Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

The focus of this program was to develop a new Proton Exchange Membrane (PEM) which can operate under hotter, dryer conditions than the state of the art membranes today and integrate it into a Membrane Electrode Assembly (MEA). These MEA's should meet the performance and durability requirements outlined in the solicitation, operating under low humidification conditions and at temperatures ranging from -20ÃÂúC to 120ÃÂúC, to meet 2010 DOE technical targets for membranes. This membrane should operate under low humidification conditions and at temperatures ranging from -20ÃÂúC to 120ÃÂúC in order to meet DOE HFCIT 2010 commercialization targets for automotive fuel cells. Membranes developed in this program may also have improved durability and performance characteristics making them useful in stationary fuel cell applications. The new membranes, and the MEAâÃÂÃÂs comprising them, should be manufacturable at high volumes and at costs which can meet industry and DOE targets. This work included: A) Studies to better understand factors controlling proton transport within the electrolyte membrane, mechanisms of polymer degradation (in situ and ex situ) and membrane durability in an MEA; B) Development of new polymers with increased proton conductivity over the range of temperatures from -20ÃÂúC to 120ÃÂúC and at lower levels of humidification and with improved chemical and mechanical stability; C) Development of new membrane additives for increased durability and conductivity under these dry conditions; D) Integration of these new materials into membranes and membranes into MEAâÃÂÃÂs, including catalyst and gas diffusion layer selection and integration; E) Verification that these materials can be made using processes which are scalable to commercial volumes using cost effective methods; F) MEA testing in single cells using realistic automotive testing protocols. This project addresses technical barriers A (Durability) and C (Performance) from the Fuel Cells section of the 2005 Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R&D Plan. In the course of this four-year program we developed a new PEM with improved proton conductivity, chemical stability and mechanical stability. We incorporated this new membrane into MEAs and evaluated performance and durability

Casimir micro-sphere diclusters and three-body effects in fluids

Our previous article [Phys. Rev. Lett. 104, 060401 (2010)] predicted that Casimir forces induced by the material-dispersion properties of certain dielectrics can give rise to stable configurations of objects. This phenomenon was illustrated via a dicluster configuration of non-touching objects consisting of two spheres immersed in a fluid and suspended against gravity above a plate. Here, we examine these predictions from the perspective of a practical experiment and consider the influence of non-additive, three-body, and nonzero-temperature effects on the stability of the two spheres. We conclude that the presence of Brownian motion reduces the set of experimentally realizable silicon/teflon spherical diclusters to those consisting of layered micro-spheres, such as the hollow- core (spherical shells) considered here.Comment: 11 pages, 9 figure

Increased Stability of PFSA Proton Exchange Membranes Under Fuel Cell Operation by the Decomposition of Peroxide Catalyzed by Heteropoly Acids

Abstract Proton exchange membranes were cast from mixtures of the 3M perfluorinated sulfonic acid ionomer, with side chain -O-(CF 2 ) 4 -SO 3 H, and various heteropoly acids (HPAs) at a 10 or 20 wt% doping level. The membrane electrode assemblies (MEAs) prepared from these membranes were subjected to a fuel cell testing protocol involving incubation to steady state, temperature challenge, accelerated testing, and post mortem analysis. The cell temperature was varied from 70 -100 ºC under relatively dry conditions, 70 ºC dewpoint, to avoid leaching of the HPA. The most important finding from this study was that the mor

Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

The focus of this program was to develop a new Proton Exchange Membrane (PEM) which can operate under hotter, dryer conditions than the state of the art membranes today and integrate it into a Membrane Electrode Assembly (MEA). These MEA's should meet the performance and durability requirements outlined in the solicitation, operating under low humidification conditions and at temperatures ranging from -20ÃÂúC to 120ÃÂúC, to meet 2010 DOE technical targets for membranes. This membrane should operate under low humidification conditions and at temperatures ranging from -20ÃÂúC to 120ÃÂúC in order to meet DOE HFCIT 2010 commercialization targets for automotive fuel cells. Membranes developed in this program may also have improved durability and performance characteristics making them useful in stationary fuel cell applications. The new membranes, and the MEAâÃÂÃÂs comprising them, should be manufacturable at high volumes and at costs which can meet industry and DOE targets. This work included: A) Studies to better understand factors controlling proton transport within the electrolyte membrane, mechanisms of polymer degradation (in situ and ex situ) and membrane durability in an MEA; B) Development of new polymers with increased proton conductivity over the range of temperatures from -20ÃÂúC to 120ÃÂúC and at lower levels of humidification and with improved chemical and mechanical stability; C) Development of new membrane additives for increased durability and conductivity under these dry conditions; D) Integration of these new materials into membranes and membranes into MEAâÃÂÃÂs, including catalyst and gas diffusion layer selection and integration; E) Verification that these materials can be made using processes which are scalable to commercial volumes using cost effective methods; F) MEA testing in single cells using realistic automotive testing protocols. This project addresses technical barriers A (Durability) and C (Performance) from the Fuel Cells section of the 2005 Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R&D Plan. In the course of this four-year program we developed a new PEM with improved proton conductivity, chemical stability and mechanical stability. We incorporated this new membrane into MEAs and evaluated performance and durability

Fundamentals of machine elements

Fundamentals of Machine Elements, Third Edition offers an in-depth understanding of both the theory and application of machine elements. Design synthesis is carefully balanced with design analysis, an approach developed through the use of case studies, worked examples, and chapter problems that address all levels of learning taxonomies. Machine design is also linked to manufacturing processes, an element missing in many textbooks. The third edition signifies a major revision from the second edition. The contents have been greatly expanded and organized to benefit students of all levels in design synthesis and analysis approaches. What’s New in This Edition: Balances synthesis and analysis with strong coverage of modern design theory Links coverage of mechanics and materials directly to earlier courses, with expansion to advanced topics in a straightforward manner Aids students of all levels, and includes tie-in to engineering practice through the use of case studies that highlight practical uses of machine elements Contains questions, qualitative problems, quantitative problems, and synthesis, design, and projects to address all levels of learning taxonomies Includes a solutions manual, book website, and classroom presentations in full color, as well as an innovative "tear sheet" manual that allows instructors to present example problems in lectures in a time-saving manner Expands contents considerably, Topics: the importance of the heat affected zone in welding; design synthesis of spur, bevel, and worm gears; selection of multiple types of rolling element bearings (including deep groove, angular contact, toroidal, needle, and cylindrical and tapered roller) using a standard unified approach; consideration of advanced welding approaches such as brazing, friction welding and spot welding; expansion of fatigue coverage including the use of the staircase method to obtain endurance limit; and design of couplings, snap rings, wave and gas springs, and hydrostatic bearings Provides case studies that demonstrate the real-world application of machine elements. For example, the use of rolling element bearings in windmills, powder metal gears, welds in blisks, and roller coaster brake designs are all new case studies in this edition that represent modern applications of these machine elements. Fundamentals of Machine Elements, Third Edition can be used as a reference by practicing engineers or as a textbook for a third- or fourth-year engineering course/module. It is intended for students who have studied basic engineering sciences, including physics, engineering mechanics, and materials and manufacturing processes

Interplay between Structure and Relaxations in Perfluorosulfonic Acid Proton Conducting Membranes

This study focuses on changes in the structure of ionomer membranes, provided by the 3M Fuel Cells Component Group, as a function of the equivalent weight (EW) and the relationship between the structure and the properties of the membrane. Wide-angle X-ray diffraction results showed evidence of both non-crystalline and crystalline ordered hydrophobic regions in all the EW membranes except the 700 EW membrane. The spectral changes evident in the vibrational spectra of the 3M membranes can be associated with two major phenomena: (1) dissociation of the proton from the sulfonic acid groups even in the presence of small amounts of water; and (2) changes in the conformation or the degree of crystallinity of the poly­(tetrafluoroethylene) hydrophobic domains both as a function of EW and membrane water content. All the membranes, regardless of EW, are thermally stable up to 360 °C. The wet membranes have conductivities between 7 and 20 mS/cm at 125 °C. In this condition, the conductivity values follow VTF behavior, which suggests that the proton migration occurs via proton exchange processes between delocalization bodies (DBs) that are facilitated by the dynamics of the host polymer. The conductivity along the interface between the hydrophobic and hydrophilic domains makes a larger contribution in the smaller EW membranes likely due to the existence of a greater number of interfaces in the membrane. The larger crystalline domains present in the higher EW membranes provide percolation pathways for charge migration between DBs, which reduces the probability of charge transfer along the interface. Therefore, at higher EWs although there is charge migration along the interface within the hydrophobic–hydrophilic domains, the exchange of protons between different DBs is likely the rate-limiting step of the overall conduction process

In-Depth Profiling of Degradation Processes in a Fuel Cell: 2D Spectral-Spatial FTIR Spectra of Nafion Membranes

We present in-depth profiling by micro FTIR of cross sections for Nafion 115 membranes in membrane-electrode assemblies (MEAs) degraded during 52 or 180 h at open circuit voltage (OCV) conditions, 90 °C and 30% relative humidity. Analysis of optical images showed highly degraded zones in both MEAs. Corresponding 2D FTIR spectral-spatial maps indicated that C–H and CO groups are generated during degradation. The highest band intensities for both groups appeared at a depth of 82 μm from the cathode in the MEA degraded for 180 h; the same bands were present but less intense at a depth of 22 μm from the cathode. Degradation at these depths is most likely associated with the location of the Pt band formed from Pt dissolution and migration into the membrane. The two degradation bands, CO and C–H, appeared at the same depths from the cathode, 82 and 22 μm, suggesting that they are generated by a common mechanism or intermediate. This result is rationalized by a very important first reaction: Abstraction of a fluorine atom from the polymer main chain and side chain by hydrogen atoms, H^•. This step is expected to cause main chain and side chain scission and to generate R_F–CF₂^• radicals that can react with H₂O₂, H₂O, and H₂ to produce both −COOH and RCF₂H groups

Novel Approaches to Immobilized Heteropoly Acid Systems for High Temperature, Low Relative Humidity Polymer-Type Membranes - Final Report

Original research was carried out at the CSM and the 3M Company from March 2007 through September 2011. The research was aimed at developing new to the world proton electrolyte materials for use in hydrogen fuel cells, in particular with high proton conductivity under hot and dry conditions (>100mS/cm at 120°C and 50%RH). Broadly stated, the research at 3M and between 3M and CSM that led to new materials took place in two phases: In the first phase, hydrocarbon membranes that could be formed by photopolymerization of monomer mixtures were developed for the purpose of determining the technical feasibility of achieving the program's Go/No-Go decision conductivity target of >100mS/cm at 120°C and 50%RH. In the second phase, attempts were made to extend the achieved conductivity level to fluorinated material systems with the expectation that durability and stability would be improved (over the hydrocarbon material). Highlights included: Multiple lots of an HPA-immobilized photocurable terpolymer derived from di-vinyl-silicotungstic acid (85%), n-butyl acrylate, and hexanediol diacrylate were prepared at 3M and characterized at 3M to exhibit an initial conductivity of 107mS/cm at 120°C and 47%RH (PolyPOM85v) using a Bekktech LLC sample fixture and TestEquity oven. Later independent testing by Bekktech LLC, using a different preheating protocol, on the same material, yielded a conductivity value of approximately 20mS/cm at 120°C and 50%RH. The difference in measured values is likely to have been the result of an instability of properties for the material or a difference in the measurement method. A dispersed catalyst fuel cell was fabricated and tested using a 150¼m thick HPA-based photocurable membrane (above, PolyPOM75v), exhibiting a current density of greater than 300mA/cm2 at 0.5V (H2/Air 800/1800sccm 70°C/75%RH ambient outlet pressure). Multiple lots of a co-polymer based on poly-trifluorovinylether (TFVE) derived HPA were synthesized and fabricated into films, Generation II films. These materials showed proton conductivities as high as 1 S/cm under high RH conditions. However, the materials suffered from compromised properties due to impure monomers and low molecular weights. Multiple lots of an HPA-immobilized fluoropolymer derived from preformed PVDF-HFP (Generation III films) were synthesized and formed into membranes at 3M and characterized at 3M to exhibit conductivity reaching approximately 75mS/cm at 120°C/40%RH using a Bekktech sample fixture and TestEquity oven (optimized membrane, at close of program). Initial fuel cell fabrication and testing for this new class of membrane yielded negative results (no measureable proton conductivity); however, the specific early membrane that was used for the two 5cm2 MEAs was later determined to have <1 mS/cm at 80°C/80%RH using the Bekktech fixture, vs. ca. 200 mS/cm at 80°C/80%RH for samples of the later-optimized type described above. Future work in this area (beyond the presently reported contract) should include additional attempts to fabricate and test fuel cells based on the later-optimized Generation II and III polymer. A manufacturing study was performed which predicted no difficulties in any future scale up of the materials