Occluded cells

F. 7.20 Sickled red blood cells occlude a blood vessel, causing hypoxia (low O2 in cells) and necrosis (cell death). 

In an alternative procedure (84), the electrolyte is pumped through the cells at such a rate that the outlet concentration is 50 g/L MnSO and 67 g/L H2SO4. This spent electrolyte is then mixed with equal parts of make-up solution containing 150 g/L MnSO and the mixture returned to the electrolysis step. The electrolysis is continued over a period of days and terrninated when the EMD layer deposited on the anode reaches a specific thickness, usually on the order of 1—3 or 6—8 mm. Following completion of the electrolysis cycle, the entire electrode assembly is removed from the cell for removal of the deposited EMD, either manually or by an automated system (85). The product is repeatedly washed with water to extract the occluded acid (83) and dried at about 85°C in air. 

Incorrect information can result if the probe is made of the wrong material and is not heat treated in the same way as the process equipment (as well as because of other problems). The probe must be as close as possible to the material from which the equipment of interest is made. Existence of a critical condition, such as weldments or galvanic couples or occluded cells in the eqmpment of concern, makes the fabrication, placement, and maintenance of the probes and monitoring system or critical importance, if accurate and useful data are to be obtained. 

Almost all cooling water system deposits are waterborne. It would be impossible to list each deposit specifically, but general categorization is possible. Deposits are precipitates, transported particulate, biological materials, and a variety of contaminants such as grease, oil, process chemicals, and silt. Associated corrosion is fundamentally related to whether deposits are innately aggressive or simply serve as an occluding medium beneath which concentration cells develop. An American... 

Passive corrosion caused by chemically inert substances is the same whether the substance is living or dead. The substance acts as an occluding medium, changes heat conduction, and/or influences flow. Concentration cell corrosion, increased corrosion reaction kinetics, and erosion-corrosion can he caused by biological masses whose metabolic processes do not materially influence corrosion processes. Among these masses are slime layers. 

Slime is a network of secreted strands (extracellular polymers) intermixed with bacteria, water, gases, and extraneous matter. Slime layers occlude surfaces—the biological mat tends to form on and stick to surfaces. Surface shielding is further accelerated by the gathering of dirt, silt, sand, and other materials into the layer. Slime layers produce a stagnant zone next to surfaces that retards convective oxygen transport and increases diffusion distances. These properties naturally promote oxygen concentration cell formation. 

A minimal mechanism for Na, K -ATPase postulates that the enzyme cycles between two principal conformations, denoted Ej and Eg (Figure 10.11). El has a high affinity for Na and ATP and is rapidly phosphorylated in the presence of Mg to form Ei-P, a state which contains three oeeluded Na ions (occluded in the sense that they are tightly bound and not easily dissociated from the enzyme in this conformation). A conformation change yields Eg-P, a form of the enzyme with relatively low affinity for Na, but a high affinity for K. This state presumably releases 3 Na ions and binds 2 ions on the outside of the cell. Dephosphorylation leaves EgKg, a form of the enzyme with two... 

Severe attack frequently occurs at a water-line, which in practice can range from structural steel partly immersed in a natural water to a lacquered tin can used for containing emulsion paint. This can be illustrated by adding increeising amounts of sodium carbonate to a sodium chloride solution in which a steel plate is partly immersed (Fig. 1.48c, d and e). With increase in concentration of the inhibitor, attack decreases and becomes confined to the water-line. The attack at the water-line is intense and is characterised by a triangular pasty mass of corrosion products bounded on the upper surface by a dark-brown membrane that follows the contour of the water-line. The mechanism of water-line attack is not clear, but it is likely that the membrane of corrosion products results in the formation of an occluded cell, in which the anolyte and catholyte are prevented from mixing. These occluded cells are discussed in more detail subsequently. 

Cells of this type, in which the anolyte and catholyte are separated from one another, are referred to as occluded cells, and they may be formed by... 

The development of acidity within an occluded cell is by no means a new concept, and it was used by Hoar s as early as 1947 in his Acid Theory of Pitting to explain the pitting of passive metals in solutions containing Cl ions. According to Hoar the Cl ions migrate to the anodic sites and the metal ions at these sites hydrolyse with the formation of HCl, a strong acid that inhibits the formation of a protective film of oxide or hydroxide. Edeleanu and Evans followed the pH changes when aluminium was made anodic in Cl solutions and found that the pH decreased from 8-8 to 5-3. 

The fact that the pH values of the pure metals were lower than the theoretical values was attributed to the formation of hydroxy-chloro complexes of the metal and to the high chloride ion concentration in the pit, and the results highlight the very pronounced decrease in pH that can occur in an occluded cell, particularly when the alloy contains high concentrations of chromium and molybdenum. They also showed that migration of chloride ions into the solution in the pit can result in a 7-12-fold increase in concentration, and that the potential in the pit is in the active region. 

The importance of occluded cells cannot be overemphasised, and Brown considers that pitting, crevice corrosion, intergranular attack, filiform corrosion and hydrogen cracking are characterised by local acidification due to hydrolysis of metal ions, and that this phenomenon is of major significance in the overall mechanism. 

This area will be passivated by the increase in pH due to the cathodically produced OH ions, and partially cathodically protected by the electrons liberated by the anodic processes within the pit. The tubercle thus results in an occluded cell with the consequent acidification of the anodic sites. Wranglen considers that in view of the fact that crystals of FeClj -4H20 are sometimes observed at the bottom of a pit the solution within the pit is a saturated solution of that salt, and that this will correspond with an equilibrium pH of about 3-5. 

Decrease in velocity will favour all forms of localised attack in which an occluded cell is involved in the mechanism, and will also favour selective dissolution of alloys that are susceptible to this form of attack. 

Occluded corrosion cell —electrochemical changes at the crack tip... 

Occluded Cell a corrosion cell of a geometry that prevents intermingling of the anodic reaction products (anolyte) with the bulk solution, resulting in a decrease in pH of the anolyte shielded areas or pits, crevices or cracks in the surface of the metal are examples. 

The results from such occluders show that Na channels differ in structure between their internal and external surfaces, have binding sites for a variety of monovalent and divalent cations, and are pharmacologically different despite very similar physiological actions in nerve, muscle, and mammalian cardiac cells. 

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