Glass-ceramics have an amorphous phase and one or more crystalline phases and are produced by a so-called "controlled crystallization" in contrast to a spontaneous crystallization, which is usually not wanted in glass manufacturing. Glass-ceramics have the fabrication advantage of glass, as well as special properties of ceramics. Glass-ceramics do not require brazing but can withstand brazing temperatures up to 700 °C.^[1] Glass-ceramics usually have between 30% [m/m] and 90% [m/m] crystallinity and yield an array of materials with interesting properties like zero porosity, high strength, toughness, translucency or opacity, pigmentation, opalescence, low or even negative thermal expansion, high temperature stability, fluorescence, machinability, ferromagnetism, resorbability or high chemical durability, biocompatibility, bioactivity, ion conductivity, superconductivity, isolation capabilities, low dielectric constant and loss, high resistivity and break-down voltage. These properties can be tailored by controlling the base-glass composition and by controlled heat treatment/crystallization of base glass. In manufacturing, glass-ceramics are valued for having the strength of ceramic but the hermetic sealing properties of glass.
Glass-ceramics are mostly produced in two steps: First, a glass is formed by a glass-manufacturing process. The glass is cooled down and is then reheated in a second step. In this heat treatment the glass partly crystallizes. In most cases nucleation agents are added to the base composition of the glass-ceramic. These nucleation agents aid and control the crystallization process. Because there is usually no pressing and sintering, glass-ceramics have, unlike sintered ceramics, no pores.
A wide variety of glass-ceramic systems exists, e.g., the Li₂O × Al₂O₃ × nSiO₂ system (LAS system), the MgO × Al₂O₃ × nSiO₂ system (MAS system), the ZnO × Al₂O₃ × nSiO₂ system (ZAS system).
The LAS system mainly refers to a mix of lithium, silicon, and aluminum oxides with additional components, e.g., glass-phase-forming agents such as Na₂O, K₂O and CaO and refining agents. As nucleation agents most commonly zirconium(IV) oxide in combination with titanium(IV) oxide is used. This important system was studied first and intensively by Hummel,^[2] and Smoke.^[3]
After crystallization the dominant crystal phase in this type of glass-ceramic is a high-quartz solid solution (HQ s.s.). If the glass-ceramic is subjected to a more intense heat treatment, this HQ s.s. transforms into a keatite-solid solution (K s.s., sometimes wrongly named as beta-spodumene). This transition is non-reversible and reconstructive, which means bonds in the crystal-lattice are broken and new arranged. However, these two crystal phases show a very similar structure as Li could show.^[4]
The most interesting properties of these glass-ceramics are their thermomechanical properties. Glass-ceramic from the LAS system is a mechanically strong material and can sustain repeated and quick temperature changes up to 800-1000 °C. The dominant crystalline phase of the LAS glass-ceramics, HQ s.s., has a strong negative coefficient of thermal expansion (CTE), keatite-solid solution as still a negative CTE but much higher than HQ s.s. These negative CTEs of the crystalline phase contrasts with the positive CTE of the residual glass. Adjusting the proportion of these phases offers a wide range of possible CTEs in the finished composite. Mostly for today's applications a low or even zero CTE is desired. Also a negative CTE is possible, which means, in contrast to most materials when heated up, such a glass-ceramic contracts. At a certain point, generally between 60% [m/m] and 80% [m/m] crystallinity, the two coefficients balance such that the glass-ceramic as a whole has a thermal expansion coefficient that is very close to zero. Also, when an interface between material will be subject to thermal fatigue, glass-ceramics can be adjusted to match the coefficient of the material they will be bonded to.
Originally developed for use in the mirrors and mirror mounts of astronomical telescopes, LAS glass-ceramics have become known and entered the domestic market through its use in glass-ceramic cooktops, as well as cookware and bakeware or as high-performance reflectors for digital projectors.