Synthesis and optical properties of poly(aryl ether ketone)s incorporating porphyrins in the backbones

A series of novel soluble poly(aryl ether ketone)s (PAEKs) based on 5,10‐bis(4‐hydroxyphenyl)?15,20‐diphenylporphyrin (cis‐DHTPP), 4,4′‐(hexafluoroisopropylidene) diphenol (6FBPA) and 4,4′‐difluorobenzophenone (DFB) were synthesized and characterized by FT‐IR, ¹H‐NMR, UV–vis and fluorescence spectroscopies. The intrinsic photophysical properties of porphyrins were preserved because of the absence of photoinduced electron transfer in the polymer chains. Investigation of the copolymers thermal properties indicated that these polymers had high glass transition temperatures and excellent thermal stabilities. The results of Z‐scan and optical limiting measurements manifested that incorporation of the porphyrin chromophore into the main chain engendered the novel PAEKs with superior nonlinear optical properties and optical limiting function, which could be effectively tuned by varying the molar ratio of porphyrin monomers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1282–1290     

Monitoring fuel quality: a case study for quinizarin marker content of unleaded petrol marketed in Greece

Fuel adulteration and cross-contamination lead to low-quality fuel products, which may cause increased environmental pollution, loss of taxes and engine problems. An establishment of a quality monitoring mechanism based on laboratory measurements may reveal problematic areas of the fuel supply chain. For the purposes of this work, 97 unleaded petrol samples were measured in order to quantify mass concentration of quinizarin, a substance used in Greece to easily mark the presence of 95 Research Octane Number unleaded petrol in other types of automotive fuels. The samples were obtained from petroleum retail stations selling different brands of fuels and located in different geographic regions of Greece. Statistical analysis of the results revealed quinizarin mass concentrations below the 3 mg L^?1 legislation specification limit and significant differences between brands and geographic regions, which may attributed to the structure of the fuel supply chain in Greece in combination with quinizarin properties and way of handling. Moreover, certain approaches were used for the calculation of decision limits for assessing compliance or non-compliance. These approaches take measurement reproducibility or estimated in-house uncertainty into account, in order to minimize the probability of false rejection.     

In situ ultrasonic measurements: a powerful tool to control the synthesis of zeolites from coal fly ash

An in situ ultrasonic diagnostic technique was applied to monitoring the hydrothermal synthesis of zeolite A and X of clear solution extracted from alkaline fused class F coal fly ash. In this context, kinetic evaluations based on in situ ultrasonic diagnostic data displayed an important approach to study the synthesis process. The impact on nucleation and crystal growth was demonstrated by variation of a few relevant parameters such as reaction temperature, amount of water, Na₂O and ageing time, including templated colloidal synthesis mixtures as model solution. To complement the kinetic analysis, ex situ techniques such as ICP, X-ray diffraction, scanning electron microscopy and dynamic light scattering were used to investigate liquid phase and reaction products extracted from the reaction mixture during the synthesis.     

Validation of primary formaldehyde gas standards prepared by dynamic thermogravimetry through a tri-national comparison of gaseous formaldehyde amount fraction

A validation study for primary formaldehyde gas standards was performed at three National Metrology Institutes: the Korea Research Institute of Standards and Science (KRISS), the National Metrology Institute of Japan (NMIJ) and the National Institute of Metrology of China (NIM). The studied materials had a nominal amount fraction of 2 μmol/mol formaldehyde in nitrogen balance and were prepared in 10-L aluminum cylinders by KRISS. The impurities in the materials were analyzed using a gas chromatograph/atomic emission detector and a Fourier-transform infrared spectrometer (FTIR). The stability of the materials was assessed for 1 year by KRISS using paraformaldehyde as a source for the primary standard gas and a cavity ring-down spectrometer (CRDS) instrument as the measurement method. The amount fraction of formaldehyde in the materials decreased linearly by 0.74 % each month. The studied materials that exhibited similar linear rates of decline were distributed to the participants. After the measurement was completed by the participants, the materials were returned to KRISS and the stability analysis based on the primary standard maintained at KRISS was repeated. NMIJ analyzed the materials using paraformaldehyde as the source of the primary standard of formaldehyde and FTIR analysis, whereas NIM used trioxane as the primary standard gas source and CRDS analysis. The results of the comparison revealed good agreement between the results and were within the expanded uncertainty of 2 % although each of them used different combinations of methods in the generation of primary gas standards and measurements.     

Glutaraldehyde crosslinking of arabinoxylan produced from corn ethanol residuals

This study investigated the possibility of substituting petroleum-based polymers with biopolymers for films and paper coatings. Arabinoxylan (AX) was extracted from distillers’ grains, a low-value corn ethanol byproduct, and modified through crosslinking with glutaraldehyde (GA) which was made into films and paper coatings. The effects of degree of substitution (DS) on film and coating properties of GA cross-linked AX, referred to as GAX, were investigated. The GAX films had markedly higher tensile strength, approximately 3 times higher than the unmodified AX films at low DS, with higher DS causing a negative effect on the film tensile strength. Compared to unmodified AX coating, paper coated with GAX also had significantly higher tensile index, presumably due to high adhesion between the coating and paper interface. When used as a coating binder with calcium carbonate pigments, GAX showed comparable performance to polyvinyl alcohol, a common industrial binder, demonstrating the potential to be substituted for the petroleum-based paper coating binder.