• Korean Chemical Engineering Research
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• v.51 no.5
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• pp.556-560
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• 2013

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for use in PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, characteristics of poly(arylene ether sulfone)(PAES) were compared with fluorinated membrane at PEMFC operation condition. I-V polarization curve, hydrogen crossover, electrochemical surface area, membrane resistance and charge transfer resistance were measured. PAES membrane showed similar performance compared with fluorinated membrane at 100% relative humidity, but the performance of PAES membrane decreased largely due to low ionic conductivity at low relative humidity.

• Membrane Journal
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• v.22 no.3
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• pp.191-200
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• 2012

New composite membranes were manufactured by impregnating post-sulfonated poly(arylene ether sulfone)s containing perfluorocyclobutane (PFCB) groups into porous polytetrafluoroethylene (PTFE) films. Two kinds of post-sulfonated poly(arylene ether sulfone)s with two different monomer ratios (sulfonable biphenylene monomer : non-sulfonable sulfonyl monomer = 6 : 4, 4 : 6) were first prepared through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition polymerization and post-sulfonation using chlorosulfonic acid (CSA). The composite membranes were then prepared by adjusting the concentrations (5~20 wt%) of the resulting copolymers impregnated in the PTFE films. The water uptake, ion exchange capacity (IEC) and ion conductivity of the composite membranes were characterized and compared with their unreinforced dense membranes and Nafion. All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR and the composite membranes were observed with scanning electron micrographs (SEM).

• Membrane Journal
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• v.25 no.5
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• pp.447-455
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• 2015

In this study, Polysulfone (PSf) and polyetherimide (PEI) as the anion exchange polymers were aminated in the different ratio whereas the polyether ether ketone (PEEK) as the cation exchange polymer was sulfonated. The bipolar membranes of SPEEK (sulfonated PEEK)/APSf (aminated PSf) and SPEEK/APEI (aminated PEI) were prepared by the double-casting method. The surfaces of bipolar membranes were fluorinated in accordance with the amination ratio and applied to produce the hypochlorite. As the amination increased, the hypochlorite concentration is also increased. Typically, for SPEEK/APSf 3 : 1 membrane, the produced hypochlorite concentration was 61.0 ppm and its durability was 220 min for the non-fluorinated membrane while for the fluorinated membrane, the concentration of 58.6 ppm and its durability lasted 570 min. Also for SPEEK/APEI 3 : 1 membrane, the hypochlorite concentrations of 60.1 ppm and 58.3 ppm for before- and after-fluorination, respectively were observed whereas the durability was remarkably developed from 150 min to 440 min. Therefore, the surface fluorination takes an important role for the development of the membrane durability.

• Membrane Journal
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• v.17 no.4
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• pp.294-301
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• 2007

To improve oxidative stability of non-fluorinated styrene-based polymer electrolyte membranes, copolymerized membranes were prepared using styrene derivatives such as p-methylstyrene, t-butylstyrene, and ${\alpha}-methylstyrene$ by monomer sorption method. Prepared membrane was characterized by measurement of weight gain ratio, water content, ion-exchange capacity, proton conductivity, and oxidative stability under the accelerated condition. It was found that each step of monomer sorption method including sorption, polymerization and sulfonation could be affected by the properties and the structures of styrenederivatives. Due to difficulty of polymerization, ${\alpha}$-methylstyrene was copolymerized with styrene or p-methylstyrene. Prepared membrane using ${\alpha}-methylstyrene$ and styrene showed higher performance and stability comparing to copolymerized membrane with styrene. However, copolymerized membranes with ${\alpha}-methylstyrene$ did not showed much improved oxidative stability comparing to styrene membrane due to their lower molecular weight. The t-butylstyrene membrane showed a low performance due to substituted bulky-butyl group which prevents sorption and sulfonation reaction. However, copolymerized t-butylstyrene membranes with p-methylstyrene showed good performance and much improved stability than the styrene membranes.

• Membrane Journal
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• v.21 no.1
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• pp.1-12
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• 2011

Partially fluorinated poly(arylene ether sulfone) block ionomer membranes with different branch degree for fuel cell applications were investigated. A sulfonable monomer, a non-sulfonable monomer and a trifunctional branching agent were synthesized and the sulfonable monomer was oligomerized to obtain block structures. The oligomer was then further polymerized with the non-sulfonable monomer and the branching agent. The mole ratio of oligomer : non-sulfonable monomer was fixed at 4:6 and the content of the branching agent was varied from 0 to 2 mol% (BBC-40Bx). Post-sulfonation of BBC-40Bx was carried out using chlorosulfonic acid (CSA) (SBBC-40Bx). All the synthesized compounds were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity (IEC), water uptake and ion conductivity of SBBC-40Bx increased with the increment of branching agent content.

• Polymer(Korea)
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• v.28 no.1
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• pp.24-34
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• 2004

Transient sorption experiments were conducted among several combinations of fluoropolymers and various organic solvents. Fully fluorinated polymer tended to exhibit ideal sorption behavior, while partially fluorinated polymers showed anomalous sorption behaviors with a drastic acceleration at the final stage of uptake. Minimization of least-squares of the measured and predicted fractional uptake, which indicated the increasing degree of deviation from Fickian diffusion, gave values of 3.0${\times}$10$\^$-4/, 1.75${\times}$10$\^$-3/, 8.68${\times}$10/sup-3/, 1.75${\times}$10$\^$-2/, respectively, for perfluoroalkoxy copolymer, poly(ethylene-co-tetrafluoroethylene), poly(vinylidene fluoride), poly(ethylene-co-chlorotrifluoroethylene). From stress-strain tests, it was confirmed that non-Fickian diffusion is closely related to the significant variation of mechanical properties (such as modulus and tensile strength) of swollen polymer. Anomalous sorption behavior stemmed from non-Fickian diffusion caused by nonlinear disruption of polar inter-segmental bonds due to solvent-induced plasticization. Thus, it is imperative to investigate the diffusion behavior of swelling solvents in partially fluorinated polymers, especially for the application to barrier materials or perm-selective membranes.

• Proceedings of the Membrane Society of Korea Conference
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• 1999.07a
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• pp.39-42
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• 1999

Perfluoropolymers represent the ultimate resistance to hostile chemical environments and high service temperature, attributed to the presence of fluorine in the polymer backbone, i.e. to the high bond energy of C-F and C-C bonds of fluorocarbons. Copolymers of Tetrafluoroethylene (TEE) and 2, 2, 4Trifluoro-5Trifluorometoxy- 1, 3Dioxole (TTD), commercially known as HYFLON AD, are amorphous perfluoropolymers with glass transition temperature (Tg)higher than room temperature, showing a thermal decomposition temperature exceeding 40$0^{\circ}C$. These polymer systems are highly soluble in fluorinated solvents, with low solution viscosities. This property allows the preparation of self-supported and composite membranes with desired membrane thickness. Symmetric and asymmetric perfluoropolymer membranes, made with HYFLON AD, have been prepared and evaluated. Porous and not porous symmetric membranes have been obtained by solvent evaporation with various processing conditions. Asymmetric membranes have been prepared by th wet phase inversion method. Measure of contact angle to distilled water have been carried out. Figure 1 compares experimental results with those of other commercial membranes. Contact angles of about 120$^{\circ}$for our amorphous perfluoropolymer membranes demonstrate that they posses a high hydrophobic character. Measure of contact angles to hexandecane have been also carried out to evaluate the organophobic character. Rsults are reported in Figure 2. The observed strong organophobicity leads to excellent fouling resistance and inertness. Porous membranes with pore size between 30 and 80 nanometers have shown no permeation to water at pressures as high as 10 bars. However high permeation to gases, such as O2, N2 and CO2, and no selectivities were observed. Considering the porous structure of the membrane, this behavior was expected. In consideration of the above properties, possible useful uses in th field of gas- liquid separations are envisaged for these membranes. A particularly promising application is in the field of membrane contactors, equipments in which membranes are used to improve mass transfer coefficients in respect to traditional extraction and absorption processes. Gas permeation properties have been evaluated for asymmetric membranes and composite symmetric ones. Experimental permselectivity values, obtained at different pressure differences, to various single gases are reported in Tab. 1, 2 and 3. Experimental data have been compared with literature data obtained with membranes made with different amorphous perfluoropolymer systems, such as copolymers of Perfluoro2, 2dimethyl dioxole (PDD) and Tetrafluorethylene, commercialized by the Du Pont Company with the trade name of Teflon AF. An interesting linear relationship between permeability and the glass transition temperature of the polymer constituting the membrane has been observed. Results are descussed in terms of polymer chain structure, which affects the presence of voids at molecular scale and their size distribution. Molecular Dyanmics studies are in progress in order to support the understanding of these results. A modified Theodoru- Suter method provided by the Amorphous Cell module of InsightII/Discover was used to determine the chain packing. A completely amorphous polymer box of about 3.5 nm was considered. Last but not least the use of amorphous perfluoropolymer membranes appears to be ideal when separation processes have to be performed in hostile environments, i.e. high temperatures and aggressive non-aqueous media, such as chemicals and solvents. In these cases Hyflon AD membranes can exploit the outstanding resistance of perfluoropolymers.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.305-309
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• 2016

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, to test the durability of sPEEK MEA (Membrane and Electrode Assembly), ADT (Accelerated Degradation Test) of MEA degradation was done at the condition that membrane and electrode were degraded simultaneously. Before and after degradation, I-V polarization curve, hydrogen crossover, electrochemical surface area, membrane resistance and charge transfer resistance were measured. Although the permeability of hydrogen through sPEEK membrane was low, sPEEK membrane was weaker to radical evolved at low humidity and OCV condition than fluorinated membrane such as Nafion. Performance after MEA degradation for 144 hours and 271 hours were reduced by 15% and 65%, respectively. It was showed that the main cause of rapid decrease of performance after 144 hours was shorting due to Pt/C particles in the pinholes.

• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.296-301
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• 2017

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, sulfonated poly (ether ether ketone) (sPEEK) membrane reinforced with poly imide was made to enhance of membrane durability. In order to test durability of single (un-reinforced) membrane and reinforced membrane MEA (Membrane and Electrode Assembly), degradation accelerated stress test was used. Before and after degradation, I-V polarization curve, hydrogen crossover current, electrochemical surface area, membrane resistance and charge transfer resistance were measured. As a result of experiments, hydrogen crossover current of reinforced MEA was lower than that of single MEA, therefor durability of reinforced MEA was higher than that of single MEA. There was not especially short phenomena in reinforced MEA after degradation accelerated stress test.

• Korean Chemical Engineering Research
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• v.54 no.2
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• pp.181-186
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• 2016

Recently, there are many efforts focused on development of more economical non-fluorinated membranes for use in PEMFCs (Proton Exchange Membrane Fuel Cells). In this study, characteristics of sulfonated Poly(ether ether ketone) (sPEEK) were compared according to degrees of sulfonation (DS), relative humidity, cell temperatures at PEMFC operation condition. I-V polarization curve, hydrogen crossover, electrochemical surface area, membrane resistance and charge transfer resistance were measured. sPEEK membrane showed high performance at high DS, high temperature and high relative humidity, in particular, performance of sPEEK membrane decreased largely due to low ionic conductivity at low DS and low relative humidity.