Heterocyclic polyimides containing siloxane groups in the main chain

BACKGROUND: Among the polymers widely studied for applications in advanced techniques, aromatic polyimides have received considerable attention due to their outstanding thermal stability associated with good electrical and mechanical properties. However, these polymers are usually difficult to process, being insoluble and without a glass transition. To improve the processing characteristics of polyimides, modification of their structure is often achieved by the introduction of flexible linkages in the macromolecular chain or various substituents on the aromatic rings. RESULTS: A series of polyimides and intermediate polyamidic acids were synthesized from aromatic oxadiazole‐diamines and a dianhydride containing a siloxane bridge (? R₂Si? O? SiR₂? ). These polymers exhibit good solubility in certain organic solvents and can be cast into thin and very thin films from their solutions. They exhibit high thermal stability with decomposition being above 440 °C and relatively low glass transition temperatures in the range 160–190 °C. These polymers show strong photoluminescence in the blue spectral region. CONCLUSION: The introduction of oxadiazole rings together with siloxane groups into the chains of aromatic polyimides gives highly thermostable polymers with remarkable solubility and film‐forming ability and that emit blue light, being attractive for applications in micro‐ and nanoelectronics and other related advanced fields. Copyright © 2009 Society of Chemical Industry     

Ethanol reforming and partial oxidation with Cu/Nb2O5 catalyst

Ethanol reforming and partial oxidation were studied on Cu/Nb₂O₅ and Ni/Al₂O₃ catalysts. Compared to the Ni/Al₂O₃ catalyst, the Cu/Nb₂O₅ catalyst presents conversion as high as Ni/Al₂O₃ catalyst, however, for the same level of formation of hydrogen it occurs at much lower temperature on the Cu/Nb₂O₅ catalyst, 200 °C lower than for the Ni/Al₂O₃ catalyst, with remarkable little formation of CO, which can be attributed to the strong interaction between copper and niobia. Temperature-programmed desorption (TPD-ethanol) and surface reactions (TPSR) of partial oxidation of ethanol showed formation of ethylene, acetaldehyde, ethane and mainly H₂ and CO₂ besides little methane. DRIFTS results are in accordance with TPD analysis and the formation of acetate species at room temperature suggests reactivity of the surface and its oxidative dehydrogenation capacity. The adsorption of ethanol gives rise to ethoxide species, which form acetate and acetaldehyde that can be oxidized to CO₂ via carbonate. A comparison with reported results for Cu/Al₂O₃ this catalyst is promising, yielding high level of H₂ with little CO production during reforming and partial oxidation reaction. The maximum H₂ formation for the partial oxidation of ethanol was 41% at ratio (O₂/Et) 0.8, increasing to 50% at ratio 1.5. The H₂/CO is around 10 for the partial oxidation and 7 for steam reforming, which is excellent, compared to the Ni/Al₂O₃ catalyst with a factor 4–8 lower.     

Catalytic activity of Fe/AC, obtained by impregnation of activated carbon in aqueous and non-aqueous media, to neutralize NO

The influence of the nature of the impregnating solutions media (aqueous or non-aqueous) on the forming of active phases is investigated in case of preparing iron catalysts, supported on activated carbon with respect to their catalytic activity in the reaction of NO reduction by CO. The catalysts are characterized by chemical analysis (AAS), BET surface area, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), magnetic susceptibility, and Mössbauer spectroscopy (MS). The catalytic investigations and TPD are carried out in a flow apparatus. Three peculiarities are observed with respect to this influence—the ratio between the separate iron species in different oxidation state of Fe species, which build up the catalytic active complexes (CAC), common participation of superficial groups of the carbon support and Fe components of the impregnating solutions as well as different dispersion of the active phase on the surface of the samples. As a result the highest catalytic activity was observed with the sample, obtained by impregnation with an aqueous solution, while with the other samples, obtained from organic solutions, the catalytic activity decreases in the order of: Methanol > Ethyl Ether > Acetone. It was assumed that the different catalytic activities are connected most probably with the process of forming of CAC during the process of preparation of the samples.     

Moisture barrier and physical properties of acetylated derivatives with increasing acetylation degree

Four acetostearin products with increasing acetylation degree were synthesized by chemical interesterification followed by fractionation/blending stages. Their physical properties and functional barrier properties were studied and compared to the properties of technical tristearin. Increasing acetylation degree (AD) modified the triacylglycerols crystal habits and probably led to an increase in acyl chain fluidity, which induced, at macroscopic levels, a decrease in solid fat content (SFC), in melting point, in surface and bulk material hydrophobicity, and an increased moisture effective diffusivity. Water vapor permeability (WVP) coefficients of the materials were partially influenced by the AD factor, but also by the development of macroscopic cracks in lipids presenting high SFC. Acetylated stearin up to 47% (acetyl mol/mol of esterified chain) presented the lowest WVP at 20 °C resulting from an adequate balance between hydrophobicity and mechanical properties of the material.     

sInfluence of starch and protein molecular interactions on the in vitro digestion characteristics of biscuits partially substituted with pulse flours

Recent research has shown that pulse-derived ingredients present a technological alternative to cereals, higher protein and fibre content, and differentiated starch characteristics. In this work, the partial substitution of pulse flours with and without heat moisture treatment (HMT) was evaluated in a biscuit model. The digestion residues at 20 and 120 min that correspond to rapidly, slowly and resistant starch from the Englyst methodology were analysed by DSC, X-Ray and ATR-FTIR. The use of pulse flours in biscuits improved their thermal stability (ΔH = 3.01 and 4.99 J/g for control and Lentil + HMT), preserving a fraction of particularly ling glucans, that influenced the decreasing in the rapidly available starch from 55.26 to 24.11 % (Control and Faba bean + HMT), and enhanced its protein's digestibility from 75.26 to 87.43 % for the same sources. Among pulses, there were similarities regarding their resistance to enzymatic hydrolysis that may help select those with better organoleptic attributes.     

Growth in height of indigenous and non indigenous Chilean children

The aim of this study was to compare growth curves of stature in indigenous and non-indigenous children belonging to two levels of poverty and to establish the onset and evolution of the deficit. Children of indigenous and non-indigenous background living in communities of extreme and low poverty in Chile were studied and their height-for-age Z-score from birth until 6 year of age were compared. Mean weight at birth was within normal range, and no differences were found in ethnicity and levels of poverty. Length at birth was below the reference with the exception of the non indigenous newborn from counties of low poverty. Deficit in growth showed an early start, furthermore in indigenous children belonging to the extreme poverty, is from birth and progress through the 18 months. At 72 months the deficit reached -1.1 z scores in the indigenous of the extreme poverty versus -0.7 in the non indigenous group. Children from the low poverty had a Z-score of -0.4 z scores at 72 months without differences between ethnias. Indigenous of the extreme poverty had less accumulative growth while the indigenous of the low poverty areas growth satisfactory without differences with the non indigenous.     

Functional polysiloxanes

Summary Carboxyester- and carboxyamido-terminated polydimethylsiloxanes were obtained through the reaction of cyclic anhydrides (succinic, maleic and phthalic anhydride) with hydroxypropyl- and aminoalkyl-terminated polydimethylsiloxanes, respectively. The reactivity of the starting compounds and the influence of the reaction conditions on the characteristics of the final products are discussed.Part 1: Eur. Polym. J., in press     

Structure–property relationship of sodium deoxycholate based poly(ester ether)urethane ionomers for biomedical applications

New sodium deoxycholate based poly(ester ether)urethane ionomers were prepared for the development of biomedical materials. A structure–property relationship in the tested biomaterials was established by cross‐examination of the dynamic mechanical and dielectric properties, attenuated total reflection–Fourier transform infrared investigation, thermogravimetric analysis, and surface morphology characterization. A stronger ionic interaction and solvation capacity of the ions and a higher ionic conductivity were manifested in the case of poly(ethylene oxide)‐rich segments than for poly(propylene oxide)‐rich segments in these polyurethane ionomers. The molecular and ionic interactions of the bile‐salt moiety with different polyether cosoft segments influenced chain packing and conformation, supramolecular organization, and the resulting surface morphological microstructures of the polyurethane biomembranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42921.     

3D printed millireactors for process intensification

The scope of the present research aims at demonstrating the 3D printing use in the manufacturing of microchannels for chemical process applications. A comparison among digital model processing applications for 3D print(slicers) and a print layer thickness analysis were performed. The 3D print fidelity was verified in several devices, including the microchannels' printing with and without micromixer zones. In order to highlight the 3D print potential in Chemical Engineering, the biodiesel synthesis was also carried out in a millireactor manufactured by 3D printing. The millireactor operated under laminar flow regime with a total flow rate of 75.25 ml ? min~(-1)(increment of about 130 times over traditional microdevices used for biodiesel production).The printed millireactor provided a maximum yield of Ethyl Esters of 73.51% at 40 °C, ethanol:oil molar ratio of7 and catalyst concentration of 1.25 wt% and residence time about 10 s. As a result of flow rate increment attained in the millireactor, the number of required units for scaling-up the chemical processes is reduced. Using the approach described in the present research, anyone could produce their own millireactor for chemical process in a simple way with the aid of a 3D printer.