In materials science, segregation is the enrichment of atoms, ions, or molecules at a microscopic region in a materials system. While the terms segregation and adsorption are essentially synonymous, in practice, segregation is often used to describe the partitioning of molecular constituents to defects from solid solutions, whereas adsorption is generally used to describe such partitioning from liquids and gases to surfaces. The molecular-level segregation discussed in this article is distinct from other types of materials phenomena that are often called segregation, such as particle segregation in granular materials, and phase separation or precipitation, wherein molecules are segregated in to macroscopic regions of different compositions. Segregation has many practical consequences, ranging from the formation of soap bubbles, to microstructural engineering in materials science, to the stabilization of colloidal suspensions.

Segregation can occur in various materials classes. In polycrystalline solids, segregation occurs at defects, such as dislocations, grain boundaries, stacking faults, or the interface between two phases. In liquid solutions, chemical gradients exist near second phases and surfaces due to combinations of chemical and electrical effects.

Segregation which occurs in well-equilibrated systems due to the instrinsic chemical properties of the system is termed equilibrium segregation. Segregation that occurs due to the processing history of the sample (but that would disappear at long times) is termed non-equilibrium segregation.

Equilibrium segregation is associated with the lattice disorder at interfaces, where there are sites of energy different from those within the lattice at which the solute atoms can deposit themselves. The equilibrium segregation is so termed because the solute atoms segregate themselves to the interface or surface in accordance with the statistics of thermodynamics in order to minimize the overall free energy of the system. This sort of partitioning of solute atoms between the grain boundary and the lattice was predicted by McLean in 1957.

Non-equilibrium segregation, first theorized by Westbrook in 1964, occurs as a result of solutes coupling to vacancies which are moving to grain boundary sources or sinks during quenching or application of stress. It can also occur as a result of solute pile-up at a moving interface.

There are two main features of non-equilibrium segregation, by which it is most easily distinguished from equilibrium segregation. In the non-equilibrium effect, the magnitude of the segregation increases with increasing temperature and the alloy can be homogenized without further quenching because its lowest energy state corresponds to a uniform solute distribution. In contrast, the equilibrium segregated state, by definition, is the lowest energy state in a system that exhibits equilibrium segregation, and the extent of the segregation effect decreases with increasing temperature. The details of non-equilibrium segregation are not going to be discussed here, but can be found in the review by Harries and Marwick.

Segregation of a solute to surfaces and grain boundaries in a solid produces a section of material with a discrete composition and its own set of properties that can have important (and often deleterious) effects on the overall properties of the material. These 'zones' with an increased concentration of solute can be thought of as the cement between the bricks of a building. The structural integrity of the building depends not only on the material properties of the brick, but also greatly on the properties of the long lines of mortar in between.

Segregation to grain boundaries, for example, can lead to grain boundary fracture as a result of temper brittleness, creep embrittlement, stress relief cracking of weldments, hydrogen embrittlement, environmentally assisted fatigue, grain boundary corrosion, and some kinds of intergranular stress corrosion cracking. A very interesting and important field of study of impurity segregation processes involves AES of grain boundaries of materials. This technique includes tensile fracturing of special specimens directly inside the UHV chamber of the Auger Electron Spectrometer that was developed by Ilyin. Segregation to grain boundaries can also affect their respective migration rates, and so affects sinterability, as well as the grain boundary diffusivity (although sometimes these effects can be used advantageously).