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Spinel group

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The spinel group is a diverse class of minerals defined by a specific chemical arrangement. These minerals crystallize in the cubic, or isometric, crystal system. This means their internal structure is organized into repeating cubes.

Spinel
Spinel

Most members of this group use oxygen as their primary anion, which is a negatively charged ion. When sulfur is used instead of oxygen, the minerals are called thiospinels. The group takes its name from the mineral spinel, which was historically called "spinel ruby." Today, the term ruby is reserved specifically for the mineral corundum.

To understand how a spinel works, we must examine its microscopic lattice. The structure begins with a cubic close-packed lattice of anions, usually oxygen. Within this lattice, there are two types of available spaces for cations, which are positively charged ions. The first type is the octahedral site, which is a larger space. The second type is the tetrahedral site, which is a smaller space. In a normal spinel structure, the B cations occupy exactly half of the octahedral holes. Meanwhile, the A cations occupy only one-eighth of the tetrahedral holes.

Spinel Mineral New York State Museum
Spinel Mineral New York State Museum

Some minerals exhibit what scientists call an inverse spinel structure. In these cases, the cations swap their expected positions. In an inverse spinel, all the A cations and half of the B cations move into octahedral sites. The remaining half of the B cations move into the tetrahedral sites. This movement is not random. It is often driven by the crystal field stabilization energy, or CFSE. This is the energy gained when certain metal ions sit in specific environments. Some ions have a strong preference for octahedral sites based on their d-electron count. Others may prefer tetrahedral sites due to their atomic orbital sizes.

Because the spinel group can incorporate many different metals, it contains many distinct sub-groups. These groups are often categorized by the B cation present in the structure. For example, aluminum spinels include minerals like Gahnite, Hercynite, Galaxite, and Pleonaste. Iron spinels include the most abundant member, magnetite, as well as Franklinite and Jacobsite. There are also chromium spinels, such as chromite, and cobalt spinels. Even vanadium spinels, like Coulsonite, belong to this group. Some spinels are even found deep within the Earth. Ringwoodite is an abundant mineral found in the Earth's mantle at depths between 520 and 660 km.

Spinels are highly significant in both nature and modern technology. Magnetite is a particularly important iron spinel. It contains both +2 and +3 iron ions. In the industrial world, spinels are used for protection. They often form during high-temperature processes. A thin layer of spinel, sometimes only a few micrometers thick, can coat a metal. This functional layer prevents oxygen or other ions from diffusing into the base metal. This process helps protect materials from oxidation and corrosion. Additionally, certain spinels are used in high energy density lithium ion batteries.

Some spinels possess remarkable magnetoelectric and multiferroic properties. These materials allow for a coupling between electric and magnetic fields. In many spinel oxides, magnetism can actually create electric polarization. These are known as type-II multiferroics. This happens because the magnetic structure breaks the symmetry of the crystal. The B-site sublattice in these minerals forms a pyrochlore network. This network consists of corner-sharing tetrahedra. This specific geometry often leads to magnetic frustration, where the magnetic spins cannot easily find a stable direction. Instead, they may form complex spirals or helices.

These complex magnetic patterns can trigger the magnetoelectric effect through two main ways. The first is the inverse Dzyaloshinskii–Moriya mechanism. Here, non-collinear spins create a local electric dipole. The second way is called exchange striction. This occurs when pairs of spins with different alignments cause the chemical bonds to change length. These tiny structural changes create a net electric polarization. Scientists study these connections to understand how magnetism and electricity interact in advanced materials. This research helps us explore the fundamental relationship between the physical forces of the universe.

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File:Spinel Mineral New York State Museum.jpg
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