This work discusses the effect of isopropyl phosphate (IP) on the transport properties of sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) as membranes for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The properties were determined as a function of SIBS sulfonation level (i.e., 24, 34, 49, and 84 mol %) and IP loading (i.e., 1, 3, 5, 11, and 15 wt %). A comprehensive material characterization study (e.g.
Graphene oxide (GO) and its sulfonated analog (sGO) have been incorporated into sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) in order to enhance its water retention and proton conductivity, while aiming to block permeant passage through the material. The polymer nanocomposite membranes (PNMs) were tested for two applications: direct methanol fuel cell and chemical and biological protective clothing. The transport properties of the membranes were determined as a function of SIBS sulfonation level (i.e., 37, 61, and 88 mol%), filler type (i.e., GO and sGO) and filler loading (i.e., 1, 3, 5, and 10 wt%). Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) confirmed the functionalization and incorporation of the fillers into SO3H SIBS. No significant changes were observed in the thermal stability or FTIR spectra of the PNMs after addition of the fillers. Dissimilar behaviors were observed for the ion exchange capacity, water absorption capabilities and transport properties of the membranes after incorporation of the fillers. Atomic force microscopy (AFM) phase images and Fenton's test results indicate that the oxidative stability of the PNMs is associated to the interconnectivity between the hydrophilic domains of the fillers and SO3H SIBS. The PNMs presented low permeability and high proton conductivity and thus, functioned adequately for both applications. POLYM. ENG. SCI., 59:E455–E467, 2019. © 2018 Society of Plastics Engineers
more » « less- PAR ID:
- 10461887
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Polymer Engineering & Science
- Volume:
- 59
- Issue:
- S1
- ISSN:
- 0032-3888
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract , FTIR, TGA, AFM, and SAXS) was performed to confirm the presence of the phosphate groups in the polymer matrix, assess the thermal stability of the proton‐exchange membranes (PEMs), and understand how the unique interactions between the phosphate and sulfonic groups influenced the nanostructure of SO3H SIBS. The transport properties, water absorption capabilities (i.e., swelling ratio, water uptake, etc.), oxidative stability, and ion‐exchange capacity (IEC) were performed to evaluate the impact of IP on the properties of the resulting solvent‐casted membranes. Results suggest that the morphology, thermal stability, and vapor permeability are governed by the sulfonation level, whereas the IEC, oxidative stability, water absorption capabilities, and the rest of the transport properties are dominated by the ionic content (i.e., sulfonic and phosphate groups) and their synergistic effects. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019 ,136 , 47009. -
ABSTRACT This study discusses the effect of carboxylated (COOH) and phosphonated (PO3H2) single‐walled carbon nanotubes (SWCNTs) on the transport properties of sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) as polymer nanocomposite membranes (PNMs) for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The properties were determined as a function of sulfonation level of SIBS, SWCNTs functionalization and loading. A comprehensive materials characterization study was performed to understand the interactions between the nanofillers and the functionalized polymer matrix, and to determine the effect of their incorporation on the resulting nanostructure of the PNMs. Results indicate that the sulfonation level is the variable that dictates nanofiller dispersion, mechanical properties, water absorption capabilities, morphology, and oxidative stability of SO3H SIBS. Meanwhile, the nanofiller loading and functionalization influenced the transport properties. The nanofillers reduced methanol permeation. PO3H2SWCNTs increased the proton conductivity but at a high sulfonation level (i.e.
, 90 mol %), the ionic interconnectivity caused a more complex morphology decreasing the transport of protons. Optimal selectivity in transport properties were found with a sulfonation level of 61 mol % and a PO3H2SWCNTs loading of 1.0 wt. % for DMFC and 0.5 wt. % for CBPC due to changes in morphology and the unique transport mechanism of permeants through the PNMs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2018 ,56 , 2475–2495 -
ABSTRACT Sulfonated, block copolymers have traditionally been studied for applications in fuel cells and chemical protective clothing, among others. As such, most investigations have focused on the evaluation of transport properties and the selectivity and permeability of the polymer membranes. This work, however, focuses on the electrical characterization of sulfonated poly(styrene–isobutylene–styrene) (SIBS) triblock copolymer thin films. More specifically, the dielectric properties of SIBS are evaluated as a function of critical parameters such as frequency, sulfonation percent, and the polymer concentration. The results show that the dielectric constant increases with sulfonation percent and polymer concentration to values as high as 13,600. This work also provides insights into the correlation of SIBS electrical properties with its chemical structure and morphology. The structure–property relationship is derived through a combination of techniques including: elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and atomic force microscopy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci.
2018 ,135 , 45662. -
Polymeric proton exchange membranes (PEMs) are vital components of fuel cells, as they enable the transport of protons while preventing the crossover of fuel and oxidant gases. However, conventional PEMs have limitations such as low use temperature, low proton conductivity, and poor mechanical and thermal stability. Various types of nanoparticles have been investigated to modify PEMs to overcome these limitations, as they can increase proton conductivity, mechanical strength, thermal stability, and chemical resistance. Metal oxides such as SiO2and TiO2have been shown to improve the proton conductivity and mechanical properties of PEMs. Carbon-based materials such as graphene oxide have been found to enhance both the proton conductivity and thermal stability of PEMs. The use of nanoparticles in modified polymeric PEMs for fuel cells shows excellent potential for improving the performance and durability of fuel cells. Future research should focus on developing cost-effective and scalable methods for nanoparticle synthesis and incorporation into PEMs. Polybenzimidazole (PBI) is the most widely studied high-temperature polymer for preparing composite PEMs. This review provides the recent development of PBI composite PEMs modified with different types of nanoparticles.
-
Abstract Early‐age hydration of cement is enhanced by slightly soluble mineral additives (ie, fillers, such as quartz and limestone). However, few studies have attempted to systematically compare the effects of different fillers on cementitious hydration rates, and none have quantified such effects using fillers with comparable, size‐classified particle size distributions (PSDs). This study examines the influence of size‐classified fillers [ie, limestone (CaCO3), quartz (SiO2), corundum (Al2O3), and rutile (TiO2)] on early‐age hydration kinetics of tricalcium silicate (C3S) using a combination of experimental methods, while also employing a modified phase boundary and nucleation and growth model. In prior studies, wherein fillers with broad PSDs were used, it has been reported that between quartz and limestone, the latter is a superior filler due to its ability to partake in anion‐exchange reactions with C‐S‐H. Contrary to prior investigations, this study shows that when size‐classified and
area matched fillers are used—which, essentially, eliminate degrees of freedom associated with surface area and agglomeration of filler particulates—the filler effect of quartz is broadly similar to that of limestone as well as rutile. Results also show that unlike quartz, limestone, and rutile—which enhance C3S hydration kinetics—corundum suppresses hydration of C3S during the first several hours after mixing. Such deceleration in C3S hydration kinetics is attributed to the adsorption of aluminate anions—released from corundum's dissolution—onto anhydrous particulates’ surfaces, which impedes both the dissolution of C3S and heterogeneous nucleation of C‐S‐H.