The electrode potential is one of the most important parameters in the thermodynamics and kinetics of corrosion. This article discusses the fundamentals of electrode potentials and illustrates the thermodynamics of chemical equilibria by using the hydrogen potential scale and the Nernst equation. It describes galvanic cell reactions and corrosion reactions in an aqueous solution in an electrochemical cell. The article explores the most common cathodic reactions encountered in metallic corrosion in aqueous systems. The reactions included are proton reduction, water reduction, reduction of dissolved oxygen, metal ion reduction, and metal deposition. The article also presents the standard equilibrium potentials measured at 25 deg C relative to a standard hydrogen electrode for various metal-ion electrodes in a tabular form.

Particle-induced x-ray emission (PIXE) is one of several quantitative analyses based on characteristic x-rays. This article provides a detailed account on the principles of PIXE, discussing the data-reduction codes used to identify, integrate, and reduce x-ray peaks into elemental concentrations. It provides information on the calibration of PIXE analysis, which is mostly performed using gravimetric standards to avoid serious absorption, refluorescence, or ion energy change corrections. A comparative study on PIXE and x-ray fluorescence is also included. Finally, the article discusses the applications of PIXE in three areas, namely, atmospheric physics and chemistry, external proton milliprobes and historical analysis, and PIXE microprobes.

Corrosion of metallic materials is governed by electrochemical kinetics, so that the general concepts developed for studying electrochemical reaction mechanisms may be applied to corrosion. This article presents the fundamental aspects of electrode kinetics. The processes of charge transfer taking place at the electrode interface within the double layer and of mass transport at the vicinity of the electrode surface are discussed. The article describes the corrosion processes, which involve anodic and cathodic reactions at specific electrode sites. Some experimental methods for devising a reliable reaction model are detailed. The article explains some reaction mechanisms for cathodic and anodic processes to illustrate the great variety of reaction mechanisms occurring at the electrode interface.

Mixtures of acids or acids and salts are of great importance to the chemical process industry (CPI) for use in digestion of solids, as a promoter in reactions, as a scale remover, and as a complexant. This article emphasizes the assessment of the performance of Ni-Fe-Cr-Mo alloys in mixed acids and salts in an objective manner. It tabulates the nominal compositions of pertinent Ni-Fe-Cr-Mo corrosion-resistant alloys. The article describes the acid and acid-plus-salt mixtures classified into the following general categories: nonoxidizing acid mixtures (H 2 SO 4 +H 3 PO 4 ), nonoxidizing acids with halides (H 2 SO 4 +HCl), oxidizing acid mixtures without halides (H 2 SO 4 +HNO 3 ), and oxidizing acid mixtures with halides (HNO 3 +HF). It also illustrates the effect of alloying elements on the corrosion rate in the nonoxidizing mixtures and oxidizing acid mixtures.

This article provides a detailed account of particle-induced x-ray emission (PIXE), covering the basic principles of PIXE analysis and calibration and quality-assurance protocols employed. A comparative study on PIXE and x-ray fluorescence is then presented. The article also discusses the applications of PIXE in atmospheric physics and chemistry, external proton milliprobes and historical analysis, and PIXE microprobes.

This article presents common conventions and definitions in corrosion, electrochemical cells, cathodic protection (CP), electricity, and oxidation. Evans diagrams for impressed current CP in neutral or basic environment and galvanic or sacrificial CP, in both neutral or basic environment and acidic environment, are illustrated.

This article provides a general introduction to the kinetics of aqueous corrosion with an emphasis on electrochemical principles. It describes the thermodynamic basis for corrosion by determining the equilibrium potentials of electrochemical reactions from the Nernst equation. A corrosion process can be controlled by the electronic conductivity of passive films when the cathodic reaction occurs on the surface of the film and by activation control of corrosion. Passivation becomes thermodynamically possible when the corrosion potential exceeds the potential corresponding to the equilibrium between a metal and one of its oxides/hydroxides. The article schematically illustrates a current-potential or polarization curve for an anodic process.

This article describes the classification of organic solvents, namely, aprotic and protic solvents and one-component and multi-component systems. It discusses the corrosion behavior in aprotic and protic solvents. The article contains a table that presents the relationship among solution conductivity, acidity, and the corrosion rates of type 304 stainless steel in protic and aprotic solvents. The article reviews important environmental variables that influence corrosion testing in organic liquids.

This article examines the understanding of persistent material changes produced in stainless alloys during light water reactor (LWR) irradiation based on the fundamentals of radiation damage and existing experimental measurements. It summarizes the overall trends and correlations for irradiation-assisted stress-corrosion cracking. The article addresses the effects of various radiation factors on corrosion. These include radiation-induced segregation at grain boundaries, radiation hardening, mode of deformation, radiation creep relaxation, and radiolysis. The article discusses a variety of approaches for mitigating stress-corrosion cracking in LWRs, in categories of water chemistry, operating guidelines, new alloys, design issues, and stress mitigation. It concludes with a discussion on the irradiation effects of irradiation on corrosion of zirconium alloys in LWR environments.

The purity of aluminum is generally characterized in one of two ways, by terminology or by the Aluminum Association designation system. This article reviews the properties of pure aluminum in purities from 99.99 percent through commercial purity, 99.00 percent. The mechanical properties of aluminum are discussed in terms of tensile properties, stress-strain relationships, and creep. The article also reviews the physical properties of aluminum, such as atomic structure and nuclear properties, atomic spectrum, crystal structure, density, thermal expansion, and thermal conductivity. It discusses the chemical properties of aluminum and presents a summary tabulation of the mechanical strength, ductility, and hardness of pure aluminum.

A potential pH diagram is a graphical representation of the relations, derived from the Nernst equation, between the pH and the equilibrium potentials (E) of the most probable electrochemical reactions occurring in a solution containing a specific element. This article describes three types of reactions for calculation and construction of E-pH diagrams: electrochemical reactions of pure charge (electron) transfer; reactions involving both electron and solvated proton transfer; and acid-base reactions of pure solvated proton transfer. It illustrates the practical use of E-pH diagrams for temperature aqueous solutions and adsorbed species and in prediction of corrosion of nickel and copper.

Gas analysis by mass spectrometry, or gas mass spectrometry, is a general technique using a family of instrumentation that creates a charged ion from a gas phase chemical species and measures the mass-to-charge ratio. This article covers gas analysis applications that do not use chromatographic separation to physically isolate components of the sample prior to analysis. It is intended to provide an understanding of gas analysis instrumentation and terminology that will help make informed decisions in choosing an instrument and methodology appropriate for the data needed. Mass-analyzer technologies for gas mass spectrometry, namely quadrupole mass filters, magnetic sector mass filters, and time-of-flight mass analyzers are covered. Common factors to consider in choosing an analyzer for static or continuous gas measurement are also described. In addition, the article presents some examples of applications of gas mass spectrometry.

Electrode potential is a key parameter in the thermodynamic and kinetic processes that drive aqueous corrosion. This article discusses the complexities associated with measuring electrode potential and explains where and how to use reference electrodes to improve measurement accuracy. It describes a three-electrode approach that compensates for measurement error stemming from nonequilibrium conditions. It also examines electrode materials and behaviors and offers insights on selection and operating conditions.

This article is a compilation of definitions of terms related to materials characterization techniques.

Radionuclide methods for wear measurement are used to measure wear continuously throughout a tribological experiment at a resolution of nanometers or micrograms per hour. This article presents an overview of radionuclide methods for wear measurement. It discusses complementary wear measurement methods to introduce the advantages of using radioactive isotopes (RI) for wear or corrosion measurements in comparison to other methods. The article provides information on radiation safety regulations and approaches to minimize external radiation exposure. It describes neutron activation, thin layer or surface layer activation, and ultrathin layer or recoil activation that are used to create radioactive isotopes in the samples to be tested. The article reviews the two common types of wear measurement setup configurations: the direct method and the indirect method. It concludes with a discussion on the practical application of wear measurement using radioactive isotopes.

This article is a compilation of terms and definitions related to materials characterization.

Vibroacoustic analysis of mechanical systems has an important role in the engineering discipline. This can be used as a monitoring tool to obtain insights about the condition of a system, identify its probable defects, and determine the time window that the maintenance should happen. This article introduces the basics of signal processing in time, frequency, and time-frequency domains. It focuses on statistical analysis of the time-domain data. Various measures of data distribution and variability are pointed out. Important signal-processing functions in the frequency domain are presented and explained with examples. The article discusses and clarifies the benefits of time-frequency domain based on short-time Fourier transform with some practical applications. The article presents the most frequently used statistical functions. It concludes with information on some real-world applications of vibroacoustic analysis.

This article describes the ideal performance of various low-temperature and high-temperature fuel cells that depends on the electrochemical reactions that occur between different fuels and oxygen. Low-temperature fuel cells, such as polymer electrolyte, alkaline, and phosphoric acid, and high-temperature fuel cells, such as molten carbonate and solid oxide, are discussed. The article contains tables that provide information on the evolution of cell-component technology for these fuel cells. It concludes with information on the advantages and limitations of the fuel cells.

This article focuses on the internal corrosion of iron and copper in potable water. It tabulates the corrosion and water-quality problems caused by materials in contact with drinking water. The article provides a theoretical description of the reduction-oxidation reactions in water to analyze the causes of corrosion of metals in contact with water. It discusses the Langelier saturation index and the Larson index for determining corrosion in potable water systems. The article describes the two major ways of mitigation against corrosion in potable water systems. The first is to line the pipe surface physically such that water and dissolved oxygen cannot reach the metal surface and the second is to add chemical inhibitors to alter water chemistry.

This article focuses on wet chemical methods that have stood the test of time in laboratories around the world. It begins with a description of the appropriateness of classical wet methods. This is followed by sections on sampling procedures, basic chemical equilibria, and wet analytical chemistry. Mechanical methods and nonoxidizing acids and/or acid mixtures for dissolving solid samples for wet chemical analysis are then reviewed. Qualitative methods that are used to identify materials by wet chemical reaction are also included. The article provides information on various methods for the separation of chemical mixtures and on the types of gravimetry and titrimetry. Strategies for removing inclusions are also included to aid in their compositional understanding. The article also briefly describes the processes involved in chemical surface studies and partitioning of oxidation states. It ends by presenting some examples of the applications of classical wet methods.