These materials are produced by calcining calcium sulfate dihydrate (gypsum).

Commercially,
the gypsum is ground and subjected to temperatures of 110 °C to 130 °C (230 °F to 266 °F) in
open containers to drive off part of the water of crystallization. This corresponds to the first
step in the reaction (Figure 9-1).
The principal constituent of gypsum-based products is calcium sulfate hemihydrate
[(CaSO4)2•H2O or CaSO4• 12 H2O].
The resulting particle is a fibrous aggregate of fine crystals with capillary pores (Figure 9-2,
A) known as plaster of Paris or dental plaster in dentistry. As the temperature is further raised,
it becomes an anhydrite. This process is known as calcination. As shown in Figure 9-1, when
gypsum is heated in a kettle, vat, or rotary kiln that maintains a wet environment; a crystalline
hemihydrate called dental stone is produced in the form of rods or prisms (Figure 9-2, B).
Because of differences in crystal size, surface area, and degree of lattice perfection, the
resulting powders are often referred to as α-hemihydrate for dental stone and β-hemihydrate
for plaster of Paris.
The β-hemihydrate crystals are characterized by their “sponginess” and irregular shape. In
contrast, the α-hemihydrate crystals are denser and have a prismatic shape. When hemihydrate
particles are mixed with water, the reaction in Figure 9-1 is reversed.
The α-hemihydrate produces a much stronger and harder dihydrate structure than that resulting
from β-hemihydrate. The chief reason for this difference is that the β-hemihydrate crystals are
more irregular in shape and porous in character and require more water to wet the powder
particles so that they can be stirred and poured.
The amount of water required can also be reduced by grinding the hemihydrate particles to
eliminate needlelike crystals and to provide better packing characteristics. It is clear that
various gypsum products require different amounts of water. These differences are accounted
for principally by the shape and compactness of the crystals.
These factors are regulated by the manufacturer and they are dependent on the type of process
used, dehydration temperatures, particle size of the gypsum to be calcined, the calcination time,
the grinding time for the final product, and addition of surface-active ingredients to the final
product. If the calcination process occurs under pressure in a 30% calcium chloride solution or
in the presence of more than 1% of sodium succinate, the resulting hemihydrate crystals will
be shorter and thicker than those produced in a closed container (Figure 9-2, C). Residual
calcium chloride or sodium succinate is removed by washing the powder with hot water. This
type of gypsum-producing product is called modified α-hemihydrate or die stone. These
crystals require even less water for mixing.