CHAPTER II

Model and Die Materials

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 Model and Die Materials

Definitions:
A model [cast]: is a replica of the teeth and/or the associated supporting
soft and hard tissues of the jaw, which is prepared from an impression.

A die: is a replica or model of a single tooth.

The materials used to make model, cast or die from an impression may be gypsum products, metals, resins,
or cements.

Impression Cast

Requirements for model and die materials

1. Mechanical properties:
a. Should have high strength to resist breakage during use.
b. Should be hard to resist scratching during use.
2. It should be able to reproduce fine details of the impression.
3. It should have little dimensional change on setting, and should remain dimensionally stable
during storage.
4. Compatibility with impression materials. There should be no interaction between the surface of
the impression and the model or die
5. Good color contrast with other materials being used
6. Ease of use and cheap.
Gypsum Products
Gypsum is a natural mineral, which is found in compact mass in nature.
Chemically, it is calcium sulphate dihydrate (CaSO4.2H2O)
It is usually white to milky yellowish in color.

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 Types of Gypsum Products
According to ADA specification No. 25, pure gypsum products, used in dentistry, are classified as, model
plaster, dental stone, high-strength stone.
All forms of gypsum products are chemically the same (calcium sulphate hemihydrate
“CaSO4.½ H2O”), but they differ in:
1. The method of manufacture
2. This leads to difference in particle size, shape, and form
3. This further leads to different W/P ratio they differ in:
4. Physical properties
5. Their use in dentistry

1. Manufacturing of different types:

Commercially, the gypsum is ground and subjected to temperature, to drive off part of the water of
crystallization (one and half molecules of water)
CaSO 4 .2H 2O heat
 CaSO 4 . 1 2 H 2O  1
110-130C 1
2HO 2
(Ca sulphate dihy drate) hemihy drate water

1) Model plaster type II (Plaster of Paris, ß-hemihydrate):

Model plaster got its term Plaster of Paris because it was obtained by burning the gypsum from deposits

near Paris, France.

CaSO 4 .2H 2O open

 air

 CaSO 4 . 1 2 H 2O  1 1 2 H 2O
(Ca sulphate dihy drate) 110130C  hemihy drate water

The powder particles are irregular in shape, large and porous.

 2) Dental stone type III (α-hemihydrate)( hydrocal):
CaSO 4 .2H 2O steam
  CaSO 4 . 1 2 H 2O 1 1 2 H 2O
pressure

Ca sulphate dihy drate autoclave 120-130C  hemihy drate

The particles are smaller, more regular in shape and less porous i.e. dense.
3) High strength stone type IV (Improved stone) (densite):

CaSO 4 .2H 2O boiling

  CaSO 4 . 1 2 H 2O 1 1 2 H 2O
30% CaCl 2

Ca sulphate dihy drate  hemihydrate

Then the chlorides are washed by hot water.

The particles are the smallest, most regular, and the least porous i.e. densest
N.B: All gypsum products are supplied in the form of powder to be mixed with water
2. Setting reaction (hardening reaction)
The crystalline theory

According to the crystalline theory the difference in the solubility of calcium sulphate dihydrate and
hemihydrate causes the setting of these materials.

On mixing hemihydrate with water the following will occur:

- Some of the hemihydrate dissolves in water, giving Ca++ and SO4-- ions, which in turn forms the
dihydrate in the solution.

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 - The solubility of the hemihydrate in water is much higher than the formed dihydrate.
- As the reaction proceeds, the concentration of the dihydrate increases rapidly to render the
solution super saturated with dihydrate. As super-saturation represent unstable condition, the
excess dihydrate start to precipitate to form nuclei of crystallization.

- More dihydrate will be precipitated around the nuclei of crystallization, leading to crystal growth.

- The reaction continues until all the hemihydrate is transformed into dihydrate.

Setting reaction: CaSO 4 . 12 H2O 1 12 H2O  CaSO 4 . 2H2O  heat (3900 cal for each gm molecule of CaSO4 .2H2O) .

3.Water/Powder ratio
By calculations
 (theoretical), chemically 100 gm of powder (CaSO4.½H2O) requires only 18.6 ml of water for
the CaSO4.2H2O to be formed. This water is known as water of crystallization or bonded water (The
needed water to complete the reaction).
- However, more water is needed practically for each 100 gm of powder in order to produce a
homogenous workable mix.
- This excess water will be present in the final product as free water.
- It will evaporate leaving the set material porous.
- It may take 7 days to loose the excess water.

Product W/P ratio ml/gm

Model Plaster 50-60/100
Dental stone 30/100
High strength stone 19-22/100

The difference in the W/P ratio is due to the difference in the particle size, shape, and the porosity of
each type of gypsum product.
4. Setting time (S.T.) :
It is the time elapsed from the beginning of mixing, until setting or hardening occurs.

- This time is divided into:

 Mixing time: The time taken from addition of powder to the water until we obtain a homogeneous
mix (not friable)

- Hand mixing 1 minute

- Mechanical mixing 20-30 seconds

 Working time (3 minutes)

Working time = time available for mixing, and use a workable mix (pouring a cast) before initial
setting.

 Loss of gloss (non workable mix)

As the reaction proceeds

- Some of the mixed water is taken up in forming dihydrate .

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 - Mix looses its gloss.

- The mass still has no measurable strength.

- It indicates partial setting.

 Initial setting time (12 minutes)

It is the time elapsed from the beginning of the mixing until partial setting occurs.

During this stage, the material will not flow.

It is possible to carve away the excess material.

 Final setting time (Several hours)

It is the time elapsed from the beginning of mixing until complete setting takes place where the
model or die will be strong and hard.

Ready to use stage: (30 minutes.)

It is the time at which the set material may be safely handled without fracture.
It may be considered as the time when compressive strength is 80% of the 1 hour compressive
strength.
Most modern products reach this stage in 30 minutes.

Measuring of setting time:

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 i- Loss of gloss:
To judge proper working time.

ii- Temperature rise:

Since the reaction is exothermic, it indicates setting.

iii- Penetration tests

This is an accurate method; they depend on resistance of the set gypsum material for
penetration by needles, which have a specific weight and definite tip diameter.

a. Vicat needle for measuring initial setting time.

b. Gillmore needles for measuring initial and final setting times.

Factors controlling the setting time:

Theoretically, according to the crystalline theory, the following will control setting time:
1. The solubility of the hemihydrate.
2. The number of nuclei of crystallization.
3. The rate of crystal growth.

a. Factors controlled by the manufacturer:

i. Fineness of the powder
The smaller the particles, the more is the wetting and the faster the rate of dissolution of the
hemihydrate.
This increases rapidly the number of nuclei of crystallization and consequently the growing
CaSO4.2H2O in a given volume.
Thus a more rapid growth rate is obtained, leading to acceleration of setting reaction and
decrease the setting time.

ii. Impurities
A small amount of calcium sulphate dihydrate 0.5-1% Terra Alba acts as nucleating agents
thus increase the number of nuclei of crystallization and a more rapid growth rate of growth is
obtained decreasing the setting time
Give reason:
Gypsum products (powder) should be protected from moisture contamination during storage?
Because moisture contamination may change some hemihydrate particles into dihydrate that
will increasing the number of nuclei of crystallization leading to too much decrease in the
setting time.

iii. Chemicals “Retarders and accelerators”

 Accelerators (e.g. 2% K2SO4)
They increase the rate of solubility of the hemihydrate in a given volume which will increase the
nuclei of crystallization in this given volume thus more rapid growth rate.
They accelerate the S.T. i.e. shorter S.T. or reduced S.T.

 Retarders (e.g. Borax, blood, saliva, or hydrocolloid)

a. coating hemihydrate particles thus reducing their solubility.(poisoning of nuclei)
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 b. Or coating the growing crystals thus inhibiting the growth rate.

They retard the S.T. i.e. longer S.T. or increased S.T.

Give reason:
1. The impression should be washed before pouring the model?
To wash the blood and saliva that act as retarder for gypsum (model material).

2. The hydrocolloid impression should contain an accelerator for gypsum model? Because the
hydrocolloid will retard the setting time of gypsum.

c. Factors controlled by the operator:

i. W/P ratio
- High W/P:
High W/P (thin mix) will lead to less powder in the mix, less nuclei of crystallization in a given
volume, so few CaSO4.2H2O crystals will be formed, slowing the growth rate. Retard S.T i.e.
longer S.T. or increased S.T.

ii. Mixing time and rate

Increasing mixing time and rate within limit will provide more nuclei of crystallization in a given
volume, more growing CaSO4.2H2O crystals will occur and rapid growth rate will be obtained.
Accelerate S.T. i.e. shorter S.T. or reduced S.T.

iii. Temperature
From 20-50C: acceleration of setting time. (As heat accelerate any chemical reaction)
Above 50C: retardation of the setting time
At 100C no reaction takes place because the solubility of hemihydrate = the solubility of
dehydrate.

5. Properties of Gypsum Products

5.1. Dimensional changes: (Setting Expansion and Hygroscopic Expansion):

a. Setting expansion: gypsum products show expansion during setting from hemihydrate to
dehydrate. It is due to outward thrusting action of the growing crystals.

N.B

i. By calculations (Theoretically), a volumetric contraction should occur during the setting reaction (7%).

ii. Because the set gypsum is greater in external volume than its crystalline volume, it follows that the set
material is porous. The final structure is composed of interlocking crystals between which pores
containing the excess water.

Linear Setting Expansion Porosity

Model plaster 0.2-0.3 45%

Dental stone 0.08 15%
High strength stone 0.05-0.07 10%
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 b. Hygroscopic expansion:
 It is the expansion of gypsum when it is allowed to set under water during initial stage of setting.
This additional water provides more room for crystal growth.

i.e. Hygroscopic expansion is a physical reaction.

 Hygroscopic expansion may be more than double the normal setting expansion in air.

Factors Affecting the Setting Expansion:

i. W/P ratio:
a. High W/P ratio

High W/P (thin mix) will lead to less nuclei of crystallization in a given volume producing few growing
CaSO4.2H2O, so their outward growing thrust is decreased

i.e. setting expansion is reduced or decreased.

N.B: the same effect on hygroscopic expansion.

b. Low W/P ratio( Answer by yourself)

ii. Mixing time and rate:

Increasing the mixing time and rate within limits will provide more nuclei of crystallization in a given
volume, producing more growing CaSO4.2H2O crystals in this volume. Increasing the outward thrust of
the growing crystals, more setting expansion (S.E.) is increased.

iii. Chemicals:
In general, chemicals regulate the shape of the growing crystals thus decreasing their thrusting action,
thus decreasing the setting expansion.

5.2. Compressive strength:

The strength of the gypsum products increases rapidly, as the material hardens after the initial
setting time.
There are two types of strength of gypsum products:
a. Wet strength (green strength or 1 hour strength):
It is the strength of the set of gypsum containing the excess water
b. Dry strength:
It is the strength obtained after the gypsum has been dried and lost the excess water.
 The dry strength is usually double the wet strength.
N.B: Gypsum products are brittle materials.

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 Factors affecting the strength:

i. W/P ratio:
The higher the W/P ratio the more excess water will remain, which eventually vaporize leaving
more pores and weaker product.

ii. Mixing time and rate:

- Increasing the mixing time and rate within limits will provide more nuclei of crystallization in a
given volume.

More growing calcium sulphate dihydrate crystals will be present in this volume, increasing the
crystalline interlocking, thus, strength will be increase.

- But over-mixing results in decreasing the strength, because the formed gypsum crystals will be
broken up and less crystalline interlocking will be obtained.

iii. Chemicals:
The chemicals regulate the shape of the growing CaSO4.2H2O crystals thus reducing the
intercrystalline cohesion and decreasing the strength

iv. Type of gypsum products:

Strength of improved stone > Strength of dental stone > Strength of model plaster.

N.B: Improved stone can be weak as model plaster if it is mixed with excess water than
the required W/P ratio

v. Dryness:
Dry strength is higher than the wet strength.

vi. Addition of wetting agents [lignosulfate]:

Addition of wetting agent will reduce the amount of water needed to wet the powder particles
thus decreasing W/P ratio. This will decrease the amount of excess water remaining in the set
mass (which will evaporate) leaving less pores and stronger product.

5.3. Surface hardness and abrasion resistance:

- Generally, the surface hardness is low, so the material is easily susceptible to scratching

- Addition of resin [polymer] to the surface of the set gypsum will increase hardness and abrasion
resistance.

5.4. Reproduction of Details:

They do not reproduce surface details accurately, because:

a) The surface of the set gypsum is porous on microscopic level

b) Air bubbles are formed at the interface of certain impressions and gypsum cast.

Other die materials:

- Silicophosphat, Amalgam, Epoxy, Acrylic resin, Ceramic die, Metal sprayed die
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- Electroplated die

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Table 1: Comparison between Dental Gypsum Products

Difference Plaster Dental stone High strength stone

Method of
Open air Autoclave 30% CaCl2
production

Particle size & Large irregular, Smaller regular, Smallest, most

shape porous less porous regular, least porous
W/P ratio 50-60/100 30/100 22/100
Setting expansion 0.2-0.3% 0.08% 0.05-0.07%

Compressive 12.5 MN/m2 31.5 MN/m2 38.5 MN/m2

strength Lowest Higher Highest

15 R.H.N
60 R.H.N 80 R.H.N
Hardness Soft
Harder Hardest
[easy to be scratched]

Porosity % after 45% 15% 10%

setting Highest Less Least

- Primary cast for - Secondary Cast for

- Secondary cast for
edentulous patients edentulous
crown and bridge
- Impression material, patients
Uses - Die for crown and
Type I - Binder in
bridge work
- Flasking investment
- Articulating material

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 Recent Advances

Since we are able today to get a digital impression directly from the patient mouth using the intraoral
scanners and have all the information present on the computer software. Using a 3D printer, we can print
a complete polymeric model or part of it.

3D printers are machines that has the ability to build up a structure layer by layer through different
techniques using information from a computer software.
.

Left: Diagram of 3D printer parts, Right: Diagram of the printer head and printed structure

Up: partial 3D printed model of 4 teeth, Down: complete 3D printed models

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 Assignment Questions

 Give reason(s):
1. Chemical additives decrease the setting expansion of gypsum products.
2. The use of excess water to mix with CaSO4. ½ H2O.
3. All types of gypsum products undergo setting expansion.
4. The amount of water needed to make a workable mix of the various types of gypsum products is
different.
5. The use of boiling water is contraindicated during mixing of gypsum products.
6. The addition of K2 SO4 accelerates the setting of gypsum products.
7. The addition of borax increases the setting time of gypsum products.
8. The finer the particles of gypsum powder, the faster the setting of the gypsum mix.
9. Decreasing the W/P ratio accelerates the setting of gypsum.
10. Increasing the mixing time and rate accelerates the setting of gypsum.

 Choose the correct answer(s):

1. The hydrocal and densite are mainly different from each other regarding their:
 Chemical composition.
 Color.
 Particles' size and shape.
 All of the above.
2. Hygroscopic expansion of gypsum products means:
 Expansion due to mixing with excess water.
 Expansion due to immersion of gypsum under water before complete setting.
 Expansion due to immersion of gypsum under water after complete setting.
 None of the above.

3. The amount of water that reacts chemically with 100 gm of improved stone powder is:
 18.6 ml.
 22 ml.
 30 ml.
 55 ml.

4. Increasing the water/ powder ratio of gypsum products:
 Increases strength.
 Increases setting expansion.
 Increases setting time.
 Decreases flow.

5. Improved stone can be obtained by heating gypsum in:

 Open air at 120oC.
 An autoclave under steam pressure at 120-130oC.
 Boiling 30% solution of Ca Cl2.

6. When hemihydrate is mixed with water:

 The hemihydrate dissolves in water to form Ca++ and SO4--.
 Dihydrate is precipitated.
 The reaction is exothermic.
 All of the above.
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 7. During setting of gypsum products, theoretically, the volume of the final dihydrate is:
 7% less than the total volume of hemihydrate and water.
 7% more than the total volume of hemihydrate and water.
 Equal to the total volume of hemihydrate and water.

8. The difference in the particle size and shape between the various gypsum products results from
the:
 Difference in the chemical formula.
 Difference in the methods of manufacturing.
 Difference in the modifiers.
 Difference in the strength.

9. Gypsum products are the result of calcination of:

 Ca SO4. ½ H2O.
 Ca SO4. 2 H2O.
 Ca SO4.

10. Plaster of Paris shows more setting expansion than dental stone because:
 Dental plaster takes higher water/ powder ratio.
 Dental stone powder particles are more regular.
 Dental plaster powder particles are more porous.

 State true or false and correct the false:

1. Gypsum is found in nature in the form of calcium sulfate hemihydrate.
2. The main difference between plaster of Paris and hydrocal is their chemical composition.
3. Increasing the W/P ratio of the gypsum mix will increase the hygroscopic expansion.

4. Mixing gypsum products with hot water at 100 oC accelerates the setting reaction.
5. The amount of water needed to produce a workable mix when mixed with hemihydrate powder
depends on the size, shape and porosity of the particles.
6. The Gillmore and Vicate penetrometers measure the final setting time of gypsum products.
7. The initial setting time of model plaster can be detected clinically by the phenomenon known as
loss of gloss.
8. All gypsum products show a measurable linear expansion during setting that results from the
outward thrust of the growing hemihydrate crystals.
9. Increasing the water/powder ratio decreases the strength of gypsum products.
10. The presence of impurities in the powder of gypsum products increases the setting time.

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