabilidade das membranas obtidas a partir das formulações com maior percentual de copolímero (EG-b-PG), com e sem argila.

Tenacificação em Nanocompósitos de Poliamida 6 e Argila

Nanocompósitos de poliamida 6 (PA6) e montmorilonita modificada com sal de amônio quaternário têm sido estudados, visando melhorar as propriedades térmicas e mecânicas. De fato os efeitos da nano-escala e da interação carga-matriz resultam em maior módulo de elasticidade e resistência à tração, porém a deformação é reduzida. Assim, nesse trabalho, optou-se por adicionar elastômeros, terpolímero de etileno-propileno-dieno (EPDM) e terpolímero de etileno-propileno-dieno modificado com anidrido maleico (EPDM-MA), ao sistema PA 6/argila organofílica para recuperar os valores de deformação. Foi utilizada montmorilonita modificada com cloreto de dimetildioctadecil amônio. A intercalação por fusão foi realizada em câmara interna de mistura. Além das propriedades mecânicas, térmicas e reológicas, foram investigadas as modificações na cristalinidade da fase PA-6 em função da adição da argila modificada, EPDM e EPDM-MA, detectando-se as variações no grau de cristalinidade e nas temperaturas de fusão e cristalização. Os difratogramas de raios-x revelaram ocorrência de intercalação/esfoliação e também modificação da forma cristalina da PA 6, indicando a formação do cristal gama

Estudo da incorporação de diferentes tipos de argilas hidrofílicas em dispersões aquosas de poliuretanos para formação de nanocompósitos

Neste trabalho foram sintetizados nanocompósitos à base de poliuretanos em dispersão aquosa (NWPUs) e argilas hidrofílicas do tipo montimorilonita (MMT) de natureza sódica e cálcica. Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA) e diisocianato de isoforona (IPDI). Os NWPUs tiveram as argilas, previamente deslaminadas em água e incorporadas à formulação no momento da dispersão do prepolímero. Dispersões aquosas (WPUs), sem a presença de argila, foram sintetizadas como base, nas quais foram variadas a razão NCO/OH e a proporção de copolímero em relação ao PPG. Nas formulações NWPUs, foram variados também o teor de argila em relação à massa de prepolímero e o tipo de argila sódica e cálcica. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR), difração de raios-x (XRD) e microscopia eletrônica de varredura (SEM). A resistência térmica dos filmes foi determinada por termogravimetria (TG) e a resistência mecânica dos filmes foi avaliada por ensaios mecânicos em dinamômetro. O grau de absorção de água dos filmes também foi determinado. A formação de nanocompósitos à base de água foi confirmada pela ausência do pico de XRD, característico das argilas empregadas na maioria dos filmes analisados. As micrografias obtidas por SEM confirmam uma dispersão homogênea das argilas na matriz poliuretânica. Os filmes à base de nanocompósitos (NWPUs) apresentaram propriedades superiores às apresentadas por aqueles obtidos a partir das dispersões sem argilas (WPUs). Os revestimentos formados a partir da aplicação das dispersões aderiram à maioria dos substratos testados (metal, vidro, madeira e papel) formando superfícies homogêneas

The effect of cationic, non-ionic and amphiphilic surfactants on the intercalation of bentonite

Surfactant-clay interactions are key for the development of new clay applications and inorganic-organic nanocomposites. Bentonite, with montmorillonite as the principal clay mineral constituent, was modified with varying concentrations of hexadecethyltrimethylammonium chloride (HDTMA), as a reference cationic surfactant, polypropylene glycol (PPG) 1200 and 2000, as non-ionic surfactants, and lecithin and Topcithin®, as amphiphilic phospholipid surfactants, according to the cation exchange capacity (CEC). The modified bentonites were characterised by X-ray diffraction, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectrometry, specific surface area and pore volume. Three intercalation regions have been identified depending on the surfactant. The non-ionic surfactant caused only a crystalline expansion of bentonite interlayers, while the cationic surfactant induced an osmotic intercalation. The amphiphilic lecithin derivatives intercalated more extensively with the bentonite matrix. The TGA and the FTIR spectra showed that, at lower concentrations, the PPGs and HDTMA adopted a disordered conformation that required more energy to degrade, while at higher concentrations, the surfactants were ordered in the interlayer space of the bentonite. The lecithin derivative surfactant had a greater thermal and conformation stability. The specific surface area reduced with increasing surfactant concentrations. This study highlights the effect of surfactant type on the interlayer space of montmorillonite in the perspective of developing novel clay functions. © 2013.

Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells Journal of Power Sources

A new type of sulfonated clay (clay-SO3H) was prepared by the ion exchange method with the sulfanilic acid as the surfactant agent. The grafted amount of sulfanilic acid in clay-SO3H was 51.8 mequiv. (100 g)(-1), which was measured by thermogravimetric analysis (TGA). Sulfonated poly(ether ether ketone) (SPEEK)/clay-SO3H hybrid membranes which composed of SPEEK and different weight contents of clay-SO3H, were prepared by a solution casting and evaporation method. For comparison, the SPEEK/clay hybrid membranes were produced with the same method.

The Effect of MMT/Modified MMT on the Structure and Performance of the Superabsorbent Composite

A series of superabsorbent composites containing Montmorillonite (MMT), modified- Montmorillonite (OMMT) and sodium acrylate were synthesized by free-radical polymerization in aqueous solution. The structure of composites was characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and the results showed that the polymer chains were grafted onto the edge and the surface of MMT or OMMT. At the same time, the equilibrium swelling ratio of the composites was investigated as a function of the clay content and the results showed that the equilibrium swelling ratio of composites was improved by the introduction of clay.

Syntheses of opened hollow clay microspheres through a spray-drying approach and their derivative clay/carbon nanotubes composites

Opened hollow microspheres of organoclays were prepared via spray drying the suspension of modified Na+-montmorillonite (Na+-MMT) with alkylsulfonate. The microstructure and thermal properties of these opened hollow spheres were characterized by means of wide-angle X-ray diffraction, field emission scanning electron microscopy, and thermogravimetric analysis. The results showed that the organoclays had larger interlayer spacing compared with pure Na+-MMT and higher thermal stability relative to the alkylsufonate.

A strategy of fabricating exfoliated thermoplastic polyurethane/clay nanocomposites via introducing maleated polypropylene

By reducing the attraction between the platelets of octaclecylammonium chloride modified montmorillonite (OMMT-C18) via pre-intercalation of maleated polypropylene (MAPP), OMMT-C18 was exfoliated in thermoplastic polyurethane (TPU) matrix during melt-mixing. Wide angle X-ray diffraction, transmission electron microscopy and thermogravimetric analysis were used to investigate the microstructure of TPU nanocomposites. Three factors (including introducing sequence, the kind and the content of MAPP) showed important effects on the dispersion degree of OMMT-C18 in TPU matrix. The results confirmed that the pre-intercalation of MAPP was necessary for the exfoliation of OMMT-C18; however, the role of MAPP in TPU nanocomposites was different from that in polypropylene nanocomposites.

A Simple Method for Preparing Carbon Nanotubes/Clay Hybrids in Water

A simple novel method for preparing multiwalled carbon nanotubes/montmorillonite (MWNTs/MMT) hybrids has been established through mixing pristine MWNTs in MMT aqueous dispersion. The principle of this method is based on the formation of stable dispersion containing both MWNTs and MMT in water, which results from strong interaction between MWNTs and MMT platelets. Sedimentation experiments, measurements of potential, and Raman spectra have been used to confirm the presence of strong interaction between MWNTs and MMT sheets. The morphology observation for the dried MWNTs/MMT hybrids shows that the obtained hybrids are homogeneous, in which MWNTs exist as the state of single nanotubes that are absorbed on the surface and edge of MMT sheets.

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene (PP)/organically modified montmorillonite (OMMT) nanocomposites. The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation. The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis (TGA). The structural evolution and composition change in the surface region of PP/OMMT nanocomposites during heating were monitored by means of X-ray photoelectron spectroscopy (XPS), ATR-FTIR and field emission scanning electron microscopy (FESEM).

Polyampholytes superabsorbent nanocomposites with excellent gel strength

A series of novel polyampholyte superabsorbent nanocomposites with excellent gel strength were synthesized by in situ solution polymerization in aqueous solution. Acrylic acid and acryloyloxyethyl trimethyl ammonium chloride (DAC) were employed as ionic monomers and montmorillonite (MMT) was used as inorganic component. The addition of cationic component could supply the positive charge in the network of nanocomposite and promote the formation of nanostructure of composites due to the interaction between DAC and clay platelets. The performance of polyampholyte nanocomposites were investigated and the result showed that the gel strength of nanocomposite hydrogel in distilled water and 0.9 wt% NaCl solution could reach 198.85 and 204.23 mJ/g, respectively, which were 13 times of the gel strength of matrix. The investigation of swelling behaviors showed that the nanocomposites had particular swelling behaviors of polyampholytes hydrogel in solution with different pH values and concentration of NaCl.