In addition to the large amount of heat liberated when a metal solidifies, there are other changes indicated by the thermal analysis of many alloys which occur after the body has become entirely solidified. These so-called transformation points or ranges may be caused by chemical reactions taking place within the solid, substances being precipitated from a "solid solution," or a sudden change in some physical property of the components, such as in magnetism, hardness, or specific gravity.

It may be difficult to comprehend that such changes can occur in a body after it has become entirely solidified, owing to the usual conception that the particles are then rigidly fixed. However, this rigidity is only comparative. The molecules in the solid state have not the large mobility they possess as a liquid, but even so, they are still moving in circumscribed orbits, and have the power, under proper conditions, to rearrange their position or internal configuration. In general, such rearrangement is accompanied by a sudden change in some physical property and in the total energy of the molecule, which is evidenced by a spontaneous evolution or absorption of latent heat.

Cooling curves of the purest iron show at least two well-defined discontinuities at temperatures more than 1,000°F., below its freezing-point. It seems that the soft, magnetic metal so familiar as wrought iron, and called "alpha iron" or "ferrite" by the metallurgist, becomes unstable at about 1,400°F. and changes into the so-called "beta" modification, becoming suddenly harder, and losing its magnetism. This state in turn persists no higher than 1,706°C., when a softer, non-magnetic "gamma" iron is the stable modification up to the actual melting-point of the metal. These various changes occur in electrolytic iron, and therefore cannot be attributed to any chemical reaction or solution; they are entirely due to the existence of "allotropic modifications" of the iron in its solid state.

FIG. 45.—Inverse Rate Cooling Curve of 0.38 C Steel.

Steels, or iron containing a certain amount of carbon, develop somewhat different cooling curves from those produced by pure iron. Figure 45 shows, for instance, some data observed on a cooling piece of 0.38 per cent carbon steel, and the curve constructed therefrom. It will be noted that the time was noted when the needle on the pyrometer passed each dial marking. If the metal were not changing in its physical condition, the time between each reading would be nearly constant; in fact for a time it required about 50 sec. to cool each unit. When the dial read about 32.5 (corresponding in this instrument to a temperature of 775°C. or 1,427°F.) the cooling rate shortened materially, 55 sec. then 65, then 100, then 100; showing that some change inside the metal was furnishing some of the steadily radiating heat. This temperature is the so-called "upper critical" for this steel. Further down, the "lower critical" is shown by a large heat evolution at 695°C. or 1,283°F.

Just the reverse effects take place upon heating, except that the temperatures shown are somewhat higher—there seems to be a lag in the reactions taking place in the steel. This is an important point to remember, because if it was desired to anneal a piece of 0.38 carbon steel, it is necessary to heat it up to and beyond 1,476° F. (1,427°F. plus this lag, which may be as much as 50°).

It may be said immediately that above the upper critical the carbon exists in the iron as a "solid solution," called "austenite" by metallographers. That is to say, it is uniformly distributed as atoms throughout the iron; the atoms of carbon are not present in any fixed combination, in fact any amount of carbon from zero to 1.7 per cent can enter into solid solution above the upper critical. However, upon cooling this steel, the carbon again enters into combination with a definite proportion of iron (the carbide "cementite," Fe3C), and accumulates into small crystals which can be seen under a good microscope. Formation of all the cementite has been completed by the time the temperature has fallen to the lower critical, and below that temperature the steel exists as a complex substance of pure iron and the iron carbide.

It is important to note that the critical points or critical range of a plain steel varies with its carbon content. The following table gives some average figures:

Carbon Content.Upper Critical.Lower Critical.
0.001,706°F.1,330°F.
0.201,600°F.1,330°F.
0.401,480°F.1,330°F.
0.601,400°F.1,330°F.
0.801,350°F.1,330°F.
0.901,330°F.1,330°F.
1.001,470°F.1,330°F.
1.201,650°F.1,330°F.
1.401,830°F.1,330°F.
1.602,000°F.1,330°F.