Membranes mechanical relaxations

In other words, the counter cation may be isolated from the bound anion by water shielding, resulting in a weakening of the interaction between the cation and anion. Hence, the effect of the counterion on the mechanical relaxation in the under-water state is not significant. It is obvious, therefore, that the enhancement of the primary relaxation upon neutralization of Nafion membranes in the dry state is mainly due to the strong ionic interactions. ... 

After extended operation of an STR PEM fuel cell with the same membrane electrode assembly (> 2500 h), autonomous oscillations were observed under conditions where the STR PEM fuel cell exhibited 5 steady states [23]. An example of the oscillations is shown in Figure 3.11.These oscillations have periods of 10 -10 s and show characteristics of a capacitively coupled switch. The oscillations transition very rapidly (<10s) between high and low states with an overshoot on the rise and undershoot and recovery on the fall. The period, magnitude and on/off times for these oscillations varied with temperature, and load resistance. Benziger and co-workers have suggested that these unusual dynamics are associated with mechanical relaxations of the polymer membrane driven by changing water content, but the detailed physical processes causing these unusual dynamics are not yet understood. 

T. Kyu and A. Eisenberg, Mechanical Relaxations in Peifluorosulfonate lonomer Membranes. In... 

Kyu T, Eisenberg A (1982) Mechanical relaxations in perfluorosulfonate-ionomer membranes. ACS Symp Ser 180 79-110... 

In an early study, Yeo and Eisenberg performed dynamic mechanical studies on H+ form Naflon membrane (EW = 1365). They note three mechanical peaks, labeled a, p, and y. The a-peak occurs at about 110°C. This relaxation was initially considered as the glass transition of the fluorocarbon matrix. The p-peak was seen at about 20°C. With increasing water content, the p-peak migrates to lower temperature, which suggested that p-peak associated with molecular motions within the ionic domains. The y-peaks at about -100°C were attributed to short-range molecular motions in the TFE phase. Later, Kyu and Eisenberg discussed dynamic mechanical relaxations for the same Naflon membrane. They found the a-peak is very... 

Kyu, T., Eisenberg, A. D. I., Mechanical relaxations in perfluorosulfonate ionomer membranes. In Perfluorinated Ionomer Membranes, Adi Eisenberg, Howard L. Yeager American Chemical Society Washington, 1982 Vol. 180, pp. 79-110. 

Contraction of muscle follows an increase of Ca " in the muscle cell as a result of nerve stimulation. This initiates processes which cause the proteins myosin and actin to be drawn together making the cell shorter and thicker. The return of the Ca " to its storage site, the sarcoplasmic reticulum, by an active pump mechanism allows the contracted muscle to relax (27). Calcium ion, also a factor in the release of acetylcholine on stimulation of nerve cells, influences the permeabiUty of cell membranes activates enzymes, such as adenosine triphosphatase (ATPase), Hpase, and some proteolytic enzymes and facihtates intestinal absorption of vitamin B 2 [68-19-9] (28). 

Although blood pressure control follows Ohm s law and seems to be simple, it underlies a complex circuit of interrelated systems. Hence, numerous physiologic systems that have pleiotropic effects and interact in complex fashion have been found to modulate blood pressure. Because of their number and complexity it is beyond the scope of the current account to cover all mechanisms and feedback circuits involved in blood pressure control. Rather, an overview of the clinically most relevant ones is presented. These systems include the heart, the blood vessels, the extracellular volume, the kidneys, the nervous system, a variety of humoral factors, and molecular events at the cellular level. They are intertwined to maintain adequate tissue perfusion and nutrition. Normal blood pressure control can be related to cardiac output and the total peripheral resistance. The stroke volume and the heart rate determine cardiac output. Each cycle of cardiac contraction propels a bolus of about 70 ml blood into the systemic arterial system. As one example of the interaction of these multiple systems, the stroke volume is dependent in part on intravascular volume regulated by the kidneys as well as on myocardial contractility. The latter is, in turn, a complex function involving sympathetic and parasympathetic control of heart rate intrinsic activity of the cardiac conduction system complex membrane transport and cellular events requiring influx of calcium, which lead to myocardial fibre shortening and relaxation and affects the humoral substances (e.g., catecholamines) in stimulation heart rate and myocardial fibre tension. 

Membrane depolarization typically results from an increase in Na+ conductance. In addition, mobilization of intracellular Ca2+ from the endoplasmic or sarcoplasmic reticulum and the influx of extracellular Ca2+ appear to be elicited by ACh acting on muscarinic receptors (see Ch. 22). The resulting increase in intracellular free Ca2+ is involved in activation of contractile, metabolic and secretory events. Stimulation of muscarinic receptors has been linked to changes in cyclic nucleotide concentrations. Reductions in cAMP concentrations and increases in cGMP concentrations are typical responses (see Ch. 21). These cyclic nucleotides may facilitate contraction or relaxation, depending on the particular tissue. Inhibitory responses also are associated with membrane hyperpolarization, and this is a consequence of an increased K+ conductance. Increases in K+ conductance may be mediated by a direct receptor linkage to a K+ channel or by increases in intracellular Ca2+, which in turn activate K+ channels. Mechanisms by which muscarinic receptors couple to multiple cellular responses are considered later. 

ATP is used not only to power muscle contraction, but also to re-establish the resting state of the cell. At the end of the contraction cycle, calcium must be transported back into the sarcoplasmic reticulum, a process which is ATP driven by an active pump mechanism. Additionally, an active sodium-potassium ATPase pump is required to reset the membrane potential by extruding sodium from the sarcoplasm after each wave of depolarization. When cytoplasmic Ca2- falls, tropomyosin takes up its original position on the actin and prevents myosin binding and the muscle relaxes. Once back in the sarcoplasmic reticulum, calcium binds with a protein called calsequestrin, where it remains until the muscle is again stimulated by a neural impulse leading to calcium release into the cytosol and the cycle repeats. 

The polycarbonate membranes are stretch-oriented during fabrication in order to improve their mechanical properties. If the membrane is subsequently heated above its glass-transition temperature ( 150°C), the polymer chains relax to their unstretched conformation and the membrane shrinks. This shrinking of the membrane around the Au nanowires in the pores causes the junction between the nanowire and the pore wall to be sealed. This is illustrated in Fig. 5, which shows voltammograms for tri-methylaminomethylferrocene (TMAFc+) before (Fig. 5A) and after (Fig. 

Under fuel cell operation, a finite proton current density, 0, and the associated electro-osmotic drag effect will further affect the distribution and fluxes of water in the PEM. After relaxation to steady-state operation, mechanical equilibrium prevails locally to fix the water distribution, while chemical equilibrium is rescinded by the finite flux of water across the membrane surfaces. External conditions defined by temperature, vapor pressures, total gas pressures, and proton current density are sufficient to determine the stationary distribution and the flux of water. 

In a subsequent communication, Elliott and coworkers found that uniaxially oriented membranes swollen with ethanol/water mixtures could relax back to an almost isotropic state. In contrast, morphological relaxation was not observed for membranes swollen in water alone. While this relaxation behavior was attributed to the plasticization effect of ethanol on the fluorocarbon matrix of Nafion, no evidence of interaction between ethanol and the fluorocarbon backbone is presented. In light of the previous thermal relaxation studies of Moore and co-workers, an alternative explanation for this solvent induced relaxation may be that ethanol is more effective than water in weakening the electrostatic interactions and mobilizing the side chain elements. Clearly, a more detailed analysis of this phenomenon involving a dynamic mechanical and/ or spectroscopic analysis is needed to gain a detailed molecular level understanding of this relaxation process. 

Cable and Moore performed DMA (dynamic mechanical analysis) studies of various Nafion membranes including the acid form. ° A tan <3 peak with maximum at 110 °C, referred to as Tg , was seen, and there is a suggestion of a shoulder on the low temperature side that might arise from another mechanism. As this membrane was dried at only 60 °C, the possibility of residual water incorporation exists. Moore and Cable concluded that the a relaxation was due to chain motions within and/or near the ion-rich domains and that the ji relaxation was... 

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