Potential drop

The Direct Current Potential Drop Method for Testing of Powder Metallurgical Parts. 

The Direct Current Potential Drop method (DCPD) has been evaluated for non destructive testing of uniaxially produced Powder Metallurgical (P/M) parts. The aim is to adapt DCPD to be functional as an ndt tool during production of parts. Defects can occur at different stages in the production cycle which means that DCPD has to be performed on components in different states and searching for different defects. 

Fig. V-14. Energy level diagram and energy scales for an n-type semiconductor pho-toelectrochemical cell Eg, band gap E, electron affinity work function Vb, band bending Vh, Helmholtz layer potential drop 0ei. electrolyte work function U/b, flat-band potential. (See Section V-9 for discussion of some of these quantities. (From Ref. 181.)...

Because of the charged nature of many Langmuir films, fairly marked effects of changing the pH of the substrate phase are often observed. An obvious case is that of the fatty-acid monolayers these will be ionized on alkaline substrates, and as a result of the repulsion between the charged polar groups, the film reverts to a gaseous or liquid expanded state at a much lower temperature than does the acid form [121]. Also, the surface potential drops since, as illustrated in Fig. XV-13, the presence of nearby counterions introduces a dipole opposite in orientation to that previously present. A similar situation is found with long-chain amines on acid substrates [122]. 

The simplest model for water at the electrode surface has just two possible orientations of the water molecules at the surface, and was initially described by Watts-Tobin [22]. The associated potential drop is given by... 

The experimental data and arguments by Trassatti [25] show that at the PZC, the water dipole contribution to the potential drop across the interface is relatively small, varying from about 0 V for An to about 0.2 V for In and Cd. For transition metals, values as high as 0.4 V are suggested. The basic idea of water clusters on the electrode surface dissociating as the electric field is increased has also been supported by in situ Fourier transfomr infrared (FTIR) studies [26], and this model also underlies more recent statistical mechanical studies [27]. 

Figure Bl.28.9. Energetic sitiration for an n-type semiconductor (a) before and (b) after contact with an electrolyte solution. The electrochemical potentials of the two systems reach equilibrium by electron exchange at the interface. Transfer of electrons from the semiconductor to the electrolyte leads to a positive space charge layer, W. is the potential drop in the space-charge layer.

On the electrode side of the double layer the excess charges are concentrated in the plane of the surface of the electronic conductor. On the electrolyte side of the double layer the charge distribution is quite complex. The potential drop occurs over several atomic dimensions and depends on the specific reactivity and atomic stmcture of the electrode surface and the electrolyte composition. The electrical double layer strongly influences the rate and pathway of electrode reactions. The reader is referred to several excellent discussions of the electrical double layer at the electrode—solution interface (26-28). 

The region of the gradual potential drop from the Helmholtz layer into the bulk of the solution is called the Gouy or diffuse layer (29,30). The Gouy layer has similar characteristics to the ion atmosphere from electrolyte theory. This layer has an almost exponential decay of potential with increasing distance. The thickness of the diffuse layer may be approximated by the Debye length of the electrolyte. 

Activation Processes. To be useful ia battery appHcations reactions must occur at a reasonable rate. The rate or abiUty of battery electrodes to produce current is determiaed by the kinetic processes of electrode operations, not by thermodynamics, which describes the characteristics of reactions at equihbrium when the forward and reverse reaction rates are equal. Electrochemical reaction kinetics (31—35) foUow the same general considerations as those of bulk chemical reactions. Two differences are a potential drop that exists between the electrode and the solution because of the electrical double layer at the electrode iaterface and the reaction that occurs at iaterfaces that are two-dimensional rather than ia the three-dimensional bulk. 

The exchange current is directiy related to the reaction rate constant, to the activities of reactants and products, and to the potential drop across the double layer. The larger the more reversible the reaction and, hence, the lower the polarization for a given net current flow. Electrode reactions having high exchange currents are favored for use in battery apphcations. 

Because some substances may preferentially adsorb onto the surface of the electrode, the composition near the iaterface differs from that ia the bulk solution. If the cell current is 2ero, there is no potential drop from ohmic resistance ia the electrolyte or the electrodes. Yet from the thermodynamic analysis it is seen that there is a measurable cell potential. The question from where this potential arises can be answered by considering the iaterface. 

Ohmic voltage drops of the protection current were exclusively involved in the processes for 7/ -free potential measurements described above. Besides this, other foreign currents can cause potential drops and falsify the potential measurement (e.g., cell currents, equalizing currents and stray currents). 

As an example, a tank farm that is to be cathodically protected by this method is shown schematically in Fig. 11-4. As can be seen in the figure, injection of the protection current occurs with two current circuits of a total of about 9 A, via 16 vertically installed high-silicon iron anodes embedded in coke. These are distributed over several locations in the tank farm to achieve an approximately uniform potential drop. The details of the transformer-rectifier as well as the individual anode currents are included in Fig. 11-4. Anodes 4, 5 and 6 have been placed at areas where corrosion damage previously occurred. Since off potentials for 7/ -free potential measurements cannot be used, external measuring probes should be installed for accurate assessment (see Section 3.3.3.2 and Chapter 12). 

Solving the one-dimensional Poisson equation with the charge density profile pc z), the electrostatic potential drop near the interface can be calculated according to... 

A typical example of an ideal polarizable interface is the mercury-solution interface [1,2]. From an experimental point of view it is characterized by its electrocapillary curve describing the variation of the interfacial tension 7 with the potential drop across the interface, 0. Using the thermodynamic relation due to Lippmann, we get the charge of the wall a (-a is the charge on the solution side) from the derivative of the electrocapillary curve ... 

The simplest circuit element is the short circuit. Figure 2-66a illustrates the concept of a short circuit. A source of emf (labeled v ) produces a current that flows relatively unimpeded through the conductor resulting in a nearly zero potential drop and an infinite current. 

Circuit elements may be connected in either a series or parallel configuration. In the series configuration, the same current flows through each and every element, and the circuit potential drop (or emf that is developed by the voltage source) is the algebraic sum of the potential drops of each individual element. For sources in series, the total emf developed is the algebraic sum of the emfs developed by each individual source. 

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