Crystal iron-carbon alloys

In order to answer these questions as directly as possible we begin by looking at diffusive and displacive transformations in pure iron (once we understand how pure iron transforms we will have no problem in generalising to iron-carbon alloys). Now, as we saw in Chapter 2, iron has different crystal structures at different temperatures. Below 914°C the stable structure is b.c.c., but above 914°C it is f.c.c. If f.c.c. iron is cooled below 914°C the structure becomes thermodynamically unstable, and it tries to change back to b.c.c. This f.c.c. b.c.c. transformation usually takes place by a diffusive mechanism. But in exceptional conditions it can occur by a displacive mechanism instead. To understand how iron can transform displacively we must first look at the details of how it transforms by diffusion. 

The role of continuous-cooling transformation diagrams in the heat treatment and control of microstructure was presented (for iron-carbon alloys) in Chapter 10. We discussed in this chapter how this type of diagram is employed in designing heat treatments to crystallize glass-ceramics. The following concept map represents this relationship for processing these materials. 

Steel is an alloy of about 2% or less carbon in iron. Carbon atoms are much smaller than iron atoms, and so they cannot substitute for iron in the crystal lattice. Indeed, they are so small that they can fit into the interstices (the holes) in the iron lattice. The resulting material is called an interstitial alloy (Fig. 5.48). For two elements to form an interstitial alloy, the atomic radius of the solute element must be less than about 60% of the atomic radius of the host metal. The interstitial atoms interfere with electrical conductivity and with the movement of the atoms forming the lattice. This restricted motion makes the alloy harder and stronger than the pure host metal would be. 

Iron-chromium alloys, free from carbon, may be prepared from chromite by the alumino-thermic method. From a study of the cooling-and freezing-point curves it has been suggested that a compound, Cr Fe, exists, but this is questioned by Janecke, who studied the iron-chromium system by means of fusion curves and by the microscopic study of polished sections of various alloys between the limits 10 Fe 90 Cr and 90 Fe 10 Cr, and came to the conclusion that the system consists of a single eutectic which can form mixed crystals with either component. The eutectic contains 75 per cent, of chromium and melts at 1320° C. The addition of chromium to iron increases the readiness of attack by hydrochloric and sulphuric acids, but towards concentrated nitric acid the alloys are rendered passive. They remain bright in air and in water. The presence of carbon increases the resistance to acids and renders them very hard if carbon-free, they are softer than cast iron. All the alloys up to 80 per cent, chromium are magnetic. Molybdenum, titanium, vanadium, and tungsten improve the mechanical properties and increase the resistance to acids. 

Interstitial solid solutions form when small atoms enter spaces between the atoms in a crystal (Figure 3.14b). The interstitial impurities must be small, with a radius less than about 60 % of the parent-structure atoms if an interstitial solid solution is to form. They are typically elements from the first row of the periodic table, such as carbon and nitrogen. Steel is the most important interstitial alloy and consists of interstitial carbon atoms in ciystals of iron. Interstitial alloys are usually very hard materials, often used as hard coatings on surfaces liable to excessive wear, such as drill bits. 

Sch] Schuermann, E., Schmidt, T., Tillmann, F., Activities of Carbon in y and a -Mixed Crystal of the Iron-Carbon-Silicon Alloys (in German), Giessereiforschung, 19(1), 25-34 (1967) (Experimental, Phase Diagram, Thermodyn., 33)... 

Hof] Hoffmeister, H., Crystal Segregations and Eutectic Carbide Precipitations in Iron-Carbon-Vanadium Alloys (in German), Arch. Eisenhuettenwes., 44(5), 349-355 (1973) (Morphology, Phase Relations, Experimental, 7)... 

Since the number of slip systems is not usually a function of temperature, the ductility of face-centered cubic metals is relatively insensitive to a decrease in temperature. Metals of other crystal lattice types tend to become brittle at low temperatures. Crystal structure and ductility are related because the face-centered cubic lattice has more slip systems than the other crystal structures. In addition, the slip planes of body-centered cubic and hexagonal close-packed crystals tend to change at low temperature, which is not the case for face-centered cubic metals. Therefore, copper, nickel, all of the copper-nickel alloys, aluminum and its alloys, and the austenitic stainless steels that contain more than approximately 7% nickel, all face-centered cubic, remain ductile down to the low temperatures, if they are ductile at room temperature. Iron, carbon and low-alloy steels, molybdenum, and niobium, all body-centered cubic, become brittle at low temperatures. The hexagonal close-packed metals occupy an intermediate place between fee and bcc behavior. Zinc undergoes a transition to brittle behavior in tension, zirconium and pure titanium remain ductile. 

Steel is an interstitial alloy of iron, in which carbon atoms occupy the interstices in the iron crystal. Adding carbon to iron to make steel introduces new properties because of the directional nature of the iron-carbon interactions. 

Heat Treatment of Steel. Steels are alloys having up to about 2% carbon in iron plus other alloying elements. The vast application of steels is mainly owing to their ability to be heat treated to produce a wide spectmm of properties. This occurs because of a crystallographic or aHotropic transformation which takes place upon quenching. This transformation and its role in heat treatment can be explained by the crystal stmcture of iron and by the appropriate phase diagram for steels (see Steel). 

But in metals it is relatively common for solid solutions to form. The atoms of one element may enter the crystal of another element if their atoms are of similar size. Gold and copper form such solid solutions. The gold atoms can replace copper atoms in the copper crystal and, in the same way, copper atoms can replace gold atoms in the gold crystal. Such solid solutions are called alloys. Some solid metals dissolve hydrogen or carbon atoms—steel is iron containing a small amount of dissolved carbon. 

A second way for a solid to accommodate a solute is interstitially, with solute atoms fitting in between solute atoms in the crystal stmcture. An important alloy of this type is carbon steel, a solid solution of carbon in iron, also shown in Figure 12-4. Steels actually are both substitutional and interstitial alloys. Iron is the solvent and carbon is present as an interstitial solute, but varying amounts of manganese, chromium, and nickel are also present and can be in substitutional positions. 

Magnicol [Magnetic columnar] A process for making Alnico (an iron-based magnetic alloy containing Al, Ni, Co, and Cu) crystallize with a columnar grain structure in order to optimize its magnetic properties. Successive additions of silicon, carbon, and sulfur are made to the initial melt. 

There are many metal alloys that contain interstitial atoms embedded in the metal structure. Traditionally, the interstitial alloys most studied are those of the transition metals with carbon and nitrogen, as the addition of these atoms to the crystal structure increases the hardness of the metal considerably. Steel remains the most important traditional interstitial alloy from a world perspective. It consists of carbon atoms distributed at random in interstitial sites within the face-centered cubic structure of iron to form the phase austenite, which exists over the composition range from pure iron to approximately 7 at % carbon. 

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