Novel Proton Conducting Membranes from the Combination of Sulfonated Polymers of Polyetheretherketones and Polyphosphazenes Doped with Sulfonated Single‐Walled Carbon Nanotubes

Intent on developing efficient proton exchange membranes used for direct methanol fuel cells as well as hydrogen fuel cells, a series of membranes based on sulfonated polyetheretherketone and sulfonated polyphosphazene‐graft copolymers is prepared by cross‐linking reaction because the former material has good enough mechanical property, while the latter is excellent in the proton transfer. The cross‐linked membranes combine the advantages of the two kinds of polymers. Among them, the membrane poly[(4‐trifluoromethylphenoxy)(4‐methylphenoxy)phosphazene]‐g‐poly {(styrene)₁₁‐r‐[4‐(4‐sulfobutyloxy)styrene]₃₃‐sulfonated poly(ether ether ketone)75 (CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75) shows a proton conductivity at 0.143 S cm⁻¹ under fully hydrated conditions at 80 °C and performs tensile strength about five times as much as did the sulfonated polyphosphazene membrane CF₃‐PS₁₁‐PSBOS₃₃. Further doping of sulfonated single‐walled carbon nanotubes (S‐SWCNTs) into the cross‐linked membranes on the screening of additives gives composite membrane CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75‐SWCNT possessing proton conductivity of 0.196 S cm⁻¹, even higher than that of Nafion 117 and a tensile strength comparable to that of Nafion 117. However, this significance of the composite membrane in the proton conduction is not observed in the test with a H₂/air fuel cell when it shows a maximal power density of 280 mW cm⁻² at 80 °C, whereas 294 mW cm⁻² is observed for CF₃‐PS₁₁‐PSBOS₃₃‐SPEEK75.

     

Effect of polyphenylene sulfide containing amino unit on thermal and mechanical properties of polyphenylene sulfide/glass fiber composites

Three kinds of high‐molecular‐weight compatibilizers [copoly(1,4‐phenylene sulfide)‐poly(2,5‐phenylene sulfide amine)] (PPS‐NH₂) containing different proportions of amino units in the side chain) were synthesized by the reaction of dihalogenated monomer and sodium sulfide via nucleophilic substitution polymerization under high pressure. The intrinsic viscosity of the obtained copolymers was 0.354–0.489 dL/g and they were found to have good thermal performance with melting point (T_m) of 271.3–281.0 °C and initial degradation temperature (T_d) of 490.0–495.7 °C. There was an excellent physical compatibility between PPS‐NH₂ and the pure industrial PPS. The results of dynamic mechanical analysis and macro‐ and micromechanical test showed that the selective compatibilizer PPS‐NH₂ (1.0) (1.0% mol aminated ratio) can improve the mechanical and interfacial properties of polyphenylene sulfide/glass fiber (PPS/GF) composite. The macro‐optimal tensile strength, Young's modulus, bending strength, and notched impact strength of 5%PPS‐NH₂ (1.0)/PPS/GF composite raised up to 141 MPa, 1.98 GPa, 203 MPa, and 6.15 kJ/m², which increased 12.8%, 9.4%, 4.1%, and 13.8%, respectively, comparing with the pure PPS/GF composite (125 MPa, 1.81 GPa, 195 MPa, and 5.40 kJ/m², respectively). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45804.     

Effects of organically modified nanoclay on the transport properties and electrochemical performance of acid‐doped polybenzimidazole membranes

Nanocomposite polyelectrolyte membranes based on phosphoric acid (H₃PO₄) doped polybenzimidazoles (PBIs) with various loading weights of organically modified montmorillonite (OMMT) were prepared and characterized for direct methanol fuel cell (DMFC) applications. X‐ray diffraction analysis revealed the exfoliated structure of OMMT nanolayers in the polymeric matrices. An H₃PO₄–PBI/OMMT membrane composed of 500 mol % doped acid and 3.0 wt % OMMT showed a membrane selectivity of approximately 109,761 in comparison with 40,500 for Nafion 117 and also a higher power density (186 mW/cm²) than Nafion 117 (108 mW/cm²) for a single‐cell DMFC at a 5M methanol feed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Partially Sulfonated Poly(vinylidene fluoride) Induced Enhancements of Properties and DMFC Performance of Nafion Electrolyte Membrane

Partially sulfonated poly(vinylidene fluoride) (SPVdF) has been prepared by incorporation of sulfonic acid groups within poly(vinylidene fluoride), using chlorosulfonic acid as the sulfonating agent. The degree of sulfonation (DS) has been varied by modulating the duration of the sulfonation reaction. Blending of SPVdF (having DS = 36.78%) with Nafion at a constituent wt.% ratio of SPVdF:Nafion = 70:30 has resulted in the fabrication of polymer electrolyte membrane with superior properties compared to pristine Nafion‐117 membrane. This particular blend composition exhibited a proton conductivity value of 3.6 × 10⁻² S cm⁻¹ (i.e. ∼12.5% increase over Nafion‐117), a methanol permeability value of 6.81 × 10⁻⁷ cm² s⁻¹ at 6M methanol concentration (i.e. ∼99.31% decrease from Nafion‐117) and a corresponding membrane selectivity value of 5.29 × 10⁴ Ss cm⁻³ (i.e. an increase of approximately two‐orders of magnitude over Nafion‐117) at 20 °C. In addition, this blend composition has also exhibited (a) better heat stability at temperatures as high as 160 °C by virtue of it possessing higher glass transition temperature, (b) higher storage modulus, (c) higher stress relaxation at high angular frequency and (d) superior DMFC performance at high methanol feed concentration in presence of humidified, as well as, non‐humidified air as the catholyte, compared to Nafion‐117 membrane.     

A Fuel‐Flexible Alkaline Direct Liquid Fuel Cell

We constructed a fuel‐flexible fuel cell consisting of an alkaline anion exchange membrane, palladium anode, and platinum cathode. When an alcohol fuel was used with potassium hydroxide added to the fuel stream and oxygen was the oxidant, the following maximum power densities were achieved at 60 °C: ethanol (128 mW cm⁻²), 1‐propanol (101 mW cm⁻²), 2‐propanol (40 mW cm⁻²), ethylene glycol (117 mW cm⁻²), glycerol (78 mW cm⁻²), and propylene glycol (75 mW cm⁻²). We also observed a maximum power density of 302 mW cm⁻² when potassium formate was used as the fuel under the same conditions. However, when potassium hydroxide was removed from the fuel stream, the maximum power density with ethanol decreased to 9 mW cm⁻² (using oxygen as oxidant), while with formate it only decreased to 120 mW cm⁻² (using air as the oxidant). Variations in the performance of each fuel are discussed. This fuel‐flexible fuel cell configuration is promising for a number of alcohol fuels. It is especially promising with potassium formate, since it does not require hydroxide added to the fuel stream for efficient operation.     

Tribological properties of porous PPS/PTFE composite filled with mesopore titanium oxide whisker

Nano‐micro hierarchical porous polyphenylene sulfide/polytetrafluoroethylene (PPS/PTFE) composites were prepared by mold‐leaching and vacuum melting process under high temperature condition. The tribological behaviors of porous PPS/PTFE composites and the synergism as a result of incorporation of both micro‐porogen (NaCl) and mesoporous TiO₂ whiskers were investigated. The effects of mesoporous TiO₂ whiskers and nonperforated TiO₂ whiskers on the friction and wear properties of PPS/PTFE composites were comparatively studied, respectively. Results indicated that the wear rate of porous PPS/PTFE composites with 30 wt % NaCl and 7 wt % mesoporous TiO₂ whiskers obtained the lowest values under the load of 100 N. Compared with pure PPS, the wear resistance of nano‐micro porous PPS/PTFE composite was enhanced by 6.45 × 10³ times, showing outstanding wear resistance. During sliding condition, grease could be squeezed through the nano‐micro pores under the coupling effect of load and friction heat, and formed a lubricanting layer on friction surface, providing self‐lubricating effect and high wear resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrochemical Analysis of a System Based on W and Ni Combined with CeO2 as Potential Sulfur‐tolerant SOFC Anode

A formulation of tungsten and nickel combined with CeO₂ (WNi‐Ce) was prepared and evaluated as sulfur‐tolerant anode for SOFC at intermediate temperature. Structural and morphological changes that take place in the system upon interactions with hydrogen sulfide were analyzed. The electrochemical performance was tested in a single cell, WNi‐Ce/LDC/LSGM/LSFC, varying H₂S concentration (0–500 ppm) at 750 °C using I–V curves, impedance spectroscopy and load demands. The highest cell performance was reached in H₂ and decrease with H₂S content increase in the fuel from 226 mW cm⁻² in pure H₂ to 108 mW cm⁻² in 500 ppm H₂S/H₂. Essentially, no decay in the cell performance was observed in the several short‐term load tests studied under several H₂S concentration (0–500 ppm) during 1h, and even in 500 ppm H₂S/H₂ during 70 h, indicating that this material could be a potential sulfur‐tolerant anode.     

New organic–inorganic hybrid membranes based on sulfonated polyimide/aminopropyltriethoxysilane doping with sulfonated mesoporous silica for direct methanol fuel cells

A series of novel composite methanol‐blocking polymer electrolyte membranes based on sulfonated polyimide (SPI) and aminopropyltriethoxysilane (APTES) doping with sulfonated mesoporous silica (S‐mSiO₂) were prepared by the casting procedure. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The crosslinking networks of amino silica phase together with sulfonated mesoporous silica improved the thermal stability of the hybrid membranes to a certain extent in the second decomposition temperature (250–400°C). The composite membranes doping with sulfonated mesoporous silica (SPI/APTES/S‐mSiO₂) displayed superior comprehensive performance to the SPI and SPI/APTES membranes, in which the homogeneously embedded S‐mSiO₂ provided new pathways for proton conduction, rendered more tortuous pathways as well as greater resistance for methanol crossover. The hybrid membrane with 3 wt % S‐mSiO₂ into SPI/APTES‐4 (SPI/A‐4) exhibited the methanol permeability of 4.68 × 10^?6 cm² s^?1at 25°C and proton conductivity of 0.184 S cm^?1 at 80°C and 100%RH, while SPI/A‐4 membrane had the methanol permeability of 5.16 × 10^?6 cm² s^?1 at 25°C and proton conductivity of 0.172 S cm^?1 at 80°C and 100%RH and Nafion 117 exhibited the values of 8.80 × 10^?6 cm² s^?1 and 0.176 S cm^?1 in the same test conditions, respectively. The hybrid membranes were stable up to about 80°C and demonstrated a higher ratio of proton conductivity to methanol permeability than that of Nafion117. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Incorporating sepiolite and kaolinite to improve the performance of SPEEK composite membranes for proton exchange membrane fuel cells

SPEEK polymer based thermally crosslinked polymer membranes are prepared by sol-gel synthesis using kaolinite and sepiolite clays as additives. Characterization tests, ie, mechanical stability, thermal gravimetric analysis, ion exchange capability, swelling properties, water uptake capacities, electrochemical impedance spectroscopy analysis, and Fourier transform infrared spectroscopy (FTIR) analysis of the membranes were conducted. The sepiolite and kaolinite addition enhanced the thermal stability and the thermal crosslinking reduced the swelling capacity of the synthesized membranes. Proton conductivity results were increased from 0.172 to 0.268 S cm⁻¹ by adding 9% of kaolinite, and to 0.329 S cm⁻¹ at 80°C by adding 9% of sepiolite to the SPEEK membrane's polymer structure. The fuel cell current density and potential measurements of 141 mA cm⁻² and 84.6 mW cm⁻² were found respectively at 0.6 V for the SPEEK/S9 membrane, whereas values of 600 mA cm⁻² and 348 mW cm⁻² were found for the Nafion commercial membrane.     

New composite membrane poly(vinyl alcohol)/graphene oxide for direct ethanol–proton exchange membrane fuel cell

This study investigated a simple synthesis of a crosslinked poly(vinyl alcohol)/ graphene oxide composite membrane with lower ethanol permeability membrane for passive direct ethanol–proton exchange membrane fuel cells (DE-PEMFCs). The chemical and physical structure, morphologies, ethanol uptake and permeability, ion exchange capacities, water uptake, and proton conductivities were determined and found that transport properties of the membrane were affected by the GO loading. The composite membrane with optimum GO content (15 wt %) exhibited the highest proton conductivity of 9.5 × 10⁻³ Scm⁻¹ at 30°C, 3.24 × 10⁻² Scm⁻¹ at 60°C, respectively and reduced ethanol permeability until 1.75 × 10⁻⁷ cm² s⁻¹. In the passive DE-PEMFC, the power density at 60°C were obtained as 5.84 mW cm⁻² higher than those by commercial Nafion 117 is 4.52 mW cm⁻². © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46928.     

Electrochemical Performance of MnO2‐based Air Cathodes for Zinc‐air Batteries

This paper compares the oxygen reduction on four MnO₂‐based air cathodes assembled in home‐made electrochemical cells, with some particular observations on α‐MnO₂ cathode. The results show that the catalytic activity decreases in the following order: electrolytic MnO₂ (EMD) > natural MnO₂ (NMD) > β‐MnO₂ > α‐MnO₂. The maximum power density of the zinc‐air battery with EMD as the catalyst reaches up to 141.8 mW cm⁻² at the current density of 222.5 mA cm⁻², which is about 60%, 20% and 10% higher than that of α‐MnO₂ (90.0 mW cm⁻² at 120.3 mA cm⁻²), β‐MnO₂ (121.5 mW cm⁻² at 150.4 mA cm⁻²) and NMD (128.2 mW cm⁻² at 207.8 mA cm⁻²), respectively. It is believed that its unique crystal structure and biggest BET surface area make EMD have the smallest charge transfer resistance (R_ct), thus EMD has the highest activity.     

Nanostructured membrane electrode assemblies from layer‐by‐layer composite/catalyst containing membranes and their fuel cell performances

In this study, two approaches are compared to develop nanostructured membrane electrode assemblies (MEA) using layer‐by‐layer (lbl) technique. The first is based on the direct deposition of polyallylamine hydrochloride (PAH) and sulfonated polyaniline (sPAni) on Nafion support to prepare lbl composite membrane. In the second approach, sPAni is coated on the support in the presence of platinum (Pt) salt, Nafion solution and Vulcan for obtaining catalyst containing membranes (CCMs). SEM and UV–vis analysis show that the multilayers are deposited on both sides of Nafion successfully. Although H₂/O₂ single cell performances of acid doped lbl composite membrane based MEA are found to be at the range of 126 and 160 mW cm^?2 depending on the number of deposited layers, the cell performance of MEA obtained from catalyst containing lbl self‐assembled thin membrane (PAH/sPAni‐H⁺)_10‐Pt is found to be 360 mW cm^?2 with a Pt utilization of 720 mW mgPt^?1. This performance is 82% higher as compared to original Nafion^®117 based MEA (198 mW cm^?2). From the cell performance evaluations for different structured MEAs, it is mainly found out that the use of lbl CCMs instead of composite membranes and fabrication of thinner electrolytes result in a higher H₂/O₂ cell activity due to significant reduction in ohmic resistivity. Also, it is observed that the use of sPAni slightly improves the cell performance due to an increased probability of the triple phase contact and it can lead to superior physicochemical properties such as conductivity and thermal stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40314.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Measuring oxygen, carbon monoxide and hydrogen sulfide diffusion coefficient and solubility in Nafion membranes

A Devanathan-Stachurski type diffusion cell made from a fuel cell assembly is designed to evaluate the gas transport properties of a proton exchange membrane as a function of cell temperature and gas pressure. Data obtained on this cell using the electrochemical monitoring technique (EMT) is used to estimate solubility and diffusion coefficient of oxygen (O₂), carbon monoxide (CO) and hydrogen sulfide (H₂S) in Nafion membranes. Membrane swelling and reverse-gas diffusion due to water flux are accounted for in the parameter estimation procedure. Permeability of all three gases was found to increase with temperature. The estimated activation energies for O₂, CO and H₂S diffusion in Nafion 112 are 12.58, 20 and 8.85 kJ mol⁻¹, respectively. The estimated enthalpies of mixing for O₂, CO and H₂S in Nafion 112 are 5.88, 3.74 and 7.61 kJ mol⁻¹, respectively. An extensive comparison of transport properties estimated in this study to those reported in the literature suggests good agreement. Oxygen permeability in Nafion 117 was measured as a function of gas pressures between 1 and 3 atm. Oxygen diffusion coefficient in Nafion 117 is invariant with pressure and the solubility increases with pressure and obeys Henry's law. The estimated Henry's constant is 3.5 × 10³ atm.     

Membrane Electrode Assembly with Ultra Low Platinum Loading for Cathode Electrode of PEM Fuel Cell by Using Sputter Deposition

Cathode electrodes of proton exchange membrane fuel cells were fabricated by using Pt sputter deposition to increase the gravimetric power density (W mg_Pt⁻¹) with reduced Pt loading. Ultra low Pt‐based electrodes having Pt loading in between 0.0011 and 0.06 mg_Pt cm⁻² were prepared by a radio frequency (RF) sputter deposition method on the surface of a non‐catalyzed gas diffusion layer (GDL) substrate by changing the sputtering time (20, 90, 180, 1050 s). The effect of cathode Pt loading on the performance of membrane electrode assembly were investigated using polarization curve, impedance, H₂ crossover and cyclic voltammetry techniques. The effect of backpressure on PEMFC performance was also investigated. Sputter1050 (0.06 mg_Pt cm⁻²) exhibited the best power density at 80 °C cell temperature and without backpressure for H₂/O₂, 100 %RH (297 mW cm⁻² and 5 W mg_Pt⁻¹ at 0.6 V). On the other hand sputter90 (0.005 mg_Pt cm⁻²) showed the peak gravimetric power density (15 W mg_Pt⁻¹ and 75 mW cm⁻² at 0.6 V). The Pt utilization efficiency increased as the Pt loading decreased. Sputter20 and sputter90 electrodes yielded insufficient electrochemical surface area (ECSA), higher charge transfer and ohmic resistance, but sputter180 and sputter1050 yielded sufficient ECSA and lower charge transfer and ohmic resistance.     

An investigation of the friction and wear behaviors of polyphenylene sulfide filled with solid lubricants

Composites of polyphenylene sulfide (PPS) filled with solid lubricant particles of graphite (C), molybdenum disulfide (MoS₂), and polytetrafluoroethylene (PTFE) were prepared by compression molding. The size of the solid lubricant particles was 3‐;5 µm. The friction and wear behaviors of the composites were examined with a pinon‐disk test rig. The worn composite pin surfaces and the transfer films formed on the counterface were analyzed with scanning electron microscopy. An X‐ray photo‐electron spectroscope (XPS) was used to characterize the chemical states of the elements in the transfer film. It has been found that graphite and PTFE as the fillers increase the wear resistance of PPS considerably, while MoS₂ as the filler decreases the wear resistance of PPS greatly. The fillers promote the decomposition of PPS and generate compounds, which accounts for the changes in the wear resistance of the composites.     

Medium-chain-length poly-3-hydroxyalkanoates-carbon nanotubes composite as proton exchange membrane in microbial fuel cell

Medium-chain-length poly-3-hydroxyalkanoates (PHA) and carboxyl group-functionalized multiwalled carbon nanotubes (MC) were used to fabricate a composite membrane for application in a double-chambered microbial fuel cell (MFC). MC was composited into PHA at 5%, 10%, and 20% w/w via ultrasound dispersion blending method. PHA-MC composite was compared with Nafion 117 as proton exchange membrane in MFC operated with palm oil mill effluent (POME) wastewater. The composite exhibited prerequisite separator membrane characteristics. The dispersion of MC in the polymer matrix increased its interfacial surface area and water uptake properties. PHA-MC10% membrane in MFC showed maximum power density of 361?mW/m², which was comparable with Nafion 117 (372?mW/m²). Internal resistance decrease, chemical oxygen demand (COD) removal, coulombic efficiency (CE), and conductivity of the PHA-MC10% were superior to Nafion 117. The environmental-friendly material could provide an alternative towards realizing practical MFC application.     

A PFSA Composite Membrane with Sulfonic Acid Functionalized TiO2 Nanotubes for Polymer Electrolyte Fuel Cells and Water Electrolysers

Titanate nanotubes (TiO₂‐NT) were functionalized with sulfonic acid functional groups and characterized with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). Results confirmed that sulfonic acid groups were grafted onto TiO₂‐NT with a uniform distribution. When the functionalized titanate nanotube (F‐TiO₂‐NT) was incorporated in perfluorosulfonic acid membranes, the membrane conductivity and water uptake were improved. Polymer electrolyte membrane (PEM) fuel cells using 5 wt.% F‐TiO₂‐NT incorporated composite membrane exhibited a peak power density of 429 mW cm^–2 with non‐humidified O₂ at 90 °C, which is about four times higher than that with Nafion 117 membrane at identical conditions. PEMWE with 5 wt.% F‐TiO₂‐NT incorporated composite membrane achieved 1,000 mA cm^–2 current density at voltages below 1.6 V at 90 °C without back pressurizing.     

Development of alcohol/O2 biofuel cells using salt-extracted tetrabutylammonium bromide/Nafion membranes to immobilize dehydrogenase enzymes

Quaternary ammonium bromide salt-treated Nafion membranes provide an ideal environment for enzyme immobilization. Because these quaternary ammonium bromide salt-treated Nafion membranes retain the physical properties of Nafion and increase the mass transport of ions and neutral species through the membrane, they are also ideal for modifying electrodes. Therefore, high current density bioanodes are formed from poly(methylene green) (an electrocatalyst for NADH) modified electrodes that have been coated with a layer of tetrabutylammonium bromide salt-treated Nafion with dehydrogenase enzymes immobilized within the layer. Ethanol/O₂ biofuel cells employing these bioanodes have yielded power densities of 1.16 mW/cm² with a single-enzyme system (alcohol dehydrogenase) and 2.04 mW/cm² with a double-enzyme system (alcohol dehydrogenase and aldehyde dehydrogenase) in the polymer layer. Methanol/O₂ biofuel cells employing these bioanodes have yielded power densities of 1.55 mW/cm² and open circuit potentials of 0.71 V.     

Corrosion protection of steel and bond durability at polyphenylene sulfide-to-anhydrous zinc phosphate interfaces

To enhance the performance of high-temperature polyphenylene sulfide (PPS) coating in protecting steels from corrosion, the cold-rolled steel surfaces were prepared with anhydrous zinc phosphate (Zn · Ph) conversion coatings containing poly(acid) anhydride as an interfacial tailoring material. The factors contributing to the formation of a good bond at the PPS/Zn · Ph joints were as follows: (1) the chemical reaction of PPS with Fe₂O₃ in the Zn · Ph layers, (2) PPS-to-poly(acid) anhydride interaction, and (3) the mechanical interlocking between PPS and the rough Zn · Ph crystal surfaces. Although such interfacial bond structures provide a superior durability of PPS/Zn · Ph joints against a hot H₂SO₄ solution, the cathodic reaction, H₂O + ½O₂ + 2e^? = 2OH^?, occurring at any defect in the PPS/Zn · Ph joint system when NaCl is present will lead to the delamination of the PPS film from the phosphated steel. This cathodic delamination was due mainly to alkali-induced dissolution of Zn · Ph layers. However, the rate of delamination for the PPS/Zn · Ph systems was considerably lower compared with that for the PPS/steel system in the absence of Zn · Ph.