Ionic polymeric membrane

Shahinpoor, M. and Mojarrad, M., Electrically-Induced Large Amplitude Vibration and Resonance Characteristics of Ionic Polymeric Membrane-Metal Composites, , Proceedings of 1997 SPIE Smart Materials and Structures Conference, vol. 3041-76, San Diego, California, March (1997)... 

By the time the next overview of electrical properties of polymers was published (Blythe 1979), besides a detailed treatment of dielectric properties it included a chapter on conduction, both ionic and electronic. To take ionic conduction first, ion-exchange membranes as separation tools for electrolytes go back a long way historically, to the beginning of the twentieth century a polymeric membrane semipermeable to ions was first used in 1950 for the desalination of water (Jusa and McRae 1950). This kind of membrane is surveyed in detail by Strathmann (1994). Much more recently, highly developed polymeric membranes began to be used as electrolytes for experimental rechargeable batteries and, with particular success, for fuel cells. This important use is further discussed in Chapter 11. 

Polymeric ionic conductors. One of the most unexpected developments in recent decades in the whole domain of electrochemistry has been the invention of and gradual improvements in ionically conducting polymeric membranes, to the... 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

Solvent polymeric membranes, conventionally prepared from a polymer that is highly plasticized with lipophilic organic esters or ethers, are the scope of the present chapter. Such membranes commonly contain various constituents such as an ionophore (or ion carrier), a highly selective complexing agent, and ionic additives (ion exchangers and lipophilic salts). The variety and chemical versatility of the available membrane components allow one to tune the membrane properties, ensuring the desired analytical characteristics. 

The selectivity here is directly proportional to complex formation constants and can be estimated, once the latter are known. Several methods are now available for determination of the complex formation constants and stoichiometry factors in solvent polymeric membranes, and probably the most elegant one is the so-called sandwich membrane method [31], Two membrane segments of different known compositions are placed into contact, which leads to a concentration polarized sensing membrane, which is measured by means of potentiometry. The power of this method is not limited to complex formation studies, but also allows one to quantify ion pairing, diffusion, and coextraction processes as well as estimation of ionic membrane impurity concentrations. 

One may think that the idea of detecting ionic compounds such as heparin using polymeric ion-selective electrodes seems very difficult due to the high charge of polyionic molecules, which makes the slope of the electrode function negligibly small for an analytical application. Indeed, for heparin-selective electrodes the theoretical slope is less than lmV decade 1 and the potential practically does not depend on heparin concentration, which means that this ISE can be useful as a reference electrode [33], Nonetheless, Ma and Meyerhoff noticed that the potential of polymeric membrane... 

Lipophilic ion exchangers traditionally used for polymeric membrane preparation are the anionic tetraphenylborate derivatives and the cationic tetraalkylammonium salts. The charges on both lipophilic ions are localized on a single (boron or nitrogen) atom, but the steric inaccessibility of the charged center, due to bulky substituents, may inhibit ion-pair formation in the membrane and provide, when necessary, non-specific interactions between ionic sites and sample ions. 

The first and very simple solid contact polymeric sensors were proposed in the early 1970s by Cattrall and Freiser and comprised of a metal wire coated with an ion-selective polymeric membrane [94], These coated wire electrodes (CWEs) had similar sensitivity and selectivity and even somewhat better DLs than conventional ISEs, but suffered from severe potential drifts, resulting in poor reproducibility. The origin of the CWE potential instabilities is now believed to be the formation of a thin aqueous layer between membrane and metal [95], The dominating redox process in the layer is likely the reduction of dissolved oxygen, and the potential drift is mainly caused by pH and p02 changes in a sample. Additionally, the ionic composition of this layer may vary as a function of the sample composition, leading to additional potential instabilities. 

SO Electrode. A gas-sensing SO2 electrode marketed by Ionics, Inc. was used to provide additional VLE data at 25°C as a function of composition. Aqueous SO2 equilibrates across a polymeric membrane with a filling solution containing about 0.1 M NaHSO-j. Ionic species do not diffuse across the membrane. A small combination glass electrode measures the pH of the filling solution. The SO2 activity (Pso ) is proportional to the activity of H+ (10"PH), because the bisulfite activity is constant ... 

To address the zinc dendrite problem in nickel-zinc cells, eVionyx claims to have developed a proprietary membrane system that is nonporous, has very high ionic conductivity, is of low cost, and can block zinc dendrite penetration even in high concentrations of KOH. The polymeric membrane has an ionic species contained in a solution phase thereof. The ionic species behaves like a liquid electrolyte, while at the same time the polymer-based solid gel membrane provides a smooth impenetrable surface that allows the exchange of ions for both discharging and charging of the cell. 

Membrane Technology The expression membrane separation covers a wide range of product separation techniques. They involve the separation of components mostly in fluid or even, sometimes, in gaseous state, through the application of the physical properties of ionic charges, diffusivity, and difference in molecular size of the compounds to be separated. It uses a wide range of inorganic and polymeric membranes, the selection of which depends on the material to be processed. 

Furthermore, in 2001, Ballard entered an alliance with Victrex to produce two new membrane alternatives. One membrane is based on sulfonated poly(arylether) ketone (a variant of PEEK) supplied by Victrex, which may be better suited to PEMFC fabrication applications. In March 2002, U.S. Patent 6,359,019 was issued to Ballard Power for a graft-polymeric membrane in which one or more trifluorovinylaromatic monomers are radiation graft polymerized to a preformed polymeric base. The strucmres of BAM membranes have been studied by way of small-angle neutron scattering (SANS) [97]. The study of the ionomer peak position suggests the existence of relatively small ionic domains compared to Nalion, despite large water content. Phase separation in the polymer matrix is possibly crucial for the membrane s mechanical and transport properties. 

Among the disadvantages, the fouling and degradation of membrane surfaces of the polymeric membrane systems under adverse chemical and thermal conditions are often cited. However, these problems may be partly overcome by proper pretreatment of the effluents, optimizing the process variables and selecting suitable membrane materials. The radioactive wastes most suited for membrane separation are characterized by chemically insignificant amounts of radionuclides and small amounts (few hundred parts per rnilhon) of inactive ionic species. 

Suitably modified fiber optic sensors can also be used for detecting gas vapors, humidity, ions, and organic compounds. Fiber inclusions that show length variation were used to develop humidity sensors, whereas ion-responsive lipid bilayers formed the basis for the detection of inorganic ions. Immobilized neutral and ionic crown ethers in polymeric membranes were designed as sensors for determination of barium and copper (Wolfbeis 2000). 

Membrane performance Is often measured by the ability of the membrane to prevent, regulate or facilitate permeation. The rate of permeation and the mechanism of transport depend upon the magnitude of the driving force, the size of the permeating molecule relative to the size of the available permanent or dynamic transport corridor and the chemical nature (dispersive, polar, Ionic, etc.) of both the permeant and the polymeric membrane material. 

Ilconich, J. B., Luebke, D. R., Myers, C., Pennline, H. W. (2006). Carbon dioxide separation through supported ionic hquids membranes in polymeric matrixes. In 23rd Annual International Pittsburgh Coal Conference, PCC—Coal-Energy, Environment and Sustainable Development, Pittsburgh. 

The nature of the supporting membrane also plays an important role in the performance of supporting ionic liquid membranes. In this context, de los Rios et al. [3] nsed two polymeric membranes, nylon and mitex, as supporting membranes. Nylon membrane was a hydrophilic polyamide membrane with a pore size of 0.45 pm and a thickness of 170 pm. Mitex membrane was a hydrophobic polytetrafluoroethylene membrane with a pore size of 10 pm and a thickness of 130 pm. It was observed that less ionic liquid was absorbed into the mitex membranes, which was explained by the different textural properties and the high hydrophobic character of these membranes, which probably restrict interaction with the hydrophilic ionic liquids used [27]. 

The use of nanofiltration membranes as supporting membranes have been also reported [28]. In this case, direct filtration of ionic liquids through the nanofiltration membrane was not possible at a gas pressure up to 7 bars. The ionic liquids with cations associated with straight or branched hydrocarbon chains were easily absorbed into the polymeric membrane allowing the nanoporous structure saturated with the ionic liquids. 

Micro fuel cell designs without polymeric membranes can overcome some PEM-related issues such as fuel crossover, anode dry-out or cathode flooding. In these membraneless laminar flow-based fuel cells (LF-EC) two or more liquid streams merge into a single microfluidic channel. The stream flows over the anode and the cathode electrodes placed on opposing side walls within the channel. The reaction of fuel and oxidant takes place at the electrodes while the two liquid streams and their liquid-liquid interface provide the necessary ionic transport [122,123]. 

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