A new bisphenol monomer, 9,9-bis(3,5-dimethoxy-4-hydroxyphenyl) fluorene, was synthesized and polymerized to form fluorene-based poly(arylene ether sulfone) copolymers containing tetra-methoxy groups (MPAES). After converting the methoxy group to the reactive hydroxyl group, the respective side-chain type sulfonated copolymers (SPAES) were obtained by sulfobutylation. The polymers were characterized by 1H NMR, thermogravimetric analysis (TGA), water uptake, and proton and methanol transport for fuel cell applications. These SPAES copolymers had good overall properties as polymer electrolyte membrane (PEM) materials, having high proton conductivity in the range of 0.061–0.209 and 0.146–0.365 S/cm at 30 and 80 °C (under hydrated conditions), respectively. SPAES-39 (IEC = 1.93 mequiv/g) showed higher or comparable proton conductivity than that of Nafion 117 at 50–95% RH (relative humidity). The methanol permeabilities of these membranes were in the range of 3.22 to 13.1 × 10–7 cm2/s, which is lower than Nafion (15.5 × 10–7 cm2/s). In comparison with some reported sulfonated poly(arylene ether sulfone)s containing pendent sulfophenyl groups, the present fluorene-based SPAES containing clustered flexible pendent aliphatic sulfonic acid groups displayed better properties, such as lower water uptake and higher proton conductivities. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for selected SPAES indicates that they are good candidate proton exchange membrane materials for evaluation in fuel cell applications.
1Sulfonated poly(arylene sulfide sulfone nitrile)s (SN) were synthesized to investigate the effects 2 of naphthalene units in the polymer backbone on membrane properties. The small and planar 3 naphthalene in the main chain induced semi-crystallinity in the polymer, as confirmed by 4 molecular simulations and wide angle X-ray diffraction patterns. The semi-crystalline SN 5 polymer membranes exhibited excellent chemical and mechanical properties, better than those of 6 their phenylene counterpart (SP). In particular, the water uptake and swelling ratio of the SN 7 membranes were much lower than those of the SP membranes. Furthermore, the SN membranes 8 exhibited a greatly reduced methanol permeability (9-17 × 10 -8 cm 2 s -1 ) compared to Nafion ® 9 117 (240 × 10 -8 cm 2 s -1 ) at 30 o C in 10 M methanol. Moreover, sulfide-and naphthalene-based 10 chemical structure and semi-crystalline nature of the SN membranes enhanced their DMFC 11 single cell performance and long-term stability during fuel cell operation. 12
Two series of random sulfonated poly-(benzothiazole-co-benzimidazole) polymers (sPBT-BI) with 70% and 60% degree of sulfonation were evaluated as proton exchange membranes. sPBT was also prepared for a comparative study. The mechanical properties of sPBT-BI were greatly enhanced by incorporation of benzimidazole (BI); sPBT-BI70-10 showed a tensile strength of 125 MPa and elongation at break of 38.9%, an increase of 56.5% and 145%, respectively, compared with sPBT. The solubility, dimensional stability, thermal properties, and oxidative stability of sPBT-BI were also improved. The ionic clusters of sPBT-BI membranes in both AFM phase images and TEM images became narrower with increasing amounts of BI while containing the same molar amount of sulfonic acid groups. This resulted in lower dimensional swelling and higher mechanical strength, but the proton conductivity decreased. However, high proton conductivity was achieved by incorporating an appropriate content of BI. PEMFC H 2 /air single cell performances and durabilities were improved by incorporation of 5% of BI units in sPBT.
Aerosol optical properties were measured and analyzed through the ground-based remote sensing Aerosol Robotic Network (AERONET) over an urban-industrial site, Nanjing (32.21° N, 118.72° E, and 62 m above sea level), in the Yangtze River Delta, China, during September 2007-August 2008. The annual averaged values of aerosol optical depth (AOD500) and the Ångström exponent (AE440-870) were measured to be 0.94 ± 0.52 and 1.10 ± 0.21, respectively. The seasonal averaged values of AOD500 (AE440-870) were noticed to be high in summer (autumn) and low in autumn (spring). The characterization of aerosol types showed the dominance of mixed type followed by the biomass burning and urban-industrial type of aerosol at Nanjing. Subsequently, the curvature (a 2) obtained from the second-order polynomial fit and the second derivative of AE (α') were also analyzed to understand the dominant aerosol type. The single scattering albedo at 440 nm (SSA440) varied from 0.88 to 0.93 with relatively lower (higher) values during the summer (spring), suggesting an increase in black carbon and mineral dust (desert dust) aerosols of absorbing (scattering) nature. The averaged monthly and seasonal evolutions of shortwave (0.3-4.0 μm) direct aerosol radiative forcing (DARF) values were computed from the Santa Barbara DISORT Atmospheric Radiative Transfer (SBDART) model both at the top of atmosphere (TOA) and bottom of atmosphere (SUR) during the study period. Further, the aerosol forcing efficiency (AFE) and the corresponding atmospheric heating rates (AHR) were also estimated from the forcing within the atmosphere (ATM). The derived DARF values, therefore, produced a warming effect within the atmosphere due to strong absorption of solar radiation.
/npsi/ctrl?lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?lang=fr Access and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1039/c2ee21992aEnergy and Environmental Science, 5, 12, pp. 9795-9802, 2012-10-18 Morphological transformation during cross-linking of a highly sulfonated poly(phenylene sulfide nitrile) random copolymer Lee, So Young; Kang, Na Rae; Shin, Dong Won; Lee, Chang Hyun; Lee, Kwan-Soo; Guiver, Michael D.; Li, Nanwen; Lee, Young Moo Journal Name Here we present a new approach of morphological transformation for effective proton transport within ionomers even at partially hydrated states. Highly sulfonated poly(phenylene sulfide nitrile) (XESPSN) random network copolymers were synthesized as alternatives to state-of-the-art perfluorinated polymers such as Nafion ® . Cross-linking reaction was effectively conducted at 250 o C by simple thermal 10 trimerisation of ethynyl groups at the chain termini that would morphologically transform the nanophase separation between the hydrophilic and hydrophobic domains, and thus form well-connected hydrophilic nanochannels for dramatically enhanced proton conduction even at partially hydrated conditions. For instance, the proton conductivity of XEPSN60 was 160% higher than that of Nafion ® 212 at 80 o C and 50% relative humidity condition. The water uptake and dimensional swelling were also reduced and 15 mechanical properties and oxidative stability were improved after a three-dimensional network formation. These properties of the XESPSN membranes suggest that they are able to be utilized as desirable polymer electrolyte materials in fuel cell applications under partially hydrated environments.
The ground-based characteristics (optical and radiative properties) of dust aerosols measured during the springtime between 2001 and 2014 were investigated over urban Beijing, China. The seasonal averaged aerosol optical depth (AOD) during spring of 2001-2014 was about 0.78 at 440 nm. During dust days, higher AOD occurred associated with lower Ångström exponent (AE). The mean AE440-870 in the springtime was about 1.0, indicating dominance of fine particles over the region. The back-trajectory analysis revealed that the dust was transported from the deserts of Inner Mongolia and Mongolia arid regions to Beijing. The aerosol volume size distribution showed a bimodal distribution pattern, with its highest peak observed in coarse mode for all episodes (especially for dust days with increased volume concentration). The single scattering albedo (SSA) increased with wavelength on dust days, indicating the presence of more scattering particles. Furthermore, the complex parts (real and imaginary) of refractive index showed distinct characteristics with lower imaginary values (also scattering) on dust days. The shortwave (SW; 0.2-4.0 μm) and longwave (LW; 4-100 μm) aerosol radiative forcing (ARF) values were computed from the Santa Barbara DISORT Atmospheric Radiative Transfer (SBDART) model both at the top of atmosphere (TOA) and the bottom of atmosphere (BOA) during dust and non-dust (dust free) days, and the corresponding heating rates and forcing efficiencies were also estimated. The SW (LW) ARF, therefore, produced significant cooling (warming) effects at both the TOA and the BOA over Beijing.
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