DEPARTMENT OF PROSTHODONTICS

SEMINAR TOPIC- GYPSUM PRODUCTS

INTRODUCTION- Gypsum products means ‘chalk’ in Greek. It is a natural

mineral which is formed as a by product of various chemical processing. It is
formed in the form of calcium sulfate dihydrate but used calcium sulfate
hemihydrate in dentistry. Other forms are satin spar, selenite, ala-blaster and
plaster of Paris.

HISTORY- it is also known as ‘Plaster of Paris’ because it was found in the small
village in Paris where there was no activity. After they found plaster of Paris
they started using in the form of art and sculptures.
Even Ala-blaster was used in building King Solomon’s temple.

TYPES- According to ADA Specification no.25-

TYPE 1- Impression Plaster
TYPE 2- Dental Plaster
TYPE 3- Dental Stone
TYPE 4- Dental Stone, high strength, low expansion
TYPE 5- Dental Stone, high strength, high expansion

PRODUCTION- The materials of gypsum products are formed by calcining

calcium sulphate dihydrate or gypsum at a temperature higher than
70°C to remove partly the water of crystallization and as the
temperature keep raising, the remaining water of crystallization is
removed.
Both plaster and stone are formed by partial dehydration of gypsum,
which produces calcium sulphate hemihydrate. Difference in properties
results from different physical nature of the powder which in turn are a
result of different manufacturing methods.
 Plaster of Paris- It is the traditional plaster which is produced by ‘Dry
calcination’ of gypsum in open container (pan, kettle or rotary kiln) at
temperature of 120-180°C since it is a open container there is no water
for reorganization of crystal morphology , that is why they show rough,
irregular shape with low density, high relative surface area and poor
packing ability. It is also called β-hemihydrate.
Dental stone- When gypsum is dehydrated under pressure and in
presence of water vapor at about 125°C in closed container. Here
sufficient water is present for through solution conversion. So the
particles produces dense prismatic crystals in hexagonal shape, high
density, small relative surface area and improved packing ability. It is
also known as α-hemihydrate.
α-hemihydrate is found to be more stronger than β because this powder
requires less water.
β-hemihydrate requires more water to float the crystal partic;es and can
be stirred.
Dental stone with high strength- when modifications are added to this
wet process, it gives hemihydrate powders with even stronger set
products. When this wet calcination is taking place, crystal habit
modifiers are added like 30% calcium chloride solution or <1% sodium
succinate producing crystals that are shorter and thicker than compared
to those with ‘only wet calcination’. The powder obtained by this is the
densest and has high strength dental stone.

PROPORTIONING-
The strength of stone α ______1______
W:P ratio
So it is advised to keep the W:P ratio as low as possible so that the
strength is increased but no so low that the mix will not flow into every
detail of impression.
It is seen that 100g of plaster requires only 18.61g of water to form
calcium sulphate dihydrate. But practically, model plaster cannot be
mixed with this less amount of water and get workable consistency.
 That is why 45g of water is recommended out of which only 18.61g of
water is used while the excess is distributed as free water in the set
mass without taking any part in chemical reaction. This excess water is
actually necessary to wet the particles during mixing.
Dental stone- 30ml of water
High strength dental stone- 24ml of water
If W:P is more- It gives thin mass, pours easily into the mould and has
inferior quality
If W:P is less- It gives thick mass, more difficult to handle, traps air
bubbles and are more stronger
W:P ratio can be measured with graduated cylinder for water volume
and weighing balance for the powder. The powder should never be
measured with scoop as particles are not packed uniformly and show air
entrapments.
This differed measurements of water is due to physical shape and nature
of crystals
MIXING- Since we always measure it as W:P ratio in gypsum products,
Water is dispersed into the mixing bowl
↓
Weighed powder is sifted in
↓
Powder is allowed to settle in the water for 30 seconds (minimizes the
amount of air incorporated into the mix during initial spatulation by
hand)
↓
Mixture is vigorously stirred with periodic wiping of the inside of the
bowl with spatula ( to ensure wetting up of all powder and breaking up
of agglomerates or lumps)
↓
Continue mixing until smooth mix is obtained, usually within a minute at
2 revolutions per second
↓
Mechanically spatulated for 20 seconds ( reduces the air entrapped in
the mix) followed by vibration immediately after mixing (minimizes air
bubbles in the set mass)
↓
The mass should run into the rinsed impression under vibration in such a
way that it pushes air ahead of it.
Commonly, the teeth part of the cast are poured in dental stone or high
strength dental stone and base is poured with model plaster for easier
trimming
↓
The gypsum material is allowed to set for 45-60minutes
**Guesswork of repeatedly adding water and powder should be
avoided, it gives an uneven set within the mass.

SETTING OF GYPSUM PRODUCTS-

Calcium sulphate hemihydrate + water = Calcium sulphate dihydrate +
heat
When calcium sulphate hemihydrate is mixed with water the product
formed is calcium sulphate dihydrate and heat in form of exothermic
reaction. The heat evolved is equivalent to the heat used in calcination.
The setting of gypsum product follows crystalline theory.
Crystalline theory- This theory was proposed by French chemist Henry
Louis Chatelier (1885). The setting reaction is explained on the basis of
difference “in solubility of hemihydrate and dihydrate”. It is seen that
hemihydrate is 10 times more soluble than the dihydrate.
Dissolution
↓
 Suspension
↓
Supersaturation
↓
Nuclei formation
↓
Growth of nuclei
↓
Crystallization
↓
Spherulite formation

Particles or crystals of hemihydrate are 1st to dissolve in water that soon

becomes saturated. In this saturated solution, nuclei of crystallization
appear and crystals of dihydrate begin to form until such time the whole
mass becomes supersaturated with dihydrate. Since dihydrate is less
soluble than hemihydrate , the dihydrate crystals precipitates out
leaving the remaining solution to dissolve more hemihydrate crystals.
The precipitated dihydrate crystals begin to grow in size throughout the
mix as needle like crystals. And this process is repeated until all the
hemihydrate is converted to dihydrate. The needle like crystals grow
long intermesh and inter-wine with each other. This stage is called
spherulite formation and this indicates the material has been set.

CONTROL OF THE SETTING TIME-

It can be controlled by manipulating-
1. Impurities
2. Fineness
3. W:P ratio
4. Mixing
5. Temperature
 6. Retarder and Accelerator

1. Impurites: if calcination is not complete and the gypsum

particles remain, it decreases setting time because it
increases nuclei of crystallization
2. Fineness: Finer the particle size, faster the mix hardens
because it increased gypsum nuclei and decreases the
setting time
3. W:P ratio: if W:P ratio is increased, setting time is
increased as only fewer nuclei are present per unit
volume
4. Mixing: The longer and rapidly the plaster is mixed ,
setting time decreases
5. Temperature: it increases setting time. At 100°C no
reaction takes place.

SETTING EXPANSION- After setting regardless of what type of gypsum product

is used, when the hemihydrate is changed to dihydrate, an expansion of the
mass can be seen. The expansion can be as low as 0.06% to as high as 0.5%
When compared , the equivalent volume of hemihydrate with water is always
more than the resultant volume of product dihydrate.
With this calcination, we can just conclude that volumetric contraction might
occur but when actually observed setting expansion occurs, this phenomenon
can be rationalized on the basis of crystallization mechanism.
As we read before, crystallization process is pictured as an outward growth of
crystals from nuclei of crystallization so one can see that the crystals growing
from the nuclei can intermesh with and onstruct the growth of adjacent
crystals. And when this process is repeated by thousands of the crystals during
growth, an outward stress or thrust develops that produces an expansion of
entire mass. Later this crystal impingement and movement result in the
production of micropores as the crystal grows outward after setting the exces
water is lost resulting in void space.

CONTROL OF SETTING EXPANSION: As ther W:P ratio is decreases and mixing

time increases there will be greater expansion. If W:P ratio is increased, only
few crystals will be present per unit volume because powder is less and water
 is more, there occurs a space between nuclei is also greater which gives less
growth interaction of dihydrate crystals and consequently less outward thrust.
So best method of controlling expansion is addition of chemicals.

HYGROSCOPIC SETTING EXPANSION:

Till now we discussed about the setting process allowed in sir that is normal
setting expansion. Now we see setting process occurs ion presence of water
known as hygroscopic setting expansion. And the expansion in hygroscopic
setting is double the amount of expansion occurring in normal setting because
additional crystal growth is permitted when hemihydrate is allowed to react
under water.
So according to this theory, there are 5 stages in expansion.
In STAGE I, initial mis is represented by three round particles of hemihydrate
surrounded by water.
In STAGE II, crystals of dihydrate are beginning to form. In normal setting
condition, the water around the particles is reduced by hydration and particles
are drawn more closely together by surface tension action of water while in
hygroscopic setting, the water of hydration is replaced and the distance
between particles remain same.
In STAGE III, the crystals of dihydrate grow and contact each other and
expansion begins. So in normal setting, water around the particles are again
decreased, the particles with the attached crystals tends to be drawn together
showing contraction which is opposed by outward thrust of the growing
crystals while in hygroscopic setting, water is again replenished from the
outside. Infact now the particles are even separated , allowing crystals to grow
and setting expansion is visible evidently.
In STAGE IV & V, In normal setting, the crystals become more entagled and
meshed while in hygroscopic, crystals continue to grow freely until they start
intermeshing, it is then when it further prevents expansion.
Ultimately, the observed setting expansion that occurs when gypsum product
sets under water is greater than which occurs during the setting in air.
Therefore, increase in hygroscopic expansion happens when there is decreased
W:P ratio and increased spatulation. Hygroscopic expansion is used in
fabrication of cast restorations.
ACCELERATORS AND RETARDERS- The addition of accelerator produces a set of
mass which makes it possible to use the plaster within 30 minutes, but the
working time will also be reduced. The rate of hardening of natural plaster has
only few minutes of working time and then hardens gradually, usually very
slow for dental use. Therefore,