Early detection of aluminum corrosion via “turn-on” fluorescence in smart coatings

In the present work we describe the successful application of spiro[1H-isoindole-1,9′-[9H]xanthen]-3(2H)-one, 3′,6′-bis(diethylamino)-2-[(1-methylethylidene)amino](“FD1”) as a “turn-on” early aluminum corrosion detector in epoxy coatings. Electrospray ionization mass spectrometry (ESI-MS) and ¹H NMR investigations have revealed that the non-fluorescent FD1 is sensitive to low pH due to its acid-catalyzed hydrolysis to Rhodamine B hydrazide (RBH) that subsequently becomes protonated to its fluorescent ring-opened form. Both clear and filled FD1-containing smart epoxy coatings were capable of sensing acidic pH produced at the anodic site of localized aluminum corrosion at a low indicator concentration (0.5 wt%), which was demonstrated by the observation of fluorescent, bright-orange areas corresponding to localized pitting corrosion of the aluminum substrate illuminated by a handheld UV lamp. Therefore, early corrosion of aluminum can be easily and nondestructively detected via our “turn-on” fluorescence strategy.     

Effect of nozzle orifice geometry on spray, combustion, and emission characteristics under diesel engine conditions

Diesel engine performance and emissions are strongly coupled with fuel atomization and spray processes, which in turn are strongly influenced by injector flow dynamics. Modern engines employ micro-orifices with different orifice designs. It is critical to characterize the effects of various designs on engine performance and emissions. In this study, a recently developed primary breakup model (KH-ACT), which accounts for the effects of cavitation and turbulence generated inside the injector nozzle is incorporated into a CFD software CONVERGE for comprehensive engine simulations. The effects of orifice geometry on inner nozzle flow, spray, and combustion processes are examined by coupling the injector flow and spray simulations. Results indicate that conicity and hydrogrinding reduce cavitation and turbulence inside the nozzle orifice, which slows down primary breakup, increasing spray penetration, and reducing dispersion. Consequently, with conical and hydroground nozzles, the vaporization rate and fuel air mixing are reduced, and ignition occurs further downstream. The flame lift-off lengths are the highest and lowest for the hydroground and conical nozzles, respectively. This can be related to the rate of fuel injection, which is higher for the hydroground nozzle, leading to richer mixtures and lower flame base speeds. A modified flame index is employed to resolve the flame structure, which indicates a dual combustion mode. For the conical nozzle, the relative role of rich premixed combustion is enhanced and that of diffusion combustion reduced compared to the other two nozzles. In contrast, for the hydroground nozzle, the role of rich premixed combustion is reduced and that of non-premixed combustion is enhanced. Consequently, the amount of soot produced is the highest for the conical nozzle, while the amount of NO_x produced is the highest for the hydroground nozzle, indicating the classical tradeoff between them.     

Influence of calcium carbonate filler and mixing type process on structure and properties of styrene–acrylonitrile/ethylene–propylene–diene polymer blends

The properties of styrene–acrylonitrile (SAN) and ethylene–propylene–diene (EPDM) blends containing different types of calcium carbonate filler were studied. The influence of mixing type process on the blend properties was also studied. Two different mixing processes were used. The first one includes mixing of all components together. The other process is a two‐step mixing procedure: masterbatch (MB; EPDM/SAN/filler blend) was prepared and then it was mixed with previously prepared polymer blend. Surface energy of samples was determined to predict the strength of interactions between polymer blend components and used fillers. The phase morphology of blends and their thermal and mechanical properties were studied. From the results, it can be concluded that the type of mixing process has a strong influence on the morphological, thermal, and mechanical properties of blends. The two‐step mixing process causes better dispersion of fillers in blends as well as better dispersion of EPDM in SAN matrix, and therefore, the finest morphology and improved properties are observed in blends with MB. It can be concluded that the type of mixing process and carefully chosen compatibilizer are the important factors for obtaining the improved compatibility of SAN/EPDM blends. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Precursor-Derived Si-B-C-N Ceramics: Oxidation Kinetics

The oxidation behavior of three precursor-derived ceramics—Si_4.46BC_7.32N_4.40 (AMF2p), Si_2.72BC_4.51N_2.69 (AMF3p), and Si_3.08BC_4.39N_2.28 (T2/1p)—was investigated at 1300° and 1500°C. Scale growth at 1500°C in air can be approximated by a parabolic rate law with rate constants of 0.0599 and 0.0593 μm²/h for AMF3p and T2/1p, respectively. The third material does not oxidize according to a parabolic rate law, but has a similar scale thickness after 100 h. The results show that at least within the experimental times these ceramics develop extremely thin scales, thinner than pure SiC or Si₃N₄.     

Durability of YSZ coated Ti2AlC in 1300°C high velocity burner rig tests

A thermal barrier coating (TBC) system survived 500 hours in aggressive, 1300°C burner rig testing. The yttria-stabilized zirconia (7YSZ) TBC was plasma sprayed on an oxidation-resistant Ti₂AlC-type MAX phase and tested in a jet fuel burner at 100 m/s, using 5 hours cycles. No coating spallation or surface recession was observed; Al₂O₃-scale growth produced a slight 2.4 mg/cm² mass gain. The coating surface exhibited craze-cracked colonies of [111]_flourite textured columns, with no visible moisture attack. The 20 μm alumina scale remained intact under the YSZ face, about twice that producing failure for TBC/superalloy systems. TiO₂ nodules, initially formed on the uncoated backside, were removed, and Al₂O₃ was etched through volatile hydroxides formed in water vapor (~10%). Overall, the test indicated exceptional stability of the YSZ/Al₂O₃/Ti₂AlC system under turbine conditions due in large part to close thermal expansion matching.     

Phase development and pore stability of yttria- and ytterbia-stabilized zirconia aerogels

High-porosity yttria- and ytterbia-stabilized zirconia aerogels offer the potential of extremely low thermal conductivity materials for high-temperature applications. Yttria- and ytterbia-doped zirconia aerogels were synthesized using a sol-gel approach over the dopant range of 0-20 atomic percent. Surface area, pore volume, and morphology of the as-dried aerogels and materials thermally exposed for short periods of time to temperatures up to 1200°C were characterized by nitrogen physisorption, scanning and transmission electron microscopy, and X-ray diffraction. The aerogels as supercritically dried all were X-ray amorphous. At a 5% dopant level, a tetragonal structure with a smaller monoclinic phase developed on thermal exposure. Mixed tetragonal and cubic phases or predominantly cubic materials were observed at higher dopant levels, depending on the dopant level, temperature and exposure time. The formation of crystalline phases was accompanied by loss of surface area and pore volume, although some mesoporous structure was maintained on short-term exposure to 1000°C. Incorporation of the smaller Yb atom into the lattice structure resulted in smaller lattice dimensions on crystallization than was seen with Y doping and favored a more highly equiaxed structure. Aerogels synthesized with 15% Y maintained the smallest particle size without evidence of sintering at 1100°C. Largest shrinkage and loss of pore volume occurred on crystallization from the amorphous phase, with further loss of pores at temperatures above 1000°C attributable to changes in lattice parameters.     

Solution Structure and Dynamics of the Small Protein HVO_2922 from Haloferax volcanii

Past sequencing campaigns overlooked small proteins as they seemed to be irrelevant due to their small size. However, their occurrence is widespread, and there is growing evidence that these small proteins are in fact functionally very important in organisms found in all kingdoms of life. Within a global proteome analysis for small proteins of the archaeal model organism Haloferax volcanii, the HVO_2922 protein has been identified. It is differentially expressed in response to changes in iron and salt concentrations, thus suggesting that its expression is stress-regulated. The protein is conserved among Haloarchaea and contains an uncharacterized domain of unknown function (DUF1508, UPF0339 family protein). We elucidated the NMR solution structure, which shows that the isolated protein forms a symmetrical dimer. The dimerization is found to be concentration-dependent and essential for protein stability and most likely for its functionality, as mutagenesis at the dimer interface leads to a decrease in stability and protein aggregation.     

Does carbon nanopowder threaten amphibian development?

Lethal and teratogenic potentials of carbon nanoparticles (CNPs) in their amorphous form were investigated by the standardized Frog Embryo Teratogenesis Assay-Xenopus (FETAX), a 96-h in vitro whole-embryo toxicity test based on the amphibian Xenopus laevis. Embryos were acutely exposed to 1, 10, 100 and 500 mg/L CNP suspensions and evaluated for lethality, malformations and growth inhibition. Larvae were processed for histological and ultrastructural analyses to detect the main affected organs, to look for specific lesions at the subcellular level and to image and track CNPs into tissues. Only the highest CNP suspension resulted in being embryolethal for X. laevis larvae, while malformed larva percentages significantly differed from controls starting from 100 mg/L. The stomach and gut were the preferential CNP accumulation sites, on the contrary, the digestive epithelium remained intact. The analyses showed the presence of isolated nanoparticles and/or aggregates in different secondary target organs. CNPs were found in circulating erythrocytes. The research confirms the good tolerance of X. laevis towards pure elemental carbon in its nanoparticulate amorphous form, but highlights the possibility of CNP transfer toward all body areas.