Recent progress of the gas diffusion layer in proton exchange membrane fuel cells: Material and structure designs of microporous layer

Proton exchange membrane fuel cells (PEMFCs) have become the most attractive power supply units for stationary and mobile applications. The operation, design characteristics, as well as performance of PEMFCs, are closely related to the multiphase transport of mass, heat, and electricity in the cell, a critical of which is the gas diffusion layer (GDL). It is very important to guarantee the transmission of water and gasses under high current density, and which is the weakness of PEMFCs at present. Microporous layer (MPL) is considered to be the key variable for mass transfer, so varieties of works focus on modification of MPL materials and its structure design. However, there is still a lack of special review to summarize and prospect the progress of MPL in recent years. This review article therefore focuses on the insights and comprehensive understanding of four critical issues of the MPL, the porosity, pore size distribution, wettability, structural design and the durability of MPL. At last, the conclusion and recommendations section summarized the future prospects and recommendations for possible research opportunities.     

Beneficial effects of wettability altering surfactants in oil-wet fractured reservoirs

In fractured reservoirs, an effective matrix-fracture mass transfer is required for oil recovery. Surfactants have long been considered for oil recovery enhancement, mainly in terms of their ability to reduce oil–water interfacial tension. These surfactants are effective when the fractured formations are water-wet, where capillary imbibition of surfactants from the fracture into the matrix contributes to oil recovery. However, another beneficial aspect of surfactants, namely their ability to alter wettability, remains to be explored and exploited. Surfactants capable of altering wettability can be especially beneficial in oil-wet fractured formations, where the surfactant in the fracture diffuses into the matrix and alters the wettability, enabling imbibition of even more surfactant into the matrix. This sequential process of initial diffusion followed by imbibition continues well into the matrix yielding significant enhancements in oil recovery.In order to test this hypothesis of sequential diffusion–imbibition phenomenon, Dual-Drop Dual-Crystal (DDDC) contact angle experiments have been conducted using fractured Yates dolomite reservoir fluids, two types of surfactants (nonionic and anionic) and dolomite rock substrates. A new experimental procedure was developed in which crude oil equilibrated with reservoir brine has been exposed to surfactant to simulate the matrix-fracture interactions in fractured reservoirs. This procedure enables the measurements of dynamic contact angles and oil–water interfacial tensions, in addition to providing the visual observations of the dynamic behavior of crude oil trapped in the rock matrix as it encounters the diffusing surfactant from the fractures. Both the measurements and visual observations indicate wettability alterations of the matrix surface from oil-wet to less oil-wet or intermediate wet by the surfactants. Thus this study is of practical importance to oil-wet fractured formations where surfactant-induced wettability alterations can result in significant oil recovery enhancements. In addition, this study has also identified the need to include contact angle term in the dimensionless Bond number formulations for better quantitative interpretation of rock–fluids interactions.     

Characteristics of Milk Powders Produced by Spray Freeze Drying

Skim and whole milk powders were manufactured at lab scale by spray freeze drying (SFD), using liquid nitrogen as the cryogen. The polydispersity of droplet/particle sizes was limited using an encapsulator nozzle to atomize the feed. Particle morphology was examined using a scanning electron microscope. Samples were compared with equivalent spray-dried powders in tests of wettability and dissolution in water. The spray freeze-dried powders were found to be highly porous, with a uniform structure of pores throughout the entire particles. When tested in water, SFD skim milk powders wetted roughly three times as fast as industrially spray-dried agglomerated skim milk powders and were observed to dissolve rapidly by breaking down into smaller particles.     

A comparative study on the effect of VUV radiation in plasma SiOx-coated polyimide and polypropylene films

Wettability of polyimide (PI) and polypropylene (PP) films have been improved using SiO_x-like thin layers deposited from a mixture of hexamethyldisiloxane (HMDSO) and oxygen in a microwave distributed electron cyclotron resonance plasma reactor. The films wettability evolution behaviors were evaluated through the results of contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The plasma depositions of SiO_x thin layers in presence of VUV radiation induce a contact angle decrease to about 7° and 35° for PI and PP films, respectively. XPS data showed that such difference in wettability is attributed to the increase of hydrophilic group's proportion at the surface of coated PI films due to VUV irradiation. AFM images showed that the PI surface topography remains relatively smooth when coated in presence of VUV radiation. However, in the case of PP films, AFM images revealed the growth of irregular structure due to a substrate etching effect supported by VUV radiation. For polymers coated without VUV irradiation, the deconvolution of the C1s peaks showed a significant decrease of CO bonds for both PI and PP substrates.     

The effect of Al content on the wettability between liquid iron and MgOAl2O3 binary substrate

In the present study, the wettability between liquid iron with two different Al contents and MgOAl₂O₃ binary substrates was studied in reducing atmosphere. The contact angles between liquid iron with 18?ppm Al and MgO, MgO·Al₂O₃, Al₂O₃ were 133.5°, 113.7°, 126.9° respectively. With the variation of the substrate composition, the contact angles for the intermediate binary phases of the three components (MgO, MgO·Al₂O₃, Al₂O₃) obeyed the Cassie theory. In the experiment using iron with 370?ppm Al, all the contact angles were higher than that using low Al-containing iron. The surface of the iron drop was covered with an oxide layer, which mainly consisted of many small particles. With the variation of the substrate gradually from MgO to Al₂O₃, the composition of the oxide layer changed from MgO·Al₂O₃ to CaOAl₂O₃. The formation of the oxide layer prevented the spreading of liquid iron, leading to the increase of the contact angle.     

EFFECTS OF NONIONIC SURFACTANTS ON PERFORMANCE OF COPPER CHEMICAL MECHANICAL POLISHING

During copper chemical mechanical polishing (Cu-CMP), the physical properties of slurry, such as the dispersion and suspension stability of abrasives, the interaction between particles and the polished surface, and the rheological characteristics, greatly affect the planarization efficiency. In this study, several nonionic surfactants were added to change the aforementioned physical characteristics of slurry and Cu-CMP performance. Their effects were investigated. The experimental results showed that Al₂O₃ slurry with 300 ppm Triton DF-16 could enhance the wettability of the Cu surface and stabilize the dispersion of abrasives in the slurry. Therefore, the passivation reaction on the Cu surface during CMP would occur uniformly, and the removal of particles during post cleaning could be improved. Cu CMP using the slurry with an adequate amount of nonionic surfactants, Triton DF-16, is proposed to reduce the surface roughness, enhancing the planarity.     

Enhanced liquid spreading due to porosity

A conceptual pore level model (Chem. Eng. Sci. 57 (2002) 3401) of spreading of liquid over internally wet porous particles is applied to explain reported rector level enhancement in wetting of trickle bed reactor (Ind. Eng. Chem. Res. 36 (1997) 5133). It is confirmed that a symbiotic relationship exists between internal and external wetting of porous particles whereby each enhances the other. Further, it is illustrated that liquid spreading in porous solids is driven more by porosity than by contact angle. A major implication of this phenomena is that liquid will spread more on less wettable (but porous) surfaces in comparison to more wettable (but nonporus) surfaces and a reinterpretation of experiments involving spreading of liquid over porous solids is required. On a large scenario, it is hoped that present exercise will be in important step towards explaining the complex reactor level macro phenomena by simple and conceptual pore level micro models.     

Ameliorating effect of silica addition in the anode-catalyst layer of the membrane electrode assemblies for polymer electrolyte fuel cells

Incorporation of silica particles through a sol-gel process into the anode-catalyst layer with a sol-gel modified Nafion-silica composite membrane renders easy retention of back-diffused water from the cathode to anode through the composite membrane electrolyte, increases the catalyst-layer wettability and improves the performance of the Polymer Electrolyte Fuel Cell (PEFC) while operating under relative humidity (RH) values ranging between 18% and 100% with gaseous hydrogen and oxygen reactants at atmospheric pressure. A peak power density of 300 mW cm⁻² is achieved at a load current-density value of 1200 mA cm⁻² for the PEFC employing a sol-gel modified Nafion-silica composite membrane and operating at 18% RH. Under similar operating conditions, the PEFC with a Membrane Electrode Assembly (MEA) comprising Nafion-silica composite membrane with silica in the anode-catalyst layer delivers a peak power density of 375 mW cm⁻². By comparison, the PEFC employing commercial Nafion membrane fails to deliver satisfactory performance at 18% RH due to the limited availability of water at its anode, acerbated electro-osmotic drag of water from anode to cathode and insufficient water back diffusion from cathode to anode causing the MEA to dehydrate.     

Design of Lu2O3-reinforced Cf/SiC-ZrB2-ZrC ultra-high temperature ceramic matrix composites: Wetting and interfacial reactivity by ZrSi2 based alloys

The wettability and infiltration of molten ZrSi₂ and ZrSi₂-Lu₂O₃ alloys into C_f/SiC and B₄C-infiltrated C_f/SiC composites were investigated to understand the interfacial interactions that occur during the development of C_f/SiC-ZrC and C_f/SiC-ZrB₂-ZrC-Lu₂O₃ materials. A significant evaporation of Si from the liquid affected the wetting behaviour of the alloy when tested in a vacuum at 1670 °C. The better wetting and spreading of the alloy over the surface was observed for the composites with lower overall porosity (12 %). On the other hand, the formation of an outer dense layer, followed up by the uniform infiltrated region up to ～ 1 mm was observed for the C_f/SiC with higher porosity (21 %). The infiltrated alloy reacted with SiC matrix to form ZrC or with B₄C-infiltrated SiC matrix to form ZrB₂-ZrC-SiC. The Lu₂O₃ particles were not wetted by the melt, and were pushed away of the reaction zone by the solidification front.     

颗粒增强钢铁基表面复合材料铸渗技术的研究与发展

从材料的选择、铸渗工艺、及铸渗应用等方面,介绍了国内外运用铸渗法制备钢铁基表面复合材料的新进展.分析了复合材料中增强相和基体间的相互作用和界面问题.提出了今后研究工作中值得重视的几个问题.