GYPSUM AND ITS PRODUCTS

LEARNING OUTCOMES

• At the end of the lecture you would be able to know the

• Types of gypsum
• Manufacturing techniques
• Setting reaction and theories related to it
• Setting expansion and
• Manipulation of Plaster of Paris
INTRODUCTION

• Gypsum is a naturally occurring mineral found in many part of the world.

• Chemically it is calcium sulfate dihydrate.(CaSO4.2H2O)
• A mixture of plaster (a gypsum product), lime, and water was used in joining the stone
blocks of ancient Egypt’s pyramids.
APPLICATIONS

• Gypsum and gypsum products are used today for many applications ,

• Building construction,

• Soil conditioning,

• Food additives,

• Pharmaceuticals,

• Medical devices,

• and dental applications.

APPLICATIONS IN DENTISTRY

• The primary applications of gypsum products in dentistry

• study models for oral and maxillofacial structures
• as Auxiliary materials for the production of dental prostheses.
• Molds for the casting of alloys( When refractory fillers it becomes more heat resistant
and is known as a gypsum-based investment)
• Cast—A reproduction of the shape and surface of a structure made in an impression of
the surface.
• Die—A reproduction of a prepared tooth made from a gypsum product, epoxy resin, a
metal, or a refractory material.
• Model—A positive likeness of an object.
Requirements of dental cast material

• Dimensional accuracy and adequate mechanical properties.

• Balancing of small expansions or contractions to help fit the denture .
• Fluid when poured into the impression, so fine detail can be recorded.
• A low contact angle reduces surface voids on the set model by encouraging surface wetting.
• Strong to resist accidental fracture and hard enough to resist abrasion during the carving of a wax
pattern.
• Compatible with all the other materials.
• For example, the set model should easily be removed from the impression without damage to its surface
and fracture of teeth.
• Good color contrast with the various waxes.
 According to ADA specification gypsum products are
classified into 5 types

1.Impression plaster (beta –hemihydrates)

CLASSIFICATION 2. Plaster of paris/dental plaster/model plaster

3. Dental stone/hydrocal/class1 stone (alpha-hemihydrate)

4. Die stone with high strength/densite/class 2 stone

5. Die stone with high strength and high setting

expansion/class3 stone/crystocol.
 According to calcination ,they are classified into
two types.

CLASSIFICATION
1.Calcium sulfate beta –hemihydrate;
obtained by dry calcinations, examples
impression plaster and dental plaster.

2. calcium sulfate alpha-hemihydrate

;obtained by wet calcination,examples dental
stone,die stone with high strength and die stone
with high strength and high setting expansion.
MANUFACTURING

• (Calcination—The process of heating a solid material to drive off volatile chemically

combined components such as water and carbon dioxide.)

• Dry calcination(beta - hemihydrate manufacturing)

• Heating gypsum mineral in a open kettle at a temperature of about 110 ͦC to 120 ͦC .

• Powder has irregular shape particules and is porous (sponginess) in nature.

WET CALCINATION(ALPHA –HEMIHYDRATE
MANUFACTURING)
Calcined under steam pressure
• In an autoclave at a
temperature of 110 ͦC
to120 ͦC.
• It has uniform size particles
and are denser.
• This is also called autoclaved
calcium sulphate
hemihydrate or hydrocal.
Calcining with small quantity
of organic acid or salt
• In an autoclave at 130 ͦC
• Product obtained is called
crystocol.
Boiling in a 30% calcium
chloride solution
• Chloride is washed away and
• Calcium sulfate hemihydrates
is dried and grounded to
desired fineness.
• The powder obtained by this
process is denser of three
methods.
DENTAL STONE
IMPROVED STONE(Scanning electron photomicrograph of
the surface of a set high-strength stone die. )
CHEMICAL • Calcium sulfate di-hydrate---------------- 110 C
ͦ to
REACTION 120 C
ͦ =calcium sulfate hemi-hydrates + water
• CaSO4.1/2H2O+3H2O= CaSO4.2H2O+3900cal/mol
• Type 4 gypsum differs from type 5 in that type 4
contains extra salts to reduce its setting expansion.
THEORIES OF GYPSUM SETTING

• 1. Crystalline (dissolution precipitation ) theory of setting

• 2. Colloidal theory
• 3. Hydration theory
COLLOIDAL THEORY

• When mixed with water , plaster enters into the colloidal state through sol
–gel mechanism.
• In the sol state , hemihydrate particles are hydrated to form dihydrate ,
thereby entering into an active state .
• As the measured amount of water is used ,the mass converts into solid
gel.
HYDRATION THEORY

It suggests that rehydrated plaster particles join together through

hydrogen bonding to the sulfate groups to form the set material.
 • It was originated in 1887 by Henry Louis Le Chatelier,
a French chemist.
• When hemihydrates mixed with water a suspension is
formed , that is fluid and workable
• Supersaturated solution is formed.
• Suitable nucleation takes place.
CRYSTALLINE
• As dihydrate crystallizes, more hemihydrates dissolves
(DISSOLUTION and process continues until hemihydrates is converted
PRECIPITATION into dihydrate. The mass thicken into needle like crystals
) THEORY OF called spherulites
SETTING • Finally, intermeshing and entangling of crystals lead to
strong solid structure, which is final set.
• The reaction rate can be followed by exothermic heat
evolved.
 Water powder ratio

PROPERTIES • Low water powder ratio,

• The mixed mass is thicker
• More difficult to handle
• Traps air bubbles easily when it is
poured into a mold
• The set gypsum is usually stronger.
• High water powder water ratio
• Free water in the set mass doesn’t take
part in the chemical reaction,
• Porosity in the structure,
• The set gypsum is weak.
• Setting time( Time elapsed from the beginning of mixing until the material hardens.)
• Initial setting
• Final setting
• Measurement of setting time
1. Loss of glossy test
2. Penetration test
3. Indentation test
4. Exothermic reaction
Vicat apparatus

• Measure the initial setting time of gypsum products.

• It consists of a rod weighing 300 g with a needle of 1-mm diameter.
GILLMORE APPARATUS

Initial set Final set

When the mix can resist penetration by a
Gillmore needle,
A tip,
diameter = 2.12 mm (1/12 inch) in
weighs =113.4 g (¼ lb)
• no measurable compressive strength, and the
cast cannot be safely removed from the
impression.
The elapsed time at which a heavier Gillmore
needle,
A tip
weighing =453.6 g (1 lb)
diameter =1.06 mm (1/24 inch)
Effect of Water/Powder Ratio (W/P) and Mixing Time on the
Setting Time of Plaster of Paris

W/P Ratio Mixing Time (min) Setting Time (min)

0.45 0.5 5.25
0.45 1.0 3.25
0.60 1.0 7.25
0.60 2.0 4.50
0.80 1.0 10.50
0.80 2.0 7.75
0.80 3.0 5.75
 • Setting time can be controlled by increasing or
decreasing,
• Solubility of hemihydrates (If the solubility of the
hemihydrate is increased, supersaturation of the dihydrate
FACTOR is achieved faster, which accelerates the rate of dihydrate
AFFECTING crystal deposition.)
SETTING • Number of nuclei of crystallization
TIME • The rate of crystal growth
• Impurity hexagonal anhydrate –decrease the setting
time
Orthorhombic anhydrate –increase the setting time.
• Temperature
temperature increase from 20to37 C ͦ the rate of
dihydrate increases and setting time decreases.

Near boiling point of water, the solubility of hemihydrate and

dihydrate are approximately equal 0.17= no reaction takes
place and plaster will not set to a harder mass of gypsum
EFFECT OF HUMIDITY

• When the relative humidity increases to 70% and above,

• Moisture in the air can cause some conversion of hemihydrate to dihydrate.
• It accelerate the reaction by providing more nuclei for crystallization.
• Further contamination by moisture causes retardation of setting as less hemihydrate
remaining to form gypsum.
• Storage in a closed container and well protected from moisture in the air is
recommended.
Effect of Spatulation

• The mixing process, called spatulation, effect the setting time and setting expansion of the
material.
• During spatulation the newly formed calcium sulfate dihydrate breaks down to smaller
crystals and forms new centers of nucleation.
• Increased amount of spatulation causes more nuclei centers to be formed, decreases
setting time.
 .
1 Potassium sulfate
ACCELERATORS
2. Sodium sulfate

3. Sodium chloride
4.Borax
 2. sodium chloride
1. Borax
more than 2%

RETARDERS
3. sodium sulfate
4. citrate ,acetate
more than 12%

5. blood,saliva
and alginate or
agar impression
materials
SETTING EXPANSION

• An expansion can be detected during change from hemihydrate to dihydrate.

• Linear expansion can be as low as 0.06 % or as high as 0.5%.
• Crystallization process is the outgrowth of crystals from the nuclei of
crystallization.
• Crystals growing from nuclei can intermesh with and obstruct the growth of
adjacent crystals
• An outward stress or thrust develops that produces expansion of the entire
mass. This crystal impingement and movements results in production of
MICROPORES
CONTROL OF SETTING EXPANSION

. Increase w/p ratio = fewer nuclei of crystallization per unit volume are
present than thick mixes, less dihydrate crystals and less outward thrust.
. Less w/p ratio = Increase setting expansion .
. potassium sulfate, sodium chloride or borax(reduces SE)
TYPES OF EXPANSIONS

• Normal setting expansion

• Hygroscopic setting expansion
NORMAL SETTING EXPANSION

• Setting expansion that occurs under normal condition that is without

water immersion is termed as normal setting expansion.
HYGROSCOPIC EXPANSION

Hygroscopic setting expansion—The expansion that occurs when

gypsum or a gypsum-bonded investment sets while immersed in water
(usually heated to approximately 38 °C [100 °F]).
• This setting expansion should be minimum for mold and cast but when
dental stone is used as binder in investment materials ,large setting
expansion is needed to compensate casting shrinkage .
• Hygroscopic expansion is more ,if
• Time of immersion in water is more.
• Less water to powder ratio .
• Longer spatulation.
• Fresh material .
• No chemicals are added.
Volumetric contraction

• The contraction of gypsum is not visible

• Measured by a dilatometer, about 7%.
Compressive strength

• When set, gypsum products show relatively high values of compressive strength.
• The compressive strength is inversely related to the W/P ratio of the mix.
• The more water used to make the mix, the lower the compressive strength.
 MANIPULATION(Hand or mechanical mixing)

The plaster or stone is usually mixed in a flexible rubber or plastic bowl using stiff bladed spatula.

The water is added first then powder is added and allow setting for 30seconds.this technique minimize
the amount of air incorporated into mix during initial spatulation.
Gypsum Mixing Water
(mL/100 g of powder)

Model plaster 37-50

Dental stone 28-32
High-strength dental stone 19-24
A vibrator is designed to promote the release of bubbles in
the gypsum mix and to facilitate pouring of the impression.
Power-driven mechanical spatulator with a
vacuum attachment.
QUESTION

• During mixing of calcium sulfate hemihydrate product with water , extra

water may be added to facilitate the mixing and pouring process, what are
the adverse changes may occur when the recommended water to
powder ratio has not been used?
• What are the effects of cold and hot water on setting time ?