Breakthrough/drainage pressures and X-ray water visualization in gas diffusion layer of PEMFC

The primary role of the gas diffusion layers (GDLs) in polymer electrolyte membrane fuel cells (PEMFC) is to maintain the delicate balance between water retention and removal in GDLs. Water management in the fuel cell is related to the breakthrough pressure at which water starts to pass through GDL, and the drainage pressure, which is maintained after the breakthrough. These pressures are both related to water management in fuel cells. Here we measured these pressures for two different GDLs and used X-ray tomography to visualize the water distributions within them. We then relate the variations in liquid pressures to the visualization and discuss water management in PEMFC.     

Phase-contrast X-ray imaging of the gas diffusion layer of fuel cells

The understanding of and in situ observation of the transport and distribution of water in carbon‐paper gas diffusion layers (GDLs) using non‐destructive imaging techniques is critical for achieving high performance in polymer electrolyte fuel cells (PEFCs). To investigate the behavior of water in GDLs of PEFCs, phase‐contrast X‐ray imaging via X‐ray interferometric imaging (XII) and diffraction‐enhanced imaging (DEI) were performed using 35 keV X‐rays. The XII technique is useful for the radiographic imaging of GDLs and in situ observations of water evolution processes in operating PEFCs. DEI provides a way for tomographic imaging of GDLs in PEFCs. Because high‐energy X‐rays are applicable to the imaging of both carbon papers and heavy materials, which make up PEFCs, phase‐contrast X‐ray imaging techniques have proven to be valuable for investigation of GDLs.     

Formation of hydrophobic coating on PMMA surface using unipolar nanosecond-pulse DBD in atmospheric air

Dielectric barrier discharge (DBD) can modify the material surface and result in complicated physical and chemical reactions to improve the surface hydrophilicity, which is proved to be an effective method for surface modification. Compared with the traditional ac-excitation DBD, the DBD using unipolar pulses can avoid local overheat of microdischarges and can improve discharge efficiency under some conditions. In this paper, DBD excited by repetitive unipolar nanosecond generator was used to improve the hydrophobicity of Plexiglass (PMMA) surface by means of the interaction between air plasma and silicone oil. The output voltage had a rise time of 40 ns and a full width at half maximum of about 70 ns. The surface hydrophobicity of the PMMA, before and after the surface modification, was evaluated via the contact angle measurement under different experimental conditions. The values of the contact angle shown in this paper were the average of eight measured values, and the standard deviations were also calculated. The surface energy including polar and dispersion components was calculated using the measured average contact angles of distilled water and polyethyleneglycol. The results showed that, as the increase of the discharge voltage, the contact angle increased but the surface energy decreased. With the increase of treatment time, the water contact angle of the modified surface increased at the beginning, and it would reach to a maximum at 7.5 min treatment, and then decreased. The effect of pulse frequency on the modification results was different at various treatment times. In addition, the possible physical and chemical reaction among the DBD plasma, silicone oil and the PMMA surface was discussed.     

Water content distribution in a polymer electrolyte membrane for advanced fuel cell system with liquid water supply

To better understand the operation of a new fuel cell design, we used magnetic resonance imaging (MRI) to measure the water content distribution in a polymer electrolyte membrane under fuel cell operation with and without a supply of liquid water. The supply of liquid water to the membrane improved the cell performance by increasing the water content in the membrane and thus reducing the electrical resistance of the membrane. The study also showed that MRI is a promising method to investigate the distribution of water in the membrane of a fuel cell under operating conditions.     

Effects of O2 and H2O plasma immersion ion implantation on surface chemical composition and surface energy of poly vinyl chloride

Oxygen and water plasma immersion ion implantation (PIII) was used to modify poly vinyl chloride (PVC) to enhance oxygen-containing surface functional groups for more effective grafting. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements. Our experimental results show that both oxygen and water PIII can greatly improve the O to C ratios on the surface. The optimal plasma processing conditions differ for the two treatments. The hydrophilicity and surface energy of the plasma-implanted PVC are also improved significantly. Our results indicate that O₂ and H₂O PIII increase both the polar and dispersion interactions and consequently the surface energy. It can be explained by the large amount of oxygen introduced to the surface and that many CC bonds are transformed into more polar oxygen containing functional groups.     

流道结构和几何尺寸对燃料电池性能影响的实验研究

流场板是质子交换膜燃料电池重要部件之一。本文对以氢气和氧气作为反应气体的质子交换膜电池的极化曲线进行了实验测定,研究了不同流场板结构、流场板深度和宽度对电池性能的影响．研究发现采用组合流道的电池性能最佳．     

Short-time plasma surface modification of HDPE powder in a Plasma Downer Reactor - process, wettability improvement and ageing effects

The effectiveness of improving the wettability of HDPE powders within less than 0.1 s by plasma surface modification in a Plasma Downer Reactor is investigated. A correlation is revealed between the XPS results (O/C-ratio) and the wettability (contact angle, polar surface tension by capillary rise method). The O₂-content in the plasma feed gas has been adjusted for best wettability properties. XPS results indicate the formation of CO and COOH functional groups on the powder surface. The O/C-ratio increased from 0.0 (no oxygen on the non-treated powder) up to 0.15 for the plasma treated HDPE powder surface. With pure O₂-plasma treatment, a water contact angle reduction from >90° (no water penetration into the untreated PE powder) down to 65° was achieved. The total surface free energy increased from 31.2 to 45 mN/m. Ageing of treated powders occurs and proceeds mostly within the first 7 days of storage. Contact angle measurements and O1s/O2s intensity ratio data support that ageing is mainly a diffusion-controlled process. Nevertheless, XPS results show the presence of oxygen functional groups even after 40 days, which explains why the powder is still dispersible in water without any addition of surfactants.     

Adsorption and diffusion of OH on Mo modified Pt(111) surface: First-principles theory

A first-principles study of adsorption and diffusion of OH on Pt and PtMo(111) surfaces is described. It confirms that the dissociation of water is much easier on PtMo than on pure Pt. Furthermore, we also found that OH binds most strongly at Mo atop site with adsorption energy of −3.32 eV, which is ∼1 eV stronger than binding to the pure Pt(111) surface. OH is much more localized on the PtMo alloy surface than on pure Pt. Both the stranger bond and the higher localization of OH contribute to the enhanced fuel cell performance with PtMo electrodes compared to pure Pt.     

Studies on behaviors of dipalmitoylposphatidylcholine and bilirubin in mixed monolayer at the air/water interface

Mixed monolayers of dipalmitoylposphatidylcholine (DPPC) and bilirubin (BR) were prepared on different subphases. The properties of DPPC/BR monolayer, such as collapse pressure (π_coll), limiting area per molecule (A_lim), surface compressibility modulus, free energy (ΔG_mix) and excess free energy (ΔG_ex), were investigated based on the analysis of the surface pressure-area isotherms on pure water. The results showed that DPPC and BR were miscible and formed non-ideal mixed monolayers at the air/water interface. With the molar fraction of BR (X_BR) increasing, the LE-LC coexistence region of DPPC monolayer was eliminated gradually. The DPPC/BR complex (M_D-B) of 1:2 stoichiometry formed as a result of the strong hydrogen bonds between the polar groups of DPPC and BR. The studies of effects of pH values and calcium ions in subphase on the DPPC/BR monolayers showed that the mixed monolayer became expanded on alkali aqueous solution and on 1 mmol/L CaCl₂ aqueous solution. The orientation of DPPC and BR at air/water interface was also discussed.     

Wettability and Surface Energy of Hydrogen-and Oxygen-Terminated Diamond Films

The contact angle and surface energy values of diamond are systemically investigated in terms of surface treatments(hydrogen-and oxygen-terminations), structure feature(single crystal diamonds and polycrystalline diamond films), crystal orientation((100),(111) and mixed(100)/(111) orientations), different fluids(probes of polar deionized water and nonpolar di-iodomethane). It is found that the hydrophobic/hydrophilic characteristic and surface energy values of diamond are mainly determined by the surface hydrogen/oxygen termination, and less related to the structural features and crystal orientation. Based on the contact angle values with polar water and nonpolar di-iodomethane, the surface energies of diamond are estimated to be about 43 m J/m~2 for hydrogen-termination and about 60 m J/m~2 for oxygen-termination. Furthermore, the varying surface roughness of diamond and fluids with different polarities examined determine the variation of contact angles as well as the surface energy values. These results would be helpful for a more detailed understanding of the surface properties of diamond films for further applications in a broad number of fields, such as optical and microwave windows,biosensors, and optoelectronic devices, etc.     

Monolayer adsorption of water on NaCl(1 0 0)

Density functional theory calculations have been applied to investigate the adsorption geometry of water overlayers on the NaCl(1 0 0) surface in the monolayer regime. Competition between H-H intermolecular repulsion and the attraction of the polar molecules to the surface ions results in the most stable structure having a 2 × 1 adsorption symmetry with an adsorption energy of 415 meV. Overlayers of 1 × 1 symmetry, as observed in experiment, have slightly lower adsorption energies. The layers are also unstable with respect to rotation of individual molecules. Multiple hydrogens/oxygens interacting with a single substrate ion can pull that ion out of the surface, although the examples considered are energetically very unfavourable. Overlayers of 1 × 1 symmetry with a coverage of one water molecule per NaCl do not have a high enough adsorption energy to wet the surface.     

Investigation on femtosecond laser irradiation energy in inducing hydrophobic polymer surfaces

This study investigates the use of ultrashort femtosecond laser pulses to induce hydrophobic properties on PMMA surfaces. The modification of surface wetting property exhibits a strong dependence on the amount of energy deposited on the PMMA surface. A simple equation has been deduced from the laser parameters to express the energy deposition. It was revealed that water contact angle (WCA) of more than 120°, with a maximum of around 125°, could be achieved when the total energy deposited per unit area on the PMMA surface ranged from 600 J/cm² to 900 J/cm² at an energy deposition rate of around 50 J/cm²/s. Beyond this range, WCA reduced with increasing amount of energy deposition. Furthermore, with higher energy deposition rate or higher laser fluence, total energy required to induce hydrophobic surfaces was reduced. Under different energy deposition, the quantity of polar groups or non-polar groups induced was responsible for the changes in WCA and thus the different surface hydrophobicity.     

Formation of functional groups on graphite during oxygen plasma treatment

Improved sample wettability was obtained by oxygen plasma functionalization of pyrolytic graphite. The samples were exposed to highly dissociated oxygen plasma with the density of 1 × 10¹⁶ m⁻³, the electron temperature of about 5.5 eV and the density of neutral oxygen atoms of 8 × 10²¹ m⁻³ for 20 s. The surface wettability was measured by a contact angle of water drop. The contact angle dropped from original 112° down to about 1°. The functional groups were detected by XPS analyses. The survey spectrum showed a substantial increase of oxygen concentration on the surface, while high-resolution analyses showed additional oxygen was bonded onto the graphite surface in the form of C-O polar functional group responsible for the increase of the surface energy.     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

压缩对不同疏水性处理气体扩散层内两相流的影响

聚四氟乙烯(PTFE)常用于调节质子交换膜燃料电池(PEMFC)中气体扩散层(GDL)的疏水性。目前虽有很多关于PTFE对GDL中水传输影响的研究,但同时考虑三维GDL微孔结构和压缩影响的研究还很缺乏。本文研究了压缩对不同接触角(不同PTFE含量)的GDL微孔结构中水传输行为的影响。通过耦合有限元方法(FEM)和流体体积(VOF)模型来模拟未压缩及压缩GDL中的两相流现象。结果表明,采用不同的接触角时,压缩对GDL内水传输行为的影响不同。压缩有利于水从GDL中排出,并促进水在GDL中的不均匀分布;压缩还促进了亲水性GDL内水在脊下的堆积,以及疏水性GDL内水在流道下方的堆积。由此可见,在进行GDL中内水传输行为研究时,应同时考虑压缩和接触角的影响。     

Quantifying phosphoric acid in high‐temperature polymer electrolyte fuel cell components by X‐ray tomographic microscopy

Synchrotron‐based X‐ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high‐temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro‐ and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40–100 wt% H₃PO₄). This renders the quantification and concentration determination challenging. The problem is solved by using propagation‐based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non‐operating fuel cell. The non‐destructive imaging methodology was verified by comparing image‐based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.     

Microscopy studies on pronton exchange membrane fuel cell electrodes with different ionomer contents

Proton Exchange Membrane (PEM) fuel cell electrodes with different ionomer contents were studied with various microscopic techniques. The morphology and surface potential were examined by Atomic Force Microscopy (AFM) and Kelvin Probe Microscopy (KPM), respectively. The particulate nature of the electrode was well displayed in the topography and phase images. The particle and pore size (Z) distributions showed the most frequent values at 30–40 nm and 20–30 nm, respectively. The particle size corresponds to the size of the carbon support for the platinum catalyst. Catalyst agglomeration was observed in high ionomer content electrodes. The surface potential images showed distinct difference to the topography images. The overall grain size was seen to increase, the pore volume to decrease, the surface roughness to decrease, and the surface potential variation to increase with the increase of ionomer content in the catalyst layer. Transmission electron microscopy (TEM) was carried out on selective electrodes to provide additional information and confirmed with the AFM results. Cyclic voltammetry (CV) showed that the electrode containing 30 wt.% ionomer has maximum catalyst utilization.     

Optoacoustic cross-section measurements for ir pulses: CO2 laser absorption by CF3I

The pulsed optoacoustic method is studied to measure absolute infrared multiphoton absorption cross sections. The influence of the thermalisation by the walls of the cell is shown to be very important at low pressure. This influence is analysed both experimentally and theoretically by solving the coupled diffusion and relaxation equations for vibrational and translational energies. The sensitivity of the method is limited by a spurious pressure signal present even with non-absorbing gases. This parasitic signal is attributed to an absorption located on the inner surface of the windows of the cell. For instance, using KCl windows, the observed spurious signal corresponds to about 10⁻⁴ of the total laser energy, transmitted from the windows to the gas. This proportion is independent on the energy fluence. Taking care of these limitations, we have measured the absorption cross section of CF₃I at the different wavelengths of the (001–020) transitions of the CO₂ laser. The typical energy fluences in these experiments were varied from 10⁻³ to 1J/cm². To be in collision free conditions, the CF₃I pressure was made equal to 0.2 Torr.     

Cold plasma-induced modification of the dyeing properties of poly(ethylene terephthalate) fibers

Surface modification of poly(ethylene terephthalate) (PET) fabrics induced by air radiofrequency (RF) plasma treatment has been investigated systematically as a function of plasma device parameters, to identify the plasma-polymer surface interactions prevailing under different operating conditions and leading to an increased color depth upon dyeing. Some tests have also been performed employing chemically inert argon as a feedstock gas. The dyeing properties of plasma-treated fibers were correlated to their topographical characteristics, determined by AFM analysis, and to their chemical surface composition, determined by XPS analysis, while the plasma-originated UV radiation was found to have no relevant effects in PET surface modification. The relative importance of plasma-induced surface processes, such as etching and grafting of polar species, is discussed in relation to their role in modifying PET dyeing properties.     

Analysis of energy consumption in heat pump and conventional driers

This paper compares energy consumptions in ehat pump driers and recirculating driers. The purpose of the analysis is to establish more general guidelines than those available in order to determine which drier configuration is a better choice at any given operating conditions. The comparison is based on computer models of the heat pump and recirculating driers. The models predict energy consumption figures for both driers operating at identical conditions (therefore extracting the same amount of water from the drying material). The results are shown as the mass of water evaporated per unit of energy input (the specific moisture extraction rate (SMER)) for both drier configurations. These values, as well as the ratio between these, are plotted in charts that show all the possible operating conditions, to enable easy comparison. The comparison presented here is based on energy consumption figures only, and therefore has the advantage of being independent of local conditions (such as economics, electricity generating efficiencies or relative values of different fuels) that are subjected to change. On the other hand, the SMER values presented can be easily modified to include the effect of local conditions in the drier selection process.