DENTAL MATERIALS II

GYPSUM MATERIALS

 Gypsum materials are widely used in dentistry, are obtained from natural
deposits of gypsum, CaSO4 • 2H2O, which when heated, loses 1.5 g mol of
water and converts to the hemihydrate, CaSO4 • ½H2O
 On mixing with water, the hemihydrate exothermically converts back to
dihydrate: CaSO4 • ½H2O + 1½H2O → CaSO4 • 2H2O + 3900cal/g mol
 There are four types of gypsum materials that are chemically identical but
differ in morphology and physical properties.

Dental gypsum products

ANSI/ADA specification
nomenclature
Type I ‒ Plaster, impression
Type II ‒ Plaster, model
Type III ‒ Dental stone
Type IV ‒ Dental stone, high strength
Traditional nomenclature
Impression plaster
Model or laboratory plaster
Class I stone, model stone
Class II stone, die stone

Type 4 die stone has a low setting expansion of 0‒0.15%

Type 5 die stone expands 0.16‒0.30% (high expansion)

Model plaster, dental stone and die stone

 Model plaster (beta-hemihydrate) is produced by heating gypsum in an
open kettle at 110‒120°C → its particles are irregularly shaped, porous and
white.
  Dental stone (alpha-hemihydrate) is produced by dehydration of gypsum in
water vapor under pressure at 125°C → has more uniformly shaped and
denser particles than plaster and is not white (yellow, blue, etc.).
 Die stone (high-strength stone) is the highest density dental gypsum, is
made by boiling gypsum in 30% CaCl2 solution, washing out residual
chlorides with 100°C water and grinding the mass to powder.

Water/powder (W/P) ratios for gypsum materials

Product W/P ratio
(g water/100g powder)
Plaster 40‒50
Dental stone 25‒30
Die stone 19‒24

Physical properties

Mixing
 For the same W/P ratio, mechanical mixing decreases setting time, increases
strength, decreases viscosity and reduces expansion.
 Spatulation speed and duration affect setting time and expansion, because
spatulation disrupts ‘precipitation centers’, forming new nuclei and reducing
the setting time.

Compressive strength
 Compressive strength is proportional to dryness.
 Set gypsum requires at least 24h and usually 7 days to lose excess H2O and
achieve adequate strength.
 Porosity in the set mass decreases strength.
 The strength of the set material is determined by the W/P mix.
Tensile strength
 Gypsum is brittle and the 1-h diametral tensile strength (DTS) is only 50%
of the dry strength.
 The ratio of DTS to compressive strength is 5‒10:1.

Surface hardness
 Surface hardness increases upon drying.
 Impregnation with resin monomers and subsequent polymerization or by
admixture of hardening solution containing colloidal SiO2 increases
hardness.
 Surface treatment with wax, oils or glycerol improves carvability but not
hardness.

Setting expansion
 Gypsum expand on setting, with W/P ratios and additives affecting
expansion (K2SO4 reducing it, NaCl increasing it).
 Setting of gypsum materials under water (hygroscopic effect) can increase
expansion up to 100%.
 After setting, there is zero dimensional change with time.

Comparative properties
 W/P ratio, setting time and setting expansion decrease while strength
increases from Type II to Type IV products.
 Use of dental stone and die stone as processing casts results from their
greater strength and abrasion resistance and ability to record more detail than
model plaster.
 DENTAL WAXES

 Denatl waxes are soft substances with poor mechanical properties and their
primary uses in dentistry are to form patterns of appliances prior to casting.
 Following the production of a dental stone model or die, the next stage in the
formation of dental appliances, dentures or restorations is the production of a
wax pattern of the appliance on the model.
 The wax pattern defines the shape and size of the resulting appliance and is
replaced by either an alloy or a polymer using the lost-wax technique.
 Denatl waxes are thermoplastic: solid at RT (room temperature), melt when
heated and harden without decomposition on cooling.
 Denatl waxes consists of two or more components which may be natural or
synthetic waxes, resins, oils, fats and pigments.
 Three categories are recognized and they are classified by composition and
application.

Categories of dental waxes

Wax type Application

Impression
Bite wax Recording occlusal and jaw relationships
Corrective wax Dental impressions
Pattern
Baseplate wax Establishing initial arch during denture making
Casting (modelling) wax Wax rims and temporary bases during denture
making
Inlay wax Making patterns for cast restorations
Processing
Boxing wax Perimeter border of impression trays during
pour-up
Sticky wax Temporary adhesive
Utility Variety applications
Classification of denatl waxes
Denatl waxes are classified by composition:
I. Natural waxes
1. Mineral
2. Plant (vegetable)
3. Animal
II. Synthetic waxes

Classification of natural waxes by origin

Mineral Plant Animal
Paraffin Carnauba Beeswax
Microcrystalline Ouricury Lanoline
Barnsdahl Candelilla Spermaceti
Ozokerite Japan wax China wax
Ceresin Cocoa butter
Montan

Mineral waxes
Paraffin wax and closely related microcrystalline wax are both obtained
from petroleum residues following distillation.

Paraffin waxes
 Paraffin waxes are straight 26‒30 carbon atom chains alkanes.
 Melting range increases with molecular weight (MW) and is decreased by
oils (≤0.5% oil).
 On solidification and cooling, they contract 11‒15 vol.% non-uniformly
down to RT because of numerous phase transitions.
 Most denatl waxes comprise paraffin waxes with other waxes, gums, oils
and resins added to modify properties.
Microcrystalline waxes
 Microcrystalline waxes are branched 41‒50 carbon atom chain hydrocarbons
of greater MW and melting range than paraffins.
 They are tougher, more flexible and exhibit lower volumetric contraction.
 They have affinity for oils that facilitates hardness and tackiness
modification.
 Microcrystalline waxes are used to modify paraffin wax properties.

Barnsdahl, Ozokerite and Ceresin waxes

 Barnsdahl increases melting range and hardness while reducing flow,
whereas 5‒15% additions of Ozokerite improve physical properties in the
melting range of 54°C.
 Ceresin additions raise paraffin wax melting range.

Montan waxes
 Montan waxes are mixtures of long‒chain esters and high MW alcohols,
acids and resins extracted from lignite.
 They are similar in properties to plant waxes being hard and brittle, raise the
melting range and hardness of paraffin waxes.

Plant waxes
This waxes are of vegetable origin, derived from trees and plants. They are
blended with paraffin wax in order to control the softening temperature and modify
properties.

Carnauba and Ouricury waxes

  Carnauba and Ouricury waxes are mixtures of straight‒chain esters,

alcohols, acids and hydrocarbons.

 They have high hardness and are brittle with high melt temperatures.

 Additions of ≤10% raise hardness and melting range by 24°C of paraffin

waxes.

Candelilla waxes
 Candelilla waxes: comprise 40‒60% hydrocarbons with free alcohols, acids,
esters and lactones.
 They harden paraffin waxes with little effect on melting range.

Japan wax
 Japan wax is a fat containing glycerides of palmitic, stearic acids and higher
MW acids that is tough, malleable and sticky.
 This wax increases tackiness and emulsifying ability of paraffin wax.

Cocoa butter
 Cocoa butter is a fat composed of glycerides of palmitic, stearic, oleic, lauric
and lower fatty acids.
 It is brittle at RT.
 Cocoa butter is used to reduce dehydration of soft tissues.

Animal waxes
Beeswax
 Beeswax is insect wax, derived from honeycombs, that is a complex mix of
esters, hydrocarbons and high MW organic acids.
  It is brittle at RT but plastic at body temperature.
 It is often blended with paraffin wax in order to modify the properties of the
latter.

Synthetic waxes

 Synthetic waxes include polyethylene, polyoxyethylene glycol, halogenated

hydrocarbon, hydrogenated waxes and wax esters.
 Polyethylene waxes have a MW of 2000‒4000 while polyoxyethylene waxes
are polymers of ethylene glycols with similar melting temperatures and
hardness to natural waxes, but are poorly compatible with other waxes.
 They are used to plasticize and toughen wax films.

Wax types and their applications

Impression waxes

 These waxes consist of a mixture of a low melting paraffin wax and beeswax in
a ratio of 3:1 which ensures a high degree of flow and ductility at mouth
temperature.
 They cannot be used for undercuts due to their inability to deform elastically.
 Corrective impression wax is used to correct small imperfections in other
impressions.
 Bite wax is widely used for recording occlusal and jaw relationships
Pattern waxes

Requirements of wax-pattern materials:

1. The wax pattern must conform to the exact size, shape and contour of the
appliance which is to be constructed.
2. No dimensional changes should take place in the wax pattern once it has been
formed.
3. After formation of the casting mould, it should be possible to remove the wax
by boiling out or burning without leaving a residue.

 Thermal effects distort pattern waxes, particularly on standing unrestrained,

distortion increasing with temperature and time.
 Uniformly heating wax, carvers and die before incremental wax application and
storing the pattern in a refrigerator, minimizes thermal distortion and stress
relaxation.

Baseplate wax
 Baseplate wax is typically 75‒80% paraffin or ceresin with additions of
beeswax, carnauba and microcrystalline waxes or resins.
 They show minimal flow at RT but 90% at 37°C.
 Baseplate wax is used for establishing initial arch during denture making.
 Denture modelling waxes are used as: wax rim, wax denture at the ‘try in’ stage

Casting (modelling) waxes

 Casting (modelling) waxes are ductile and must bend over double without
fracture at RT.
 These have similar flow behaviour to inlay waxes, with a maximum flow of
10% at 35°C and at least 60% flow at 38°C.
 Casting waxes are used as: wax rims and temporary bases during denture
making.

Inlay waxes
 Inlay waxes contain 60% paraffin, 25% carnauba, 10% ceresin and 5%
beeswax, with flow adjusted by the carnauba content, higher melting range
paraffins and/or ≤1% resin.
 Type I inlay wax for indirect patterns is soft with greater flow below and above
oral temperature and less thermal contraction than Type II inlay wax, used for
the direct technique.

Processing waxes

Boxing wax
 Perimeter border of impression trays during pour-up.

Sticky wax
 Sticky wax is composed of beeswax and rosin (colophony), it is sticky when
melted but hardens to a tack-free, brittle material at RT.
 Sticky wax is used as temporary adhesive in fractured dentures, models, etc.

Utility wax
 Variety applications.
 Wax properties

Melting and thermal expansion

 Waxes have melting ranges rather than a melting temperature and large thermal
expansions/contractions.
 The latter are modifiable but not eliminated by compounding.
 Expansion coefficients vary with temperature, and are greater for mineral than
for plant waxes due to weaker secondary valence forces. Higher forces of plant
waxes are due to their high ester content.
 Phase transitions cause waxes to have ≥2 rates of thermal expansion.

Mechanical properties
 Strength, proportional limit and elastic modulus are low and temperature
dependent, and decrease with temperature rise.
 The elastic modulus of paraffin wax decreases 91% from 24° to 30°C and that
of carnauba wax decreases 58% from 23° to 37°C.

Flow
 Flow depends on temperature and the magnitude and duration of load
application.
 The flow increases near to the melting range, more so for mineral than for plant
waxes.