Ferromagnetic and antiferromagnetic materials

Ferromagnetic materials

Iron is a typical ferromagnet. Not all bars of iron are magnets; the existence of magnetism is determined by the nature of the domains within the bar. A domain is a region of a crystal in which all the ions are ferromagnetically aligned in the same direction. A bar may be composed of many domains, each having a different magnetic orientation. Such a bar would not appear to be magnetic. 

Each piece of the bar is magnetic, but the domains have moments that point in different directions, so the bar has no net moment. If the bar of iron is placed in a strong magnetic field, however, the bar becomes magnetic. The field causes the bar to become a single domain with all moments aligned along the external field. The domains do not rotate their moments; instead, the walls between domains move. The domain with a moment along the field grows, while the others become smaller. If removed from the magnetic field, the iron bar will remain magnetized for a considerable time period. Nearly all bars of iron are polycrystalline: they have many small grains of single crystals, which are packed together with random orientation. A grain could be a single domain, a domain could include many grains, or a large grain could have several domains.

Ferromagnetic materials change their magnetic ordering at a characteristic temperature T_c called the Curie temperature. The Curie temperatures for three common ferromagnetics—iron, cobalt, and nickel—are 1,043 K; 1,394 K; and 631 K, respectively. For temperatures below T_c the magnetic moments of the ions are aligned and the crystal is magnetic. For temperatures above T_c the crystal is not ferromagnetic, since the individual atomic moments are no longer aligned. Above T_c the moments have short-range order but not long-range order. Short-range order means there is local ordering. If a moment points in one direction, its neighbours have a tendency to point in the same direction. This tendency is maintained over several lattice sites but is not maintained for long distances. Long-range order is the tendency for moments to align for large distances. For temperatures a few degrees below T_c the moments have strong short-range order but only a small amount of long-range order, so the bar is not very magnetic. The tendency for long-range order increases at lower temperature. The Curie temperature is the point where long-range order begins as the temperature is lowered.

If an iron bar is heated to a temperature above T_c, the bar is no longer magnetic. If the bar is then cooled to a temperature below T_c, the grains become magnetic, but they orient their moments in random directions, so the bar as a whole is not magnetic. A bar can be demagnetized by heating the bar and then cooling it. By inserting it in a large magnetic field, the bar can be remagnetized.

Ferromagnetism is found in many insulators as well as metals. Chromium bromide (CrBr₃) is an insulator since chromium is trivalent and a bromine atom needs one electron to complete its outer shell. The trivalent chromium atoms each have a moment, and these align ferromagnetically below the Curie temperature of 37 K. Gadolinium chloride (GdCl₃; T_c = 2.2 K) and europium oxide (EuO; T_c = 77 K) are two other examples among many.

Antiferromagnetic materials

Many crystals have magnetic ions that are ordered in arrangements other than ferromagnetic. In antiferromagnetic ordering, the moments pointing in one direction are balanced by others pointing in the opposite direction, with the result that the substance has no net magnetization. The exchange interaction between ions in this case has the opposite sign and favours the alternate arrangements of spins. The sign of the exchange interaction between ions depends on the length of the covalent bond and the bonding angles; it may have either orientation. The characteristic temperature associated with antiferromagnetism is called the Néel temperature T_N. Below T_N the ions are antiferromagnetically ordered, while above this temperature there is no long-range antiparallel order. Some examples of antiferromagnetic crystals are manganese oxide (MnO; T_N = 116 K), manganese sulfide (MnS; T_N = 160 K), and iron oxide (FeO; T_N = 198 K). Manganese oxide is an insulator since manganese atoms are divalent and oxygen atoms accept two electrons. The manganese ion has a fixed magnetic moment. The crystal structure of manganese oxide is the same as that of sodium chloride shown in Figure 3B. Below the Néel temperature the atomic unit cell doubles in size to include two atoms of each type of ion. This is necessary because below T_N neighbouring manganese atoms have moments in the opposite direction and are no longer equivalent; the unit cell must therefore include one moment in each of the two directions. Fluorides such as manganese fluoride (MnF₂), iron (II) fluoride (FeF₂), cobalt fluoride (CoF₂), and nickel fluoride (NiF₂) are other crystals that exhibit antiferromagnetic ordering of the transition metal ions.