**1. Introduction**

294 Corrosion Resistance

Zhu, D. & Miller, R. A. (1997). Determination of Creep Behavior of Thermal Barrier Coatings

2011, Available at http://gltrs.grc.nasa.gov/reports/1997/TM-113169.pdf

Under Laser Imposed Temperature and Stress Gradients, NASA Technical Memorandum 113169, Report Number ARL-TR-1565, Date of access: 15th of August

> The corrosion of metals is a destructive process regarding to the basic modern constructional material with a great importance for the nowadays industry and in many cases represents an enormous economic loss. Therefore, it is not a surprise that the research on the corrosion and corrosion protection of metallic materials is developed on a large scale in different directions and a wide range of engineering decisions. For all that, the improvement of corrosion behaviour of metals and alloys still stays as one of the most important engineering problems in the area of materials application and it is one of the fundamental parts of modern surface engineering.

> Special attention is usually focused on the corrosion behaviour of steels as the most commonly used engineering material, because of the limited corrosion resistance for many basic types of these alloys. In more cases they are selected not for their corrosion resistance and important properties are strength, easy fabrication and cost, but there are a lot of exploitation conditions requiring high corrosion resistance. For such a purpose is developed the special group of stainless steels which covers with a high level of certainty these requirements. The stainless steels have an excellent corrosion resistance, but it is not always attended with high strength, hardness and wear resistance. Together with the higher price of the high-alloy steels these are the main restriction for many applications and open up a wide field of opportunities for the surface modification as a method for combination of corrosion resistance along with high strength, hardness and wear resistance.

> Surface modification in a wider sense includes all types of surface treatments and coatings that result in change in composition and microstructure of the surface layer. There are different methods for modifying the surfaces of structural alloys, dictated by the performance requirements of the alloy in its service environment. One of the approaches, traditional for the steels, is to modify the surface region of engineering alloys via diffusion of different elements and forming a layer with determinate chemical composition, microstructure and properties. These are the commonly used in practice methods for thermochemical treatment of metals which extended with the methods for physical vapor deposition and chemical vapor deposition form the basic modern techniques for surface engineering regarding to metals. Another approach involves coating of alloy surfaces via plasma spraying, electrospark deposition, modifying the surface by ion implantation or sputter deposition of selected elements and compounds, etc. In recent years a particular

Improvement of Corrosion Resistance of Steels by Surface Modification 297

economy is remarkable high. Because of that the carbon steels and in many cases low-alloy steels are the most used constructional metallic materials for surface engineering on the base

The diffusion coatings are products of thermally activated high temperature processes, that form on the metallic surface chemically bonded layer with determinate chemical composition, structure and properties. For decades a variety of diffusion coatings have been developed and used to improve the properties of metallic surface. There are several kinds of coating methods among which the most commonly used and with the most widely

Thermochemical treatment technologies for surface modification of steels have been very well investigated and developed on research and industrial level. These are methods by which nonmetals or metals are penetrated into the metallic surface by thermodiffusion after chemical reaction and adsorption. By thermochemical treatment the surface layers change their chemical composition, structure and properties and in many cases this modified surface can work in conditions which are impossible for the bulk material. Carburizing, nitriding, carbonitriding, nitrocarburizing, boronizing, chromizing, aluminizing and zinc coating are the most popular methods for industrial application. Only carburizing from all these methods could not perform the requirements to form coatings on the surface with high corrosion resistance in the most cases of steel treatment. The other techniques often are used for improvement of the corrosion behaviour of steels by surface modification and more of

Nitriding is a thermochemical treatment in which nitrogen in atomic or ionic form is introduced by diffusion process into the metallic surface and in the case of steels is based on the solubility of nitrogen in iron (Davis, 2001, 2002; Pye, 2003). The unique of the nitriding process were recognized by the Germans in the early 1920s. It was used in the applications

Nitrided steels offer improved corrosion and oxidation resistance. The nitrided surface of an alloy steel or tool exhibits increased resistance to saltwater corrosion, moisture and water. The treatment temperature is usually between 500 and 550 ºC for periods of 1 to 100 h depending of the nitriding method, type of steel and the desired depth of the layer. Since nitriding does not involve heating the steel to austenitic temperatures and quenching to martensite is not required, nitriding can be carried out at comparatively low temperatures and thus produce diffusion coating with high quality without deformations of the workpiece.

This technique is of great industrial interest as it forms structures with hard nitride surface layers, so that the global mechanical performance, hardness, wear resistance and corrosion resistance of steels are greatly improved. In recent years new and innovative surface

them increase the wear resistance and hardness of the treated materials.

of diffusion coatings.

that required: High torque

 High wear resistance Abrasive wear resistance Corrosion resistance

High surface compressive strength

industrial application is thermochemical treatment.

**2.1 Diffusion coatings obtained by nitriding** 

attention is directed to the advance methods for surface modification of metals such as laser surface treatment, ion beam surface treatment and electrical discharge machining, which give a modified surface with specific combination of properties in result of nonequilibrium microstructural characteristics.

The obtained by all these methods surface layers can be classified in several ways. Based on the mechanism of the treating process, they can be categorized as:


In the overlay coatings, an additional material is placed on the substrate by techniques such as physical vapor deposition (PVD), flame or plasma spraying, etc. The coating in these cases has a mechanical bond with the metallic surface, without much diffusion of the coating constituents into the substrate.

In diffusion coatings a chemical bond is formed with the metallic surface and is obtained a diffusion layer with modifying chemical composition in the depth of the layer. These coatings are formed generally at high temperatures and include such methods as thermochemical treatment and chemical vapor deposition (CVD). Thermochemical treatment is one of the fundamental methods for surface modification of metals and alloys by forming of diffusion coatings. The plain carbon steels and low-alloy steels are mainly treated by these methods to form on the surface layers with high hardness, wear resistance and corrosion resistance, but these methods are also often used to modify the surface of high-alloy steels, cast irons, nonferrous metals and for obtaining of layers with determinate chemical composition, structure and properties.

The recast layers are obtained after attacking the metallic surface with high energy stream such as laser, ion beam or electrical discharge for a very short time and pulse characteristics that involve local melting of the surface and after that rapidly cooling. The recast layer can be with the same chemical composition as the substrate, but with different microstructure and properties in result of nonequilibrium phase transformations during the rapidly cooling, or with a different chemical composition, microstructure and properties in result of attending diffusion process of surface alloying. In recent years of scientific and practical interests is the electrical discharge machining (EDM) for obtaining of recast layers with different characteristics and properties, mainly high hardness, wear resistance and corrosion resistance.

Typical cases of surface modification are diffusion coatings and recast layers, which will be the objectives of this chapter.
