Article No : a08_251

Dental Materials
ROBERT G. CRAIG, formerly The University of Michigan, Ann Arbor, MI, United States
DIETER WELKER, formerly Klinikum der Friedrich-Schiller-Universit€at Jena, Jena,
Germany
JOSEF ROTHAUT, Wieland Dental & Technik GmbH & Co. KG, Pforzheim, Germany
KLAUS GEORG KRUMBHOLZ, DeguDent GmbH, Hanau-Wolfgang, Germany
KLAUS-PETER STEFAN, ESPE Dental AG, Seefeld, Germany
KLAUS DERMANN, formerly Degussa-H€uls AG, Hanau-Wolfgang, Germany
HANS-JOACHIM REHBERG, formerly Bayer AG, Leverkusen, Germany
GERTRAUTE FRANZ, formerly Universit€atskrankenhaus Eppendorf, Hamburg, Germany
KLAUS MARTIN LEHMANN, formerly Klinikum der Philipps-Universit€at Marburg,
Marburg, Germany
MATTHIAS BORCHERT, BIOS Dental GmbH, Bohmte, Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 96 3.2.4. Quality Requirements . . . . . . . . . . . . . . . . . 118

1.1. Direct Materials. . . . . . . . . . . . . . . . . . . . . 96 3.2.5. Ceramic Fused to Titanium . . . . . . . . . . . . . 118
1.2. Indirect Materials . . . . . . . . . . . . . . . . . . . 98 3.3. Dental Ceramics for Fixed Restorations . . 118
1.3. Auxiliary Materials . . . . . . . . . . . . . . . . . . 100 3.3.1. Jacket Crowns . . . . . . . . . . . . . . . . . . . . . . . 118
2. Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 3.3.2. Newer Developments. . . . . . . . . . . . . . . . . . 119
2.1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 101 4. Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.2. Metallic Materials for Fillings . . . . . . . . . . 102 4.1. Cements Setting by Neutralization Reaction 121
2.2.1. Pure Gold . . . . . . . . . . . . . . . . . . . . . . . . . . 102 4.1.1. Zinc Phosphate Cements . . . . . . . . . . . . . . . 121
2.2.2. Silver Amalgams . . . . . . . . . . . . . . . . . . . . . 102 4.1.2. Silicate Cements . . . . . . . . . . . . . . . . . . . . . 122
2.2.3. Copper Amalgams . . . . . . . . . . . . . . . . . . . . 104 4.1.3. Silicophosphate Cements . . . . . . . . . . . . . . . 122
2.2.4. Gallium Alloys . . . . . . . . . . . . . . . . . . . . . . 104 4.1.4. Zinc Polycarboxylate Cements . . . . . . . . . . . 122
2.3. Metallic Materials for Prosthetic 4.1.5. Glass Ionomers . . . . . . . . . . . . . . . . . . . . . . 122
Restorations . . . . . . . . . . . . . . . . . . . . . . . . 104 4.1.6. Resin-Modified Glass Ionomers . . . . . . . . . . 124
2.3.1. Precious Metal Casting Alloys . . . . . . . . . . . 105 4.1.7. Polyacid-Modified Composites . . . . . . . . . . . 124
2.3.2. Nonprecious Metal Casting Alloys . . . . . . . . 110 4.2. Cements Based on Complex Formation . . . 124
2.3.3. Casting Alloys for Removable Dentures . . . . 111 4.2.1. Zinc Oxide – Eugenol Cements . . . . . . . . . . 124
2.4. Brazing Alloys . . . . . . . . . . . . . . . . . . . . . . 111 4.2.2. Calcium Hydroxide Cement . . . . . . . . . . . . . 125
2.5. Metallic Materials for Implants . . . . . . . . . 113 4.2.3. Other Chelating Cements . . . . . . . . . . . . . . . 125
2.6. Metals and Alloys for other Purposes . . . . 113 4.3. Standards. . . . . . . . . . . . . . . . . . . . . . . . . . 125
3. Dental Ceramic Materials . . . . . . . . . . . . . 114 5. Synthetic Resins. . . . . . . . . . . . . . . . . . . . . 125
3.1. Ceramic Teeth . . . . . . . . . . . . . . . . . . . . . . 114 5.1. Denture Base Resins . . . . . . . . . . . . . . . . . 125
3.1.1. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . 114 5.1.1. Heat-Cured Polymers. . . . . . . . . . . . . . . . . . 126
3.1.2. Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . 115 5.1.2. Cold-Cured Polymers. . . . . . . . . . . . . . . . . . 126
3.1.3. Quality Requirements . . . . . . . . . . . . . . . . . 116 5.1.3. Light-Cured Polymers . . . . . . . . . . . . . . . . . 127
3.2. Dental Ceramic Fused to Metal Restorative 5.1.4. Microwave-Cured Polymers . . . . . . . . . . . . . 127
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 116 5.1.5. Other Denture Resins. . . . . . . . . . . . . . . . . . 127
3.2.1. Thermal Expansion . . . . . . . . . . . . . . . . . . . 117 5.2. Acrylic Teeth . . . . . . . . . . . . . . . . . . . . . . 128
3.2.2. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . 117 5.3. Crown and Bridge Veneer Resins . . . . . . . 128
3.2.3. Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . 117 5.3.1. Heat-Cured Resins. . . . . . . . . . . . . . . . . . . . 128

! 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a08_251.pub2
96 Dental Materials Vol. 11

5.3.2. Light-Cured Resins . . . . . . . . . . . . . . .... . 128 6.1.1. Alginates. . . . . . . . . . . . . . . . . . . . . . .... . 133

5.4. Resin – Metal Bonding . . . . . . . . . . .... . 129 6.1.2. Elastomers . . . . . . . . . . . . . . . . . . . . .... . 133
5.5. Resins for Orthodontics . . . . . . . . . . .... . 129 6.2. Rigid Materials . . . . . . . . . . . . . . . . .... . 136
5.6. Restorative Resins . . . . . . . . . . . . . . .... . 129 6.2.1. Plaster of Paris . . . . . . . . . . . . . . . . . .... . 136
5.6.1. Paste – Paste Systems . . . . . . . . . . . . .... . 130 6.2.2. Zinc Oxide – Eugenol Pastes . . . . . . . .... . 136
5.6.2. Light-Cured Polymers . . . . . . . . . . . . .... . 131 6.2.3. Resins. . . . . . . . . . . . . . . . . . . . . . . . .... . 136
5.6.3. Ormocer-Based Filling Materials . . . . .... . 131 6.2.4. Thermoplastic Impression Materials . . .... . 136
5.6.4. Sealant Resins . . . . . . . . . . . . . . . . . . .... . 131 7. Dental Waxes. . . . . . . . . . . . . . . . . . .... . 137
5.6.5. Resin – Tooth Bonding . . . . . . . . . . . .... . 131 8. Other Model and Die Materials . . . . .... . 138
5.6.6. Toxicology . . . . . . . . . . . . . . . . . . . . .... . 132 9. Dental Gypsum Products . . . . . . . . . .... . 138
5.7. Standards. . . . . . . . . . . . . . . . . . . . . .... . 132 10. Dental Investments . . . . . . . . . . . . . .... . 142
6. Impression Materials . . . . . . . . . . . .... . 132 References . . . . . . . . . . . . . . . . . . . . .... . 144
6.1. Elastic Materials . . . . . . . . . . . . . . . .... . 133

1. Introduction Some dental materials are primarily used for

Dental materials are used for the replacement of
destroyed or lost structures (hard tooth substance,
teeth, soft tissues of the mouth, tissues of the head)
and for the restoration of disturbed functions
(masticatory, phonetic, esthetic, physiognomic)
of the orofacial organ. They are involved in the
morphological, physiological, and psychological
reconstitution of the patient (curative effect). At
the same time they prevent structural decay and
functional failure (preventive effect). Their use
takes into account biological and technical as-
pects. This is documented by the large number of
international standards (ISO). There is a require-
ment for chemical biocompatibility (lack of tox-
icity, allergenicity, mutagenicity, cancerogeni-
city), functional biocompatibility (strength,
environmental resistance), and technical func-
tionality (handling, ergonomics, economy). Some
dental materials are incorporated permanently or
temporarily in the orofacial organ; legally, they
are similar to medicinal products. Other materials
are used for the production of tooth restorations
and do not come into contact with the patient’s
tissues. From the standpoint of industrial hygiene
they must be completely harmless to the user
(dentist, dental technician, dental assistant).
There are may uses for dental materials:
. Reconstruction of decayed tooth structure
(enamel, dentin) by fillings and crowns
. Replacement of missing teeth by partial or full
dentures
. Surgical prostheses and epitheses in orofacial
prosthetics
preventive purposes (sealants for developmental
pits and grooves in the biting surfaces of teeth and
athletic mouth guards to reduce forces applied to
teeth during contact sports).
According to their handling dental material
can be grouped in the following way:
. Direct restorative materials, which are pro-
cessed in the mouth
. Indirect restorative materials, which are fabri-
cated outside the mouth
1.1. Direct Materials
Pure Gold. Gold foil can be formed into
solid gold of nearly theoretical density by me-
chanically condensing it directly into a retentive
cavity preparation. By means of small-diameter
condenser tips, the gold is work-hardened to have
properties comparable to a 90 % gold – 10 %
copper cast alloy. Electrolytically produced pow-
dered gold containing 0.5 % calcium may be
substituted for gold foil. These restorations have
low mechanical properties and are restricted to
small non-stress-bearing applications in posteri-
or teeth because of aesthetics.
Silver Amalgam. Silver amalgam is sup-
plied as a powder consisting mainly of silver,
with a balancing amount of tin, copper, and
minor elements. These amalgams are classified
as low-copper (< 6 %) and high-copper (13 –
30 %) types. The powder is mixed with mercury
to form a plastic mass which is condensed into a
retentive cavity preparation. The surface is
Vol. 11
carved shortly after placement; depending on the
product, the surface may be finished and polished
immediately or at a second appointment. Amal-
gam is used in posterior teeth because of its gray
appearance and is successful in stress-bearing
restorations. In badly decayed teeth, amalgam
may be retained by threaded metallic pins placed
into dentin, which extend into the amalgam. It
can be used to build up the crown of a tooth (a
core) on which a cast restoration is placed.
Polymers and Composites. Difunctional
oligomers and monomers, usually mixed with
fillers, are used to fill developmental pits and
fissures in the occlusal surfaces of enamel to
prevent caries. Before placement, the enamel is
etched with acid, rinsed, and dried. Etching
provides for mechanical retention of the sealant.
The sealants are formulated to be polymerized in
situ by a chemical-activated or light-activated
free-radical mechanism. The treatment is most
successful on the teeth of children soon after
eruption.
Anterior teeth with small to moderate frac-
tures or decay can be restored with composites.
They contain an inorganic filler of various parti-
cle sizes, as well as difunctional acrylate oligo-
mers and monomers. Composites are today only
rarely available as two pastes for the chemically
activated type and mostly as a single paste for the
light-activated type. After cavity preparation, an
adhesive is applied on enamel and dentin and
polymerized. The peripheral enamel is etched
with acid, rinsed, and dried. Equal volumes of the
chemically activated type are mixed, syringed or
packed into the preparation, and allowed to po-
lymerize. For the light-activated type, the paste is
placed into the cavity preparation and polymer-
ized by exposure to light. Setting occurs prompt-
ly, and final finishing to proper contour is done.
When the proper shade is used, the boundary
between the restoration and the tooth is difficult
to detect.
Cervical caries or eroded areas of teeth are
generally restored with glass ionomers. They
consist of a powder and a liquid (an acid-soluble
glass and an aqueous solution of polyacrylic
acids). The exposed dentin is cleaned, and an
adhesive is applied. Any peripheral enamel is
etched with acid. The components are spatulated
to a thick paste and packed into the prepared area.
Leached metal ions from the powder and the
Dental Materials 97
polymer acid react; a similar reaction may occur
between the calcium from the tooth and the
polymer acid to form an adhesive bond. Finishing
is delayed for 24 h because of the slow comple-
tion of the reaction. This method is most success-
ful for cervical restoration; its functions are to
restore the contour of the tooth, thus increasing
periodontal health, and to reduce the sensitivity
of the tooth.
Composites have been used in posterior teeth,
but the lack of wear resistance has restricted their
application to situations in which aesthetics is
essential. Composites with higher filler content
and wear resistance have been developed, and
restoration of posterior teeth with composites has
increased.
Agents are available to bond enamel and
dentin with composites. The bonding agents are
organic compounds with a variety of functional
groups. They are applied to the cavity preparation
before the composite, but the adhesive bond is
weak.
Composites are used as cores in severely
broken-down teeth and, in combination with the
acid-etch technique, as veneers on severely dis-
colored or deformed anterior teeth.
Cements. Cements are classed as luting ce-
ments (attaching a cast gold restoration to a tooth)
or base cements (support for an amalgam resto-
ration). Chemically, they are classified as (1) zinc
phosphate, (2) zinc oxide – eugenol and mod-
ifications, (3) zinc polyacrylate, (4) glass iono-
mer, or (5) resin and composite cements. The
applications of cements are listed in Table 1.
Zinc phosphate cement is supplied as a pow-
der (mainly ZnO) and a liquid (mainly H3PO4 in
water). The ratio of powder to liquid is higher for
a base than for a luting cement. The acid – base
reaction is exothermic, and the cement is mixed
on a cool glass slab to control the temperature.
The mix is then placed on the restoration and
tooth, and the excess is forced out when the
restoration is seated. A base cement is stiffer
and is packed into the bottom of the cavity
preparation and contoured. It is acidic when
placed, and the pulp is protected with a varnish
on the dentin. Cements have low thermal con-
ductivity and high stiffness and strength; they
provide thermal insulation for the pulp and me-
chanical support for the restoration. Zinc phos-
phate cement can also serve as a temporary
98 Dental Materials Vol. 11

Table 1. Applications of cement types and liquids (aqueous solution of acrylic acid
Cement type Applications
copolymers). They are spatulated, and the ce-
menting consistency is used to retain cast metal
Zinc phosphate retention of restorations restorations. The cement sets promptly, but the
and orthodontic bands;
high-strength bases; chemical reaction is completed slowly and the
temporary restorations cement margin should be protected with varnish
Zinc oxide – eugenol temporary and permanent from saliva for a day.
retention of restorations; Resin cements are powders (acrylic polymers
low- and high-strength
bases; temporary restorations; and sometimes fillers) and liquids (acrylic mono-
root canal sealers; gingival mers), whereas composite cements are usually
surgical tissue pack two pastes containing diacrylate oligomers, dia-
Zinc polyacrylate retention of restorations crylate monomers, fillers, and polymerization
and orthodontic bands;
temporary restorations; initiator systems. They are used for the retention
high-strength bases of crowns and bridges. In combination with the
Glass ionomer retention of restorations etching of enamel, these cements are used to
Resin and composite retention of crowns, attach orthodontic brackets to teeth without
bridges, and orthodontic
brackets; retention of bands. The acrylic cements are better with plastic
acid-etched bridges brackets, whereas the resin composites are better
for metal brackets. The latter are also used to
attach bridges to acid-etched enamel and acid-
restoration while a permanent restoration is being etched base metals.
made.
Zinc oxide – eugenol (ZOE) cements have a Liners. When dental decay in dentin ex-
variety of applications (Table 1). Unmodified tends near or to the pulp, a liner is needed. If a
ZOE consists of a powder or paste (mainly ZnO) thin layer of sound dentin exists, a paste – paste
and a liquid or second paste (mainly eugenol). No zinc oxide – eugenol liner is used as an obtun-
significant heat is produced during the mixing or dent and to protect the pulp. If decay extends to
the formation of the chelate, zinc eugenolate. the pulp, a calcium hydroxide liner is needed to
Unmodified ZOE has low strength and is used in stimulate the deposition of reparative dentin in
a thin layer as a liner, as a root canal sealer (to fill the area of exposure. The calcium hydroxide
a root when the pulp has been extirpated), or as a materials are usually supplied as two pastes
surgical pack for areas around the teeth where which are mixed together and set by the reaction
gingival tissue has been removed for periodontal of a disalicylate and calcium. Liners are used in
reasons. The cement has an obtundent effect on thin layers, have very low strengths, and have
the pulp. therapeutic value. High-strength bases are placed
Polymers added to ZOE improve its strength on top of them to give mechanical support.
and allow it to be used for temporary restorations
or for the temporary retention of crowns and Varnish. Dilute solutions of natural or syn-
bridges. When 2-ethoxybenzoic acid is substitut- thetic polymers in organic solvents are used as
ed for part of the eugenol and alumina is added, a varnishes. They form a thin plastic film over
high-strength cement results that can be used for freshly cut dentin and reduce the diffusion of
permanent cementation. material components into the tubules to the pulp.
Zinc polyacrylate cements are usually pow-
ders (mainly ZnO) and liquids (mainly aqueous
solutions of copolymers of acrylic acid). They are 1.2. Indirect Materials
spatulated, with thin mixes used to retain restora-
tions or orthodontic bands, and thick mixes used Cast Restorations. Alloy classes are gold –
as bases. Although the mixes are acidic, they copper, palladium – silver, nickel – chromium,
have a much smaller effect on the pulp than cobalt – chromium, and cobalt – chromium –
phosphoric acid. nickel. They are fabricated by the lost-wax meth-
Glass ionomer cements are powders (acid- od: a wax or plastic pattern of the restoration is
soluble glass containing high levels of fluorine) placed in a refractory investment (see Section
Vol. 11
Auxiliary Materials). After the investment has
hardened, it is heated to remove the wax and to
expand the mold. Molten alloy is forced into the
space occupied by the pattern, usually by cen-
trifugal force. The investment and metal are then
cooled, and the restoration is finished.
Gold casting alloys are of types 1 to 4 with
increasing copper and other non-noble metal
content. Type 1 is soft and used for non-stress-
bearing restorations; type 2 is stronger and used
for simple posterior stress-bearing restorations;
type 3 is still harder and stronger, and is used for
complex posterior crown and bridge restorations;
and type 4, the strongest, can be used in remov-
able partial dentures. Types 3 and 4 contain
enough copper for their as-cast hardness to be
increased by heat treatment.
The price of gold has increased the use of
palladium – silver, cobalt – chromium, and
nickel – chromium alloys for crowns and
bridges. They are generally harder and stronger
than type 3 gold alloys. They have higher melting
points than gold alloys and must be cast in high-
temperature investments.
Removable partial denture frameworks are
almost always cast from nickel – chromium,
cobalt – chromium or cobalt – chromium –
nickel alloys because of their lower cost and
higher stiffness (about twice that of gold alloys).
Partial denture frameworks are so large that free-
standing patterns distort during investing. Pat-
terns are formed on refractory investment models
of the upper or lower teeth. The pattern and the
model are then invested to produce the mold used
in the casting process. Plastic base and artificial
teeth (Section Auxiliary Materials) are attached
to the framework to produce the denture. These
alloys have higher melting points and hardness,
and lower density, than gold alloys and are more
difficult to finish.
Wrought Metals. Wrought wires of 18 – 8
stainless steel, cobalt – chromium – nickel,
nickel – titanium, and titanium – molybdenum
are used in orthodontics in biomechanical de-
vices to move teeth by the application of forces.
After treatment, these appliances are removed.
The stiffness of 18 – 8 stainless steel and co-
balt – chromium – nickel is the highest, fol-
lowed by titanium – molybdenum and then
nickel – titanium. Fabrication of the appliances
often involves soldering or spot-welding, which
Dental Materials 99
must be done carefully so that minimal damage to
the wrought metal occurs.
Stainless steel is also employed in the manu-
facture of small tapered files and reamers used to
clean out the root canals of infected teeth during
endodontic treatment.
Preformed wrought shell crowns of stainless
steel, nickel – chromium, or tin- and aluminum-
based alloys are used for semipermanent and
temporary restoration of children’s primary
teeth. They are supplied in a multitude of sizes
for different teeth. The best size is selected,
trimmed, and adapted to the correct shape. It is
then cemented with a permanent or temporary
cement.
Feldspathic, aluminous, and crystallizable
glass ceramics are used for the preparation of
full anterior crowns. In the first two, the crowns
are built up on a die of the prepared tooth covered
with platinum foil. Ceramic powder is mixed
with water, and the slurry is painted on the
matrix. Water is removed by vibration, blotting,
baking, and firing. The crown is built up initially
with more opaque ceramics; then more translu-
cent ceramics are used toward the surface. Char-
acterization results in a restoration that matches
the appearance of natural teeth. Aluminous cera-
mics have alumina added to the feldspar to im-
prove resistance to fracture.
Ceramic crowns are retained with a dental
cement. Because they are brittle and lack high
strength, ceramic crowns are used mainly on
anterior teeth where appearance is primary.
Ceramics are used to manufacture artificial
teeth for dentures. These teeth are held in position
by acrylic polymers and by mechanical retention
of pins in anterior, and diatoric holes in posterior,
teeth. The teeth are available in a variety of
shades, sizes, types, and shapes.
Ceramics and Metal – Ceramic Combi-
nations. A thin metal coping is cast to fit the
tooth. Special ceramics that bond to the metal are
applied to the outside surface. The completed
crown has a strong metallic substructure covered
with an aesthetic outer layer. These combinations
have superior strength compared to ceramic re-
storations and can be used for posterior as well as
anterior crowns and bridges.
Metals that have been used are gold-, nickel-,
and palladium-based alloys. Feldspathic cera-
mics with matching thermal expansion properties
100 Dental Materials
are essential. They are also retained in the mouth
with dental cements.
Full ceramic crowns and small bridges can be
made using press ceramics. In this process a
ceramic pellet is heated to a soft stage and pressed
into a form inside of an investment material
similar to casting a metal crown. The material
is a glass ceramic reinforced by leucite crystals.
Another way to produce full ceramic crowns
and small bridges is to use aluminum oxide or an
aluminum oxide/zirconium oxide ceramic to
build up the crown on a refractory die, loosely
sinter it so that it does not shrink, and infiltrate it
with a glass. For a more toothlike appearance it
must be veneered with a veneering ceramic like a
metal framework.
CAD/CAM techniques can also be used to
prepare full ceramic restorations. When this
technique is used to prepare frameworks from
aluminum oxide or yttrium-stabilized zirconium
oxide, even wide-span bridges can be made out of
full ceramic. The framework must be veneered
with a veneering ceramic which has a thermal
expansion coefficient that fits to the framework.
Since milling of a framework out of densely
sintered zirconium oxide ceramic is time-
consuming a computer technique is used to pre-
calculate sinter shrinkage and produce an en-
larged framework out of presintered material.
The enlarged framework is then dense sintered
to a fitting framework.
Ceramics are today only rarely used to manu-
facture artificial teeth for dentures. These teeth
are held in position by acrylic polymers and by
mechanical retention of pins in anterior, and
diatoric holes in posterior, teeth. The teeth are
available in a variety of shades, sizes, types, and
shapes.
Polymers. Acrylic polymers and copoly-
mers are used for partial and complete denture
bases, soft and hard denture liners, artificial
denture teeth, crown and bridge facings, and
temporary materials. They are usually processed
by a dough-molding technique, and free-radical
polymerization is initiated either by heat or by a
chemical. Shrinkage is controlled by mixing
three parts of polymer and one part of monomer
(usually methyl methacrylate) to form a dough.
The mixture is packed or pressed into a sectional
mold formed by the lost-wax technique. The
mold is formed by investing a denture where the
Vol. 11
artificial teeth are supported by a wax denture
base. Pressure is maintained on the mold until the
monomer has polymerized. The flask is then
removed from the appliance and the plastic base
is finished. A pour processing technique is some-
times used, in which a mixture of polymer and
monomer is poured into the sectional mold.
The tissue-bearing surface of a denture may be
made of a soft polymer such as plasticized acrylic
or a silicone rubber for patients who have special
problems wearing dentures.
The facial surfaces of anterior metallic crown
copings may be coated with tooth-colored ac-
rylics for aesthetic reasons. The polymer is mixed
or delivered as a paste with diacrylate monomers
having a low vapor pressure. They can be pro-
cessed in an oven or cured by light or microwaves
without investing because of the low volatility of
the monomers. Acrylic denture teeth are also
manufactured by means of dough molding. They
are available in a wide range of shades, types, and
geometries. They are softer and less wear resistant
than ceramic teeth but can be chemically bonded
to the acrylic denture base. Temporary restora-
tions are made directly in the mouth from
polymer – monomer mixes, with the aid of an
impression. They are then retained with a tempo-
rary cement until the permanent restoration is
made.
Athletic mouth protectors are made by form-
ing in a vacuum, a sheet (3 mm) of polyethyl-
ene – poly(vinyl acetate) copolymer over a mod-
el of the athlete’s upper teeth. After cooling, the
excess is cut away with scissors and the edges are
flame-polished. When worn, these protectors
nearly eliminate oral injuries in contact sports.
1.3. Auxiliary Materials
Impression Materials. Since diagnostic
and therapeutic measures in the oral cavity are
restricted, a working model must be created out-
side the mouth. This is done by physically trans-
ferring information from the patient to the dental
laboratory by a two-step inversion process:
1. Impression taking: a plastic material is
brought into contact with the object to be
reproduced and removed as an impression
(negative) after hardening by cooling or
chemical reaction
Vol. 11
2. Model production: the impression is filled
with a die material to give a model (positive)
The model must correspond to the shape and
dimensions of the morphological situation in the
mouth and, if necessary, give an instantaneous
picture of functional sequences. Impression and
die materials form an integrated whole. For the
application of the impression material to the
object to be reproduced, rigid impression trays
are necessary. They are available prefabricated
from metal or resin or custom made in the dental
laboratory from light-polymerizable filler-con-
taining polymers (composite materials).
Models and Dies. Models and dies are usu-
ally made from one of three types of gypsum
material and, less frequently, from plastics (usu-
ally epoxy) and metals (electroformed silver or
copper). Gypsum materials are compatible with
all impression materials, whereas epoxies are
compatible with some rubber impressions. Den-
tal compound and addition silicones are compat-
ible with copper forming, whereas most rubbers
are compatible with silver forming.
Plaster, stone, and improved stone gypsum
products are supplied as powders that are mixed
with water to a heavy slurry which is vibrated into
impressions. The strength, accuracy, and cost
increase from plaster to improved stone.
Epoxy materials are supplied as an epoxide
paste and a liquid amine catalyst. The fluid mix is
poured into the rubber impression. They set
slowly compared to gypsum materials.
Electroforming of rubber impressions is done
by painting the impression with finely divided
metal powder; this surface is then made the
cathode in an electroplating system. Pure copper
or silver is used as the anode, and electroforming
is carried out by using the appropriate electrolyte
and direct current (d.c.). Plating is continued until
more than 1 mm has been deposited; the remain-
ing space is then filled with acrylic plastic or
improved stone.
Pattern Materials. Patterns to be used in
the lost-wax technique are most often made from
wax and occasionally from acrylic plastics, sup-
plied as a powder and a liquid. Inlay, crown, and
bridge patterns are made from harder waxes
which are built up in increments on the model
or die. Accurate wax patterns are possible when
Dental Materials 101
the thermal expansion and stress relaxation prop-
erties of the wax are taken into consideration.
Denture bases are prepared from softer waxes,
which keep the artificial teeth in the correct
relationship before the base is invested and pro-
cessed in acrylic plastic.
Dental Casting. The lost-wax technique in
combination with centrifugal casting is the most
common way to make dental castings. The free-
standing wax pattern or the wax pattern on a
refractory investment model is invested in a ring
by using gypsum-, phosphate-, or silicate-bonded
investment. The latter two are used with high-
melting alloys. In addition to the binder, the
investment consists of silica materials. It is mixed
with water or special liquids and poured around
the pattern in the ring. After setting, the wax or
plastic pattern is burned out (480 – 980 ! C, de-
pending on the technique). The alloy is melted
and then cast into the mold. The shrinkage of the
wax pattern during mold formation and of the
alloy on cooling is compensated for by careful
control of the setting and thermal expansion of
the investment.
2. Metals
2.1. Introduction
Metals and alloys are widely used materials in
modern dentistry. In restorative dentistry metallic
materials are used for fillings for periodontal and
endodontic treatment; prosthetic dentistry uses
metals for crowns and bridges, partial dentures
and implant suprastructures; and for orthodontic
treatment, the elastic and shape-memory effects
of metals and alloys are utilized. Finally in dental
implantology, titanium metal is almost exclusive-
ly used for its osseointegration capabilities.
Depending on the specific application, the
required physical properties and processing
characteristics vary widely. For instance, an
amalgam filling material must first be a plastic
mass, which allows the dentist to pack it into the
dental cavity; it must then harden so that the
filling can be contoured with a sharp instrument
shortly after placement; finally, it must harden
rapidly, so the patient can chew an hour or two
after the filling has been placed. Root canal posts
and implants must be made of rigid, strong
102 Dental Materials
materials with a high elastic limit. They are
mostly prefabricated because of requirements
for precision, surface properties, and strength.
Other requirements for certain applications (in-
dications) may be a certain coefficient of ther-
mal expansion or melting range if the metal
framework is to be veneered with a tooth-col-
ored ceramic material.
General requirements for all dental materials
result from the requirements to be met by a
finished dental restoration in the oral cavity and
from interactions with the biological and chemi-
cal processes of the patient. The quality of the
restoration, which ultimately guarantees long-
term success in the mouth, is determined not
only by the material but also by the quality of
its dental and technical processing. These three
areas – medicine, processing technology, and
materials science – cannot be regarded indepen-
dently of each other.
The most important medical requirements on
dental alloys are:
. Corrosion and tarnish resistance in the mouth
. Biocompatibility
. Esthetics
No material should be introduced into the oral
cavity that can corrode under the sometimes-
aggressive conditions that prevail there, that is,
dissolve with the formation of considerable
amounts of metal ions. Tarnished layers, which
can develop by the reaction of metal ions with
constituents of the saliva, are also undesirable
because they lead to esthetically unsatisfactory
results.
The requirement for a good biocompatibility
of a material is closely related with the require-
ment for corrosion resistance. This means that
materials which come into contact with the body
of the processor or of the patient must not cause
any harm to health. When a new alloy is formu-
lated, a high corrosion resistance must be en-
sured, which in addition to the composition can
be improved further by a homogeneous, fine-
grain microstructure. An appropriate processing
procedure in the laboratory also plays an impor-
tant role here. However, since even highly cor-
rosion resistant alloys release minimal amounts
of ions into solution, elements that have a proven
high allergenic or toxic potential, such as Cd, Be,
Pb, and Ni, must not be used.
Vol. 11
2.2. Metallic Materials for Fillings
2.2.1. Pure Gold
In the past, the filling of tooth cavities by cold-
weldable pure gold was rather popular. Today
this technique is less important, because it is time
consuming and inconvenient to the patient.
Gold for fillings is available in different
shapes: gold foil of 1 mm thickness or rolled into
cylinders (Gold Cylinder, Williams Gold Ltd.);
electrolytically deposited mat gold in strips par-
tially wrapped in gold foil; and gold powder
encased in gold foil (Williams Gold Ltd.); par-
tially sintered chemically deposited gold powder
[12], [13]. One type contains a small addition of
calcium to improve work hardening (Electraloy
RV, Williams Gold Ltd.). The pieces must be
annealed and allowed to cool; they are then
inserted immediately into the cavity and con-
densed by malleting with hand instruments or
electric condensers [13]. Direct plastic gold fill-
ings are advisable only for small cavities on the
occlusal surfaces or near the neck of the tooth.
Larger fillings with two or more surfaces must be
made by the inlay casting technique.
2.2.2. Silver Amalgams
Amalgams are alloys of mercury with other
metals. Silver amalgams were introduced to den-
tistry at the beginning of the last century. The
dentist mixes an alloy powder with mercury to
obtain a plastic mass. This plastic amalgam is
then packed into the prepared tooth cavity. It
begins to harden after a few minutes; the surface
can be shaped by carving after 10 min or less; and
after 1 – 2 d, the amalgam is completely hard-
ened, and can be polished.
Properties. Today many different types of
alloys are available for amalgams. They consist
of finely divided Ag – Sn – Cu alloys, some-
times with small additions of zinc, mercury,
indium, or noble metals. They are distinguished
by the following criteria
Silver content: >65 % or 40 – 60 %
Copper content: 10 – 30 % or <6 %
Vol. 11
Grain size: <150 mm or <60 mm
Shape: cut filings or atomized spherical particles
Number of alloys: single alloy or particles from different alloys
Until around 1970, only alloys with high silver
content and low copper content were used. These
conventional alloys mainly consist of the inter-
metallic phase Ag3Sn (g), which reacts with
mercury to form two new intermetallic phases
(g 1 and g 2):
Ag3 SnðgÞþHg ! Ag3 Hg4 ðg 1 ÞþSn8 Hgðg 2 ÞþAg3 Sn
An excess of Ag3Sn remains in the hardened
amalgam; its g 2 phase is the weakest and most
prone to corrosion. Corrosion products are tin
oxides and tin oxide chlorides. The mercury from
the corroding g 2 phase diffuses back into the
amalgam and causes mercuroscopic expansion
[14] which damages the margins of the filling.
Since 1965, alloys with higher copper content
have been developed. Instead of Sn8Hg, the
mercury-free phase Cu6Sn5 (h0 ) is formed, which
is less prone to corrosion; it has the additional
advantage of making the matrix phase Ag3Hg4
more creep resistant.
The first amalgams that were free of the g 2
phase were the dispersion-type alloys, which
contain about 30 % of spheres (< 35 mm) of the
Ag – Cu eutectic (28 % Cu) in addition to the
conventional Ag3Sn filings [15]. The initial re-
action with mercury is similar to that of the
conventional alloys, which is followed by
Sn8 HgþAg=Cu ! Cu6 Sn5 þAg3 Hg4
This diffusion-controlled reaction takes place
within 1 – 7 d.
Atomized alloys consisting of Ag3Sn and
Cu3Sn with an extremely fine duplex structure
were later developed to eliminate the g 2 phase in
dental amalgams. The silver content is 40 –
60 %, and the copper content 13 – 29 % [16],
[17]. The reaction with mercury is:
Ag3 Sn=Cu3 SnþHg ! Ag3 Hg4 þCu6 Sn5
An excess of unchanged particles remains in
the completely hardened amalgam. The non-
gamma-2 amalgams with higher copper content
yield much more stable margins and brighter
Dental Materials 103
polished fillings than the conventional low-cop-
per amalgams.
Some of the cut alloys are preamalgamated to
accelerate the wetting and reaction with mercury.
For this purpose, the alloy powder is treated with
a mercury salt solution, which precipitates mer-
cury at the surface of the particles. Zinc is also
added as a deoxidizer; it slightly increases the
strength of the amalgam but, if contaminated
with moisture, has the disadvantage of producing
hydrogen, which causes delayed expansion or
blisters.
Production. Filings are produced by cutting
annealed ingots of alloy (10 – 20 kg) in a ma-
chine with a rotating milling cylinder and water
cooling. They are ground, sieved, annealed under
protective gas, etched with acid or preamalga-
mated (see above), rinsed, and dried (Fig. 1).
Spherical alloy particles are produced directly
from the melt by pouring it through a hole in the
bottom of the crucible and atomizing the melt
stream with high-pressure nitrogen. The atom-
ized droplets solidify while falling or are
quenched in water, forming small spheres or
irregular particles. The powder is sieved and
annealed in a reducing atmosphere or etched
with acid.
Cut filings or atomized particles are either
used as a single-alloy powder or mixed according
to different manufacturing prescriptions. By an-
nealing, the rate of reaction with mercury (setting
time, working time for the dentist) and the setting
Figure 1. Remission electron microscopy (REM) photo-
graph of Luxalloy-non-gamma 2
104 Dental Materials
expansion of the alloy can be influenced and
optimized.
Standards. Amalgams were the first dental
materials to be standardized. The following in-
ternational standards exist: ISO 24234 (Dentist-
ry – Mercury and Alloys for Dental Amalgam).
Handling. In earlier times, the alloy powder
and mercury were mixed in a glass mortar with
pestle. Today, electric mixing devices produce
the amalgam paste in 6 – 30 s. The recom-
mended ratio of mercury to alloy depends on the
type of particles. The range is 0.9 – 1.2:1, with
less mercury used for spherical powders and
more for filings. An excess is expressed by the
dentist during compression into the cavity. Ratio,
mixing frequency, and mixing time influence the
properties of the amalgam before and after hard-
ening. A low ratio causes a dry amalgam paste
and porosities in the filling. An extended mixing
time may change the setting expansion into a
contraction.
Toxicology and Occupational Health. The
mercury release from amalgam into water or
saliva was found to be very low: 2.4 – 3.8 mg/
cm2 during the first day from fresh amalgam and
0.1 – 0.3 mg/cm3 per day from completely hard-
ened amalgam. Tooth brushing twice a day in-
creases this amount to 0.5 – 0.8 mg/cm2 per day.
The daily uptake of mercury from normal food is
7 – 12 mg, and can be as high as 40 – 50 mg with
one meal of fish [18]. The daily dose from
amalgam fillings is below 10 mg [80].
Spilled mercury and amalgam waste can be a
source of mercury vapor and therefore hazardous
for the dentist and his staff. Spillage must be
avoided by using modern dispensing and mixing
devices, and by keeping wastes in closed boxes
under thiosulfate solution. By this means, the
mercury concentration in dental offices can be
kept below 10 mg/m3. The TLV and MAK of
mercury are 50 and 100 mg/m3, respectively.
In the mouth, a protective layer of saliva
suppresses the evaporation of mercury. The up-
take of mercury by breathing through the mouth
was found to be less than 0.1 mg/m3 for an
amalgam surface of 1 cm2 [19]. Contact between
amalgam fillings and gold restorations in the
mouth should be avoided, because the different
potentials of these materials can lead to the
Vol. 11
following disadvantages: elevated corrosion, dis-
coloration, and metallic taste. Allergic reactions
to mercury in amalgam fillings are observed only
in very rare cases.
2.2.3. Copper Amalgams
In former times, copper amalgams were used in
childrens’ temporary teeth. They were supplied
in the form of tablets with about 35 % copper and
65 % mercury. They had to be plasticized by
heating above 128 ! C, and they hardened on
cooling to form the phase Cu7Hg6 [20]. The
heating process is a dangerous source of mercury
vapor. The corrosion resistance of copper amal-
gams is poor.
2.2.4. Gallium Alloys
Gallium has a melting temperature of 30 ! C. A
eutectic alloy with indium and tin is liquid at
room temperature and can be used to form a paste
similar to the amalgam paste. When it is mixed
with an alloy similar in composition to an amal-
gam alloy with silver, copper and tin and in one
case 9 % palladium, it hardens in the same way.
Since the vapor pressure of liquid gallium at
mouth temperature is close to that of solid iron
at this temperature, evaporation of gallium is of
no concern.
The problem with this type of filling material
is that gallium is not as noble as mercury. This
means corrosion rates are higher than those for
amalgam. The alloy tends to undergo dark dis-
coloration in the mouth and the corrosion rate of
gallium from this type of alloy is two orders of
magnitude higher than that of mercury from
amalgam. Therefore biocompatibility of this type
of alloy is by no means better than that of
amalgam.
2.3. Metallic Materials for Prosthetic
Restorations
The wide span of qualities required in materials
for restorative devices has led to a variety of
metallic dental materials. Castings are used for
rebuilding partly damaged teeth (inlays, onlays,
Vol. 11
crowns) and for replacing missing teeth (bridges,
partial dentures). Cast fillings, crowns, and
bridges are permanently fixed to the tooth or
abutment with a dental cement; removable par-
tial dentures are usually held in position by clasps
or telescoping parts attached to the adjacent
teeth. Prefabricated precision attachments are
also used as interlocking devices for the revers-
ible fixation of partial dentures. Brazing is the
most commonly used technique when metallic
parts of a dental restoration must be joined, but
other techniques, such as laser welding, are
becoming increasingly popular.
To achieve a lifelike appearance of the artifi-
cial dentures, tooth-colored polymeric and ce-
ramic coatings (veneers) are applied to the metal
substructure. Depending on the veneering mate-
rial and the technique of application, the sub-
strate alloys must have very specific properties.
Since the ceramic veneer is fired onto the metallic
dental framework, alloys suitable for this
technique must fulfill specific requirements con-
cerning thermal expansion, melting range, and
bonding characteristics to the ceramic material.
Alloys for this porcelainfused-to-metal tech-
nique are usually referred to as PFM alloys or
simply porcelain alloys. Metallic dental restora-
tions are usually manufactured by a specific
dental casting technique. Other means of
manufacturing inlays, crowns, and bridges are
milling, sintering, or electroforming [81–83].
2.3.1. Precious Metal Casting Alloys
Due to their high corrosion resistance, precious
metals are well suited for use in the oral cavity,
where the metals come in contact with saliva,
which contains hydrogen ions Hþ (pH value of up
to 3) and oxygen.
A measure for the stability of a metal is its
electrochemical standard potential (relative to
the standard hydrogen electrode):
Al % 1.7 Co % 0.3
Ti % 1.6 Cu þ 0.4
Zn % 0.8 Hg þ 0.8
Cr % 07 Ag þ 0.8
Fe % 0.4 Pd þ 1.0
Ni % 0.3 Au þ 1.4
Dental Materials 105
Figure 2. Corrosion resistance of binary gold and palladium
alloys
The more positive the potential, the more
corrosion-resistant the element. Due to their very
high values, precious metals are not attacked by
hydrogen ions. As shown in Figure 2, the high
electrochemical potential of gold and palladium
is retained in binary alloys provided the Au or Pd
content exceeds 50 atom % in all phases of the
alloy.
Gold has a melting point of 1063 ! C and a
coefficient of thermal expansion of ca.
14.6 & 10%6 K%1 and therefore offers ideal
properties as a dental material. The warm yellow
color is highly esteemed due to its positive
influence on the esthetics in the oral cavity. The
platinum group metals all have a significantly
higher melting point, so that, with the exception
of palladium, none of these elements can be
considered as a base for dental alloys.
In comparison with gold, palladium has a
lower density and a lower price, so that material
costs for restorations with palladium-base alloys
are considerably lower. Palladium, however, is
white. Since the coefficient of thermal expansion
and melting point are outside the range required
for ceramic alloys, considerable amounts of al-
loying elements have to be used to meet the
requirement profile for PFM alloys.
Platinum is used as alloying element, espe-
cially in high-gold alloys, to increase the strength
and to raise the melting point. Ruthenium and
iridium are used as additives for grain refinement.
Tables 2 and 3 give an overview of the various
base systems used as dental alloys with their
main alloying elements. A differentiation is
made between alloys suitable for ceramic veneer-
ing (PFM alloys) and alloys mainly used for
106 Dental Materials Vol. 11

Table 2. Composition of typical precious metal dental alloys

Composition, wt %

Alloy Au Pt Pd Ag Cu Sn Zn In Ga Others

Gold-alloys for inlays, crowns, and bridges (not for ceramic veneering)
Degulor A 87.5 – 1.0 11.5 – – – – – Ir
Degulor C 74.0 2.4 2.0 13.5 7.0 – 1.0 – – Ir
Degulor M 70.0 4.4 2.0 13.5 8.8 – 1.2 – – Ir
Stabilor G 58.0 0.1 5.5 23.3 12.0 – 1.0 – – Ir
Stabilor NF IV 55.0 – 9.9 29.0 – 1.0 1.0 4.0 – Ir
Silver-alloys for inlays, crowns, and bridges (not for ceramic veneering)
Palliag M 2.0 – 27.4 58.5 10.5 – 1.5 – – Ir
Pallatop (Clasp) 12.0 – 20.0 51.0 15.6 – ? ? ? Re
Gold alloys for ceramic veneering
Degudent G 86.0 10.4 – – – – – 1.5 – Ta, Rh
BiOcclus 4 85.8 11.0 – – – – 0.5 1.7 – Ta, Rh
Degudent H 84.4 8.0 5.0 – – – – 2.5 – Ta
Degutan 80.2 4.0 13.5 – – 2.1 – – – Ir
Degudent U 77.3 9.8 8.9 1.2 0.3 0.5 – 1.5 – Ir, Re, Fe
Degunorm 73.8 9.0 – 9.2 4.4 – 2.0 1.5 – Ir
Gold-Palladium alloys for ceramic veneering
Deva 4 51.1 – 38.5 – – – – 9.0 1.2 Ir
Degubond 4 49.6 – 29.0 17.5 – 3.0 – – 0.5 Ta, Ir, Re
Palladium and alloys for ceramic veneering
Degupal G 4.5 – 77.3 7.2 – 4.0 – – 6.0 Ge, Ru
Bond-on 4 1.0 1.0 79.7 – 5.0 6.5 – – 6.0 Ru
Pors-on 4 – – 57.8 30.0 – 6.0 2.0 4.0 – Ru
Palliag LTG – – 36.9 56.0 – 3.0 4.0 – – Ir

Table 3. Physical properties of typical precious metal dental alloys

0.2 % proof stress, MPa

Alloy CTE*, 10%6 K%1 Melting range, ! C s h

Gold-alloys for inlays, crowns, and bridges (not for ceramic veneering)
Degulor A 1030 – 1080 80 –
Degulor C 900 – 975 330 350
Degulor M 900 – 970 400 620
Stabilor G 860 – 940 400 830
Stabilor NF IV 940 – 1065 310 555
Silver-alloys for inlays, crowns, and bridges (not for ceramic veneering)
Palliag M 950 – 1040 320 940
Pallatop (Clasp) 950 – 965 530 863
Gold alloys for ceramic veneering
Degudent G 14.7 1045 – 1140 420 470
BiOcclus 4 14.5 1040 – 1140 360 530
Degudent H 14.4 1100 – 1210 480 600
Degutan 14.0 1190 – 1280 545 635
Degudent U 14.0 1150 – 1260 470 580
Degunorm 16.8 900 – 990 340 500
Gold-Palladium alloys for ceramic veneering
Deva 4 13.8 1235 – 1315 425 545
Degubond 4 14.7 1160 – 1280 390 550
Palladium and alloys for ceramic veneering
Degupal G 14.3 1170 – 1295 585 585
Bond-on 4 14.0 1155 – 1290 575 575
Pors-on 4 15.2 1175 – 1275 340 650
Palliag LTG 16.5 1050 – 1130 330 510
*
Coefficient of thermal expansion
Vol. 11
Figure 3. Au – Ag – Cu ternary system
unveneered restorations or for veneering with
dental acrylics (C þ B alloys).
High-Gold Alloys. Alloys on the base of
Au – Ag – Cu have been used for the
manufacturing of dental restorations since the
introduction of the casting technique. The Au –
Ag – Cu ternary system is shown in Figure 3.
While a complete miscibility of the components
is possible in the Au – Cu and Au – Ag systems
over the entire range of concentration, the solu-
bility of silver in copper and of copper in silver is
only limited. With decreasing temperature, this
solubility gap increasingly extends in the direc-
tion of the gold corner. Alloys with a composition
in the range of the solubility gap can be hardened
by heat treatment [86]. During this process, pre-
cipitates that are rich in copper or silver are
formed and increase the hardness and strength
of the alloy. Figure 4 shows the structure of the
Degulor M alloy in the soft and hardened
condition.
By means of slight variations in the silver and
copper contents, the extent of precipitate and thus
the mechanical properties of these alloys can be
varied. Consequently, it is possible to design
optimum alloys for the various clinical indica-
tions. A further improvement of these alloys is
achieved by adding platinum and iridium. Due to
the grain-refining effect of these elements, den-
dritic solidification and thus an inhomogeneous
element concentration within the grain (segrega-
tion) can be avoided. The fine-grain microstruc-
ture also leads to an improved corrosion and
tarnish resistance; ductility and strength are in-
Dental Materials 107
Figure 4. Microstructure of Degulor M in the hardened and
soft states A) Hardened, soft þ 15 min/400 ! C/air; B) Soft,
15 min/750 ! C/Ar, H2O
creased. Table 2 lists the composition and Ta-
ble 3 the properties of Degulor alloys for various
indications, together with a selection of other
DeguDent alloys.
In the past high-gold alloys based on Au –
Ag – Cu could be veneered with resin materials
based on poly(methyl methacrylate) (PMMA) to
give the restoration a tooth-colored appearance.
Esthetically higher grade restorations, however,
could only be obtained by veneering with ceram-
ic materials that are fused to the alloy at ca.
980 ! C. Since the solidus temperature of the
alloys based on Au – Ag – Cu lies below this
temperature, these alloys could not be used for
this purpose. Newly developed low-fusing (hy-
drothermal) ceramic materials allow for ceramic
veneering of this type of alloys.
Since the difference between the firing tem-
perature of the ceramic and the solidus tempera-
ture of the alloy should be at least 100 ! C, the
solidus temperature of such an alloy must be
raised above the melting point of gold (1063 ! C).
Therefore, platinum and palladium are used as
alloying elements (Fig. 5). However, the addi-
tion is limited by the requirement for a maximum
liquidus temperature of 1300 ! C.
Palladium as an alloying element can be used
very effectively to raise the melting range
108 Dental Materials
Figure 5. Ternary Au – Pt – Pd phase diagram with iso-
therms of the solubility gap and some liquidus temperatures
because, in contrast to platinum, it widens the
melting range considerably less. A very wide
melting range increases the tendency to develop
segregations during solidification of the alloy.
However, because of the unlimited miscibility of
Au and Pd only a solid-solution hardening is
possible that does not result in an adequate
strength of these alloys. Moreover, palladium
adversely affects the gold color. In contrast,
platinum permits precipitate hardening at Pt
contents exceeding about 6 wt % (Fig. 5) [87].
Therefore, palladium, which raises the melting
range, and platinum, which increases the melting
range and hardenability, are usually added to
high-gold PFM alloys. Moreover, since alloys
with high strength are required, especially for
Vol. 11
long-span bridges, nonprecious metals such as
copper, tin, indium, iron, etc. are added to these
alloys in concentrations up to 2 wt %. Since in
systems with such complex structures and prop-
erties a theoretical description with phase dia-
grams is not possible, the development of dental
alloys usually requires considerable experimen-
tation with different alloy formulations. Results
of such development efforts are often reflected in
patents [88–90].
Alloying elements such as tin, indium, iron,
etc., efficiently harden high-gold PFM alloys but
they also lower the melting range. For compen-
sation, palladium is added. Due to the decoloriz-
ing effect of palladium, gold-base high-strength
ceramic alloys are therefore nearly white. Ta-
ble 3 lists the properties of high-gold Degudent
alloys. Aside from increasing the strength, the
nonprecious metals are significant for a good
bond between alloy and veneering ceramics.
During oxidation and veneering, these additives
are oxidized near and at the surface and support
the wetting of the alloy by the glass phase of the
dental ceramics [91].
The development of new low-fusing dental
ceramic materials such as Duceragold (firing
temperature ca. 740 – 780! C) made it possible
for the first time to develop a golden-yellow,
high-strength alloy (Degunorm) which is suitable
even for large-span bridges and partial dentures.
Degunorm and Duceragold have been marketed
as the Golden Gate System since 1993. The alloy
is mainly derived from Degulor M, which has
been known since the mid-1950s. By lowering
the Cu content to 4.4 % and removing the Pd the
veneering characteristics and color were opti-
mized (see Tables 2 and 3).
Gold-Reduced Alloys. With the sharp in-
crease of the gold price in 1982, high-gold alloys
became increasingly unaffordable for many pa-
tients and for health insurance systems, leading to
an increased consumption and development of
alloys with a reduced gold content. The Au –
Ag – Cu alloy base is similar to that of high-gold
alloys but the gold content is reduced to ca. 60 %
and the silver content is increased by more than
20 %. The palladium content is ca. 5 %. Due to
the low atomic weight of palladium compared
with gold, it can replace almost twice the amount
of gold and platinum in these alloys, so that the
corrosion resistance is also ensured. Due to their
Vol. 11
Pd and lower gold content these alloys no longer
display the intensive yellow color of the Degulor
group alloys. Typical examples are the Stabilor
alloys (Tables 2 and 3).
Improper handling of these alloys can lead to
porosities on the surface of dental castings. These
porosities can lead to the formation of so-called
aeration elements. Due to the different oxygen
contents on the surface of the alloy and inside the
shrinkage cavities, a difference in the electro-
chemical potential results between the two areas.
In copper-containing alloys, copper ions go into
solution inside the pore, migrate out of the pore,
and react with anions in the saliva to form a
dark discoloration around the shrinkage cavity
(tarnish).
This potential problem provided the impetus
for the development of copper-free, gold-base
alloys, based on the ternary system Au – Ag –
Pd. In contrast to the Au – Ag – Cu system,
however, all binary systems and the ternary
system have no miscibility gaps. Precipitate
hardening is therefore not possible.
The ternary system Au – Pd – In has a solu-
bility gap like the binary-edge systems Au – In
and Pd – In. It should therefore be possible to
achieve an increase in strength by alloying an
adequate amount of indium to the Au – Pd – Ag
base. The range of the solid solution of In in this
ternary basis is the narrowest at medium gold
contents, so that only little indium has to be
alloyed to obtain precipitate hardening.
The C & B alloys are not suitable for ceramic
veneering. Since there was also a demand for
economical alloys for ceramic veneering, it was
necessary to reduce the platinum content in
addition to the gold content. Therefore, Au – Pd
was chosen as the base system. To achieve a
noticeable cost reduction, the gold content was
reduced to 50 – 60 % and the palladium content
was raised to 35 – 40 %. Due to the strong
decolorizing effect of palladium all these alloys
are white.
The high proportion of palladium results in a
considerable rise of the melting range to values
far above 1400 ! C. To lower the melting range,
elements such as indium, zinc, tin and to a slight
extent also gallium have to be alloyed to consid-
erably lower the melting range. At the same time
the severe lattice distortions introduced by these
alloying elements cause strong solid-solution
hardening. A typical product is Deva 4 (Tables 2
Dental Materials 109
and 3). The high precious metal content of this
alloy (ca. 90 wt %) ensures good corrosion resis-
tance in the mouth. The higher content of non-
precious elements in comparison with high-gold
alloys, however, can make these alloys more
sensitive to processing errors.
Palladium Alloys. Attempts to develop
low-gold (or even gold-free) precious metal den-
tal alloys date back to the 1930s, where following
the depression Ag – Pd alloys were introduced
as dental casting alloys. When manufactured
properly, dental restorations made from these
alloys show reasonable clinical behavior, but a
slight darkening may occur over time as a result
of the high silver content of these alloys and the
tendency of silver to tarnish if it comes into
contact with sulfur. Silver-base alloys that con-
tain up to 5 % gold are still widely used, e.g.,
Palliag M (see Tables 2 and 3).
In the field of PFM alloys the development of
low-gold Pd alloys dates back to the early 1970s,
when Pd – Ag alloys were first introduced for
veneering with dental ceramics. However, due to
the tendency of Ag-containing alloys to frequent-
ly cause greenish discolorations in the dental
ceramic materials available at that time, a higher
acceptance of Pd alloys for ceramic veneering
came only when first Ag-free versions were
developed in the late 1970s as a response to
soaring gold prices and with the introduction of
nongreening ceramic in the early 1980s (e.g.,
Duceram).
To obtain Pd-base alloys suitable for dental
ceramic veneering materials and for melting and
casting with standard laboratory equipment the
melting range of palladium has to be lowered by
at least 250 ! C, while the coefficient of thermal
expansion has to be increased to a minimum of
14.0 & 10%6 K%1. For this purpose, low-melting
metals are used for alloying. The element with
the strongest influence in lowering the melting
temperature is gallium (Fig. 6). Tin, copper, and
cobalt also lower the melting temperature signif-
icantly, whereas indium and silver have only a
minor effect. Silver, copper and cobalt are
completely soluble in palladium, whereas galli-
um, tin, and indium have solubility limits in
palladium of 10, 17, and 18 wt %, respectively,
at 700 ! C [92].
In contrast to high-gold alloys, in which a
finely dispersed second phase with a high content
110 Dental Materials
Figure 6. Influence of various metals on the liquidus tem-
perature of binary Pd alloys
of precious metal is required to increase the
strength, second phases are undesired in palladi-
um-base alloys. To obtain a single-phase alloy,
the amount of gallium and copper have to be
reduced distinctly (Fig. 7). The ternary phase
diagram shows that with decreasing copper con-
tent the area of the solid solution crystal also
becomes wider, but even outside the two-phase
region the formation of a second phase is possible
as a result of additional alloying elements. A
further reduction in the risk of undesired segre-
gation and the formation of second phases can be
achieved by grain refinement.
Palladium and silver, similar to palladium and
copper, are completely miscible. Silver, howev-
er, can be alloyed to a high degree since it does
Figure 7. Ternary phase diagram Pd – Cu – Ga
Vol. 11
not lead to any formation of oxide during the
firing of veneering ceramics. Typical Pd – Ag
alloys contain ca. 30 wt % silver. As additional
alloying elements, tin, indium, and zinc are
preferably used to provide the required mechani-
cal characteristics and CTE values by solid-so-
lution and precipitate hardening. They also lower
the melting range.
At 1000 ! C silver has a vapor pressure of ca.
100 mbar. During the firing of ceramic materials,
which is performed under vacuum (about
50 mbar), silver evaporates from the surface of
the alloy and is partly deposited on the surface of
the ceramic, often resulting in a greenish discol-
oration. New types of ceramics which are insen-
sitive to discoloration by silver have been devel-
oped (e.g., Duceram).
2.3.2. Nonprecious Metal Casting Alloys
Nickel-Base Alloys. Although Co – Cr and
Ni – Cr alloys with adequate tarnish and corro-
sion resistance have been available since about
1930, noble-metal alloys are still the materials of
choice for cast inlays, crowns, and bridges. Ef-
forts to fuse dental ceramics to nonprecious
alloys were first successful only around 1970,
when Ni – Cr alloys were used that are similar to
creep- and sag-resistant superalloys for high-
temperature applications such as furnaces and
turbines. Chromium forms a passive layer on
these alloys, which prevents further corrosion.
The basic composition is usually 80 % nickel and
20 % chromium. Specific additives (e.g., Mo,
Nb, Ta, and Al) are necessary to obtain the
desired properties and control carbide formation.
Manganese provides sulfidation resistance,
while boron and silicon lower the melting range,
and beryllium improves castability as well as the
alloy – ceramic bond.
Advantages of CFM alloys based on the Ni –
Cr system are the low density, lower thermal
conductivity, the high yield strength, and the
modulus of elasticity, which is almost twice that
of precious metal alloys. However, the handling
of these tough alloys is not as easy as that of
precious metal alloys, and high-temperature lab-
oratory equipment is required for processing on a
consistently successful basis. The technical pro-
cedure is extremely sensitive, and technicians
must be specially trained. Common problems
Vol. 11
include miscasts, poor fit, porcelain fracture,
weak joints when brazed after ceramic firing,
and extended finishing time.
The biocompatibility of nickel alloys is an-
other point of concern. Nickel can cause allergic
dermatitis. Therefore, the use of nickel-contain-
ing alloys is contraindicated in nickel-sensitive
patients. Technicians must also be aware of this
potential risk. Moreover, nickel dust is consid-
ered a carcinogen. Cancer of the respiratory tract
has been particularly well documented in persons
who are occupationally exposed to nickel; there-
fore, precautions must be taken to avoid inhala-
tion of nickel dust during processing. Beryllium
is of concern mainly to the dental technician
because it may provoke beryllosis.
Cobalt-Base Alloys. Primarily because of
the hazards associated with nickel and beryllium,
alloys have been developed that do not contain
these elements. The Co – Cr – Mo casting al-
loys used for removable dentures (Section 2.3.3)
are not useful for the CFM technique, because
they are not scale resistant, their oxides react
unfavorably with the ceramic veneer, and their
thermal expansion does not match that of the
common brands of dental ceramics. Special al-
loys have been developed to overcome these
problems. Some Co – Cr alloys are on the mar-
ket, with tungsten instead of molybdenum as a
main constituent or with titanium partially repla-
cing chromium. The latter alloys are especially
prone to severe oxidation at elevated temperature
and must be melted and cast under vacuum.
Strength, melting range, and thermal expansion
of these Co – Cr CFM alloys are higher than
those of the Ni – Cr alloys. A completely modi-
fied processing technique is necessary to obtain
acceptable results [5], [6], [7].
Titanium and Titanium Alloys. Formerly,
titanium and titanium alloys were only used for
implants, but pure titanium has become increas-
ingly popular as casting alloy. Advantages of
titanium are biocompatibility, low density, and
low thermal conductivity. A disadvantage is that
titanium undergoes a phase transformation dur-
ing cooling from solidification temperature to
room temperature. The high-temperature
a-phase is stabilized by impurities, especially
oxygen. Contamination of the surface creates a
brittle surface layer called a-case. Since titanium
Dental Materials 111
is a very reactive metal it must be cast under an
atmosphere with a very low oxygen content, and
the investment material must be chemically more
stable than for other dental castings. The low
density is not only an advantage but also a
disadvantage, since higher casting forces are
required to obtain void-free castings. In this
context the low X-ray opacity of titanium is an
advantage because radiographs can be used to
determine whether the casting is free of voids.
Recently, ceramic materials for veneering
titanium have been introduced into the market
(e.g., Duceratin). Clinical observations have in-
dicated that titanium veneered with these dental
ceramic materials still has a higher risk of frac-
ture and failure of the metal – ceramic bond.
[81], [84]. However, acrylic resin veneers give
better results on titanium than on precious-metal
or other nonprecious-metal dental alloys [85].
2.3.3. Casting Alloys for Removable
Dentures
Removable partial dentures are commonly cast
of suitable alloys, whereas complete dentures
are now rarely made of metal; for orthodontic
appliances, wires made of stainless steel or
nickel – titanium alloys are generally used. The
removable partial denture, which is primarily
supported by the mucosa, is usually held in
position by clasps around the remaining natural
teeth. The clasps and the denture base are often
cast simultaneously as one piece of a single
alloy by using a specific investment casting
technique. Co – Cr alloys are mainly used for
this purpose (e.g., Biosil F; Tables 4 and 5).
Esthetically more pleasing devices to attach a
removable partial denture to natural teeth or to a
fixed partial denture are telescoping crowns or
industrially prefabricated attachments (see
Section 2.6).
2.4. Brazing Alloys
Brazing, commonly called soldering in the dental
profession, is the operation most extensively
used in dental laboratories for joining two pieces
of a metallic dental appliance together. Spot
welding is used occasionally, and laser welding
is becoming increasingly popular.
112 Dental Materials Vol. 11

Table 4. Composition of typical base metal dental alloys

Composition, wt %

Alloy Co Cr Ni Mo Mn Fe Nb W Si Others

Biosil F 64.8 28.5 – 5.3 0.5 – – – 0.5 C

Duceranium U 0.5 21.5 59.0 4.5 0.4 3.5 3.2 5.0 0.8 C, Cu
Duceralloy U 59.0 25.0 – – 0.3 2.0 2.0 10.0 0.8 C, V, Al
NPG 4.3 1.7 3.0 Cu, Al, Zn
Rexillium III 0.5 13.0 76.0 3.0 – – – – 1.0 Ti, Be, Ga
Remanium GM 800 63.5 30.0 – 5.0 0.2 – – – 1.0 C
Remanium 2000 61.5 25.0 – 7.0 – – – 5.0 1.5

Brazing alloys are used in the form of strips,
rods, or ingots. Brazing is frequently conducted
in electrical furnaces or by means of a gas –
oxygen torch between 750 and 1150 ! C. A
brazing flux dissolves or removes oxide and has
a positive effect in promoting rapid wetting and
spreading of the brazing filler metal. Because
brazing must be conducted at temperatures that
are 20 – 150! C above the liquidus temperature
of the filler metal without fusing the parent
metal, a suitable brazing alloy has to be chosen
for the particular combination of metals to be
joined.
Noble-Metal Alloys. Because brazed joints
must be corrosion resistant in the oral environ-
ment, noble-metal alloys are the filler materials
of choice. Brazing alloys based on the Au –
Ag – Cu system are called gold solders. They
usually contain 50 – 75 % gold, up to 10 % plat-
inum group metals, balance silver and copper,
plus up to 15 % zinc and, occasionally, minor
additions of indium or tin to lower the melting
range. These yellow-colored gold solders are
suitable for all joining purposes in the fabrication
of fixed restorations, except for joining prior to
firing the ceramic veneer. For this application,
high-melting Au – Ag alloys are used, which
contain 60 – 80 % gold and up to 10 % platinum
metals, but only trace amounts of base metals.
When the joint should not differ in color from
white parent alloys, Au – Pd – Ag brazing alloys
are available. Although they contain up to 45 %
copper, zinc, tin, and indium, some of these have
acceptable corrosion resistance if the noble metal
content is not less than 40 %. These white brazing
alloys are preferred in the fabrication of ortho-
dontic appliances, removable partial dentures,
and ceramic-veneered restorations made of
base-metal casting alloys.
Brazing alloys of Ag – Cu – Zn, sometimes
used for joints in removable appliances, cannot
be accepted for long-term use, because of their
low corrosion resistance. Furthermore, the braz-
ing operation itself reduces the passivation of
some base-metal parent alloys, which can result
in mechanical breakdown of the appliance be-
cause of corrosion of the joint.
Alloys of Au – Ni with about 80 % gold, are
used particularly for direct brazing of a clasp wire
to denture bases cast from Co – Cr alloy. Fusion
of a high-melting Au – Ni brazing alloy to one
part of a restoration made of a base-metal alloy,
prior to brazing it with a gold solder to another
part made of a noble-metal alloy [1], [3], [4], is
also common.

Table 5. Physical properties of typical precious metal dental alloys

0.2 % proof stress, MPa

Alloy CTE *, 10%6 K%1 Melting range, ! C s h

Biosil F 1320 – 1380 700

Duceranium U 14.5 1325 – 1328 325 335
Duceralloy U 14.4 1280 – 1330 550 550
NPG 1012 – 1068 210
Rexillium III 14.2 1232 – 1288 510 580
Remanium GM 800 1240 – 1410 710
Remanium 2000 13.8 1290 – 1415 600
Vol. 11
Base-Metal Alloys. So far the only base-
metal brazing alloys commonly used in joining
base-metal CFM alloys prior to firing the ceramic
veneer are Ni – Cr – Si – B alloys, e.g.,
BNi74CrFeSiB 980 – 1080 (ISO 3677 designa-
tion for nickel-based solder containing 14 % Cr,
4.54 % Fe, 4.5 % Si, 13 % B, and having a
working range of 980 – 1080 ! C).
2.5. Metallic Materials for Implants
Since the early 1970s alloplastic implants have
become increasingly important. They are used as
replacements for missing teeth and for retaining
full dentures. All implant materials must be
highly corrosion resistant in the oral cavity as
well as in the bone structure. They must also be
strong enough to withstand mastication forces.
Implants are either supported by the jaw bone
(subperiosteal implants) or fixed in the jaw bone
(endo-osseous and endodontic implants). Sub-
periosteal implants are fabricated, according to
an impression of the jaw bone, in a dental labo-
ratory by using the lost-wax method with a Co –
Cr – Mo casting alloy. Individually shaped im-
plant frameworks are obtained, which allow a
prosthesis to be fixed on the posts passing
through the gum. Nowadays this kind of implant
is not very popular anymore because of problems
with the fixation of the implant on the bone.
For endo-osseous and endodontic (transfixa-
tion) implants, prefabricated parts of various
alloys are available from the dental industry.
They are fixed in the jawbone. Titanium and
titanium-based alloys are most important be-
cause of their favorable chemical and physical
properties and their excellent biocompatibility
(e.g., Ti with 6 % Al and 4 % V, or Ti with 5 % Al
and 2.5 % Fe). Tantalum is also highly biocom-
patible, but because of its high density and poor
mechanical properties, it is not yet used as an
implant material on a wide basis. Wrought co-
balt-based alloys, such as Co – Cr – W – Ni and
Co – Ni – Cr – Mo, have also been used as im-
plant materials. Formerly, stainless steel with ca.
18 % Cr, 14 % Ni, and 3 % Mo was used as
implant material, but its corrosion resistance and
hence its biocompatibility are not as good as of
other alloys [8].
Good incorporation of implants into the jaw
bone requires a rough surface, while the surface
Dental Materials 113
of the transmucosal part has to be smooth.
Roughening of the surface is done by spray
coating of titanium with titanium or by sand-
blasting or etching. The difficulty in all-cases is
to keep the surface free from foreign material
which may reduce biocompatibility.
To enhance the healing process and to provide
a bioactive surface some implants are provided
with a surface layer of hydroxyapatite or similar
calcium phosphate compounds. The problem
with these layers is that the adherence to the
metal surface is too weak to withstand the shear
forces during the insertion process. Chipped-off
parts from the surface may create problems
during the healing process.
Implants are also available completely made
from ceramic material, mainly aluminum oxide,
or from carbon glass or carbon fiber. The disad-
vantage of the carbon implants is the black color,
which is visible through the gum.
A survey of materials approved in general
implant surgery is given in the ISO Standard
Series 5832.
Implant systems are most successful when
prefabricated endodontic and endo-osseous im-
plants are provided along with the corresponding
root canal and bone-cutting instruments,
respectively.
Because of the different techniques of placing
implants, various shapes of implants are avail-
able. Blades, screws, and hollow cylinders are
used mainly for endo-osseous implants [9], [10].
After a root resection, endodontic implants must
be inserted through the root canal into the jaw-
bone. The usual implant shapes are therefore
limited to needles, pins, and screws [11].
2.6. Metals and Alloys for other
Purposes
For other applications and operations in dentistry
besides casting and brazing, metals and alloys are
used in the form of either prefabricated parts or
semifinished materials.
Root Canal Posts. Because of the severely
corrosive conditions in crevices, highly corro-
sion-resistant materials must be used for root
canal posts which are inserted into the root of
a nonvital tooth as a retention for the artificial die.
114 Dental Materials
Some prefabricated root canal posts are made
solely of noble metals (e.g., 80 % Pt – 20 % Ir or
60 % Au – 20 % Pd – 20 % Pt), and others from
titanium or a titanium alloy with 6 % Al and 4 %
V. Stainless steel is not well suited for root canal
posts, even if the posts are gold plated, because of
its low corrosion resistance. Prefabricated posts
come in different shapes and dimensions for
different root sizes and purposes.
Precision Attachments. An important ap-
plication of noble-metal alloys is in prefabricated
precision attachments. Various anchors, hinges,
bar joints, etc., are available, which are based
largely on the male – female principle. They are
used to couple different parts of a prosthesis (e.g.,
a removable partial to a fixed partial denture) and
to achieve fastening and accurate location of the
prosthesis. The advantage of these attachments is
that the prosthesis or parts of it can be removed
for inspection and repair, for cleaning, and for
care of the adjacent oral tissue. Depending on the
construction, indication, and intended joining
technique (brazing, casting onto), precision at-
tachments are made of high-melting, nonoxidiz-
ing alloys (e.g., Pt with 20 % Ir or Au with 15 –
25 % Pt and 15 – 25 % Pd) or of high-strength
alloys based on the Au – Ag – PGM system or
the Ag – Pd – Cu system.
Platinum Foils. A particular application of
platinum foils (about 25 mm thick) is in the
fabrication of full ceramic crowns (jacket
crowns), in which a foil cap must conform to
the die onto which a particular alumina porcelain
is fired. After the firing operation, the platinum
foil is removed, leaving a gap for cementation.
An alternative to this full ceramic crown is the
platinum-foil-reinforced ceramic crown, in
which the cap made from the foil is conditioned
in such a way that the dental ceramics commonly
used for veneering cast metal substrates can be
fused to it, and the composite crown then cemen-
ted. Successful conditioning techniques are tin
plating and oxidizing, fusing of gold bonding
agents, or covering with a gold brazing alloy [1],
[3], [4].
Tools, Sheets, Bands, and Wires. Stainless
steel is the material from which not only instru-
ments and tools for dentistry are fabricated, but
Vol. 11
sheets, bands, wires, etc., for intraoral applica-
tion are made as well. Usually the 18 – 8 variety
of austenitic steel is employed, whose corrosion
resistance depends on proper processing, e.g.,
heat treatment or cold working. Occasionally,
Ni – Cr and Co – Cr alloys are also used.
Orthodontic Materials. Arch bars, springs,
and bands in orthodontic appliances are generally
made of stainless steel and are constructed and
joined by spot welding or, occasionally, by braz-
ing with silver solder. Both these joining tech-
niques can reduce corrosion resistance, but this is
acceptable because such appliances are used
temporarily. Nickel – titanium alloys have also
become popular for use in orthodontic appli-
ances. Stainless steel is also employed for pre-
fabricated screws and brackets in orthodontic
appliances; for matrix bands to support the filling
material packed into the tooth cavity; and for pins
to improve the retention of large amalgam or
resin restorations.
3. Dental Ceramic Materials [21–23]
3.1. Ceramic Teeth
As early as 1774, DUCHATEAUX
^ and CHEMANT
"
reported the use of ceramic powders for fabri-
cation of teeth. FONZI, in 1808, was the first to
fire platinum posts into teeth as anchoring ele-
ments. Ceramic teeth were manufactured in
1838 (ASH, England) and 1844 (S. S. WHITE,
United States). Since 1950, demand for ceramic
teeth has diminished continuously. Today, arti-
ficial teeth fabricated from resin materials are
preferred due to their lower price and easier
processibility.
3.1.1. Raw Materials
The formula for table china was the starting point
for the development of ceramic powders for
teeth; as a rule, this porcelain is composed of
50 % kaolin, 25 % feldspar, and 25 % quartz.
Teeth made from this material, while functional-
ly acceptable, were faulty aesthetically because
of their excessively white opaqueness. The high
content of kaolin is responsible for this white
Vol. 11
opacity because of the highly refractive, highly
dispersed mullite that forms from kaolin during
firing. For this reason, the proportion of kaolin in
the formula was greatly decreased or eliminated.
However, the mechanical properties of dental
porcelain suffered as a result.
The formulas for today’s dental porcelain
powders usually include more than 90 % of a
mixture of feldspar and quartz, the quartz com-
ponent being 15 – 25 % of the mix. For this
reason, the term ‘‘porcelain tooth’’ has been
replaced in the newer literature by ‘‘ceramic
tooth.’’
Feldspar. Feldspar is the most important
raw material, in ceramic powders. High demands
are made on its quality: it should be largely free of
foreign phases and low in iron content because of
the danger of discoloration. Norwegian and
Swedish feldspars are well suited because they
consist largely of orthoclase (K2O ' Al2O3 ' 6
SiO2), with the following typical composition
(mass fractions in percent):
SiO2 65.0
Al2O3 18.5
K2O 12.5
Na2O 2.5
CaO 0.2
Fe2O3 0.02
Quartz. The quartz used must have a similar
purity. Quartz decreases the melting range of the
feldspar – quartz mixture and provides sufficient
rigidity to the ceramic mass during firing by
increasing its viscosity. This assures that the
formed contours of the tooth are not lost during
firing. Furthermore, the quartz content affects
several important properties of the ceramic ma-
terial: flexural strength, thermal expansion, re-
sistance to thermal shock, and opacity. These
properties depend not only on the proportion of
quartz but, significantly, on how much of the
quartz passes into the glassy phase and how much
remains in the crystalline phase.
Occasionally, minor amounts of opacity-in-
ducing materials such as kaolin, mullite, or car-
borundum are added to the mixture. Addition of
flux powders, such as soda or calcite, can reduce
the melting temperature.
Dental Materials 115
3.1.2. Fabrication
The raw materials are crushed first in a jaw
crusher or chaser mill and then ground in ball
mills before being mixed in accordance with the
prescribed formula (maximum particle size
150 mm). To achieve better results, the mixtures
are customarily fritted first. For this step, the raw
materials are placed in fireclay containers and
fired between 1200 and 1400 ! C until the feld-
spar has melted completely and the quartz has
largely dissolved in the mass. The glass blocks
that result from this process are again crushed and
ground to a fine powder (maximum particle size
100 mm).
The starting material for tooth fabrication thus
prepared must now be given a color. A large
number of differently colored ceramic powders
are needed, because manufacturers offer approx-
imately 20 different shades of teeth. Further-
more, every tooth is built up of several differently
opaque and variously shaded layers. The natural
appearance required cannot be attained in any
other way. Shading is provided by the pigments
ordinarily used in ceramics, e.g., red-brown spi-
nels (Fe, Zn, Cr, Al oxides) and yellow vanadi-
um-containing ZrO2. Precise control of the color
values and the transparency of the powders are
prerequisite to achieve the desired tooth colors.
The fluorescence of natural teeth is imitated by
using special fluorescing pigments or by adding
lanthanide oxides to the starting frit. The colored
powders are converted to plastic masses by use of
appropriate organic additives, e.g., starch paste
or oils.
Shaping teeth requires much manual effort.
Two-part metal molds are generally used. The
labial layers of the tooth are placed in one-half
of the mold and the lingual layers in the other.
Posterior teeth are formed from occlusal and
basal halves. To permit retention of the com-
pleted teeth in the denture base material, pre-
cious-metal shells (largely palladium) are
mounted on the back of the anterior teeth.
After firing, gold-plated posts are soldered to
these shells. For posterior teeth, retention is
provided by dovetail-shaped undercuts in the
base region.
The filled halves of the form are pressed
together for joining. When they are heated to
150 – 200 ! C, the organic components lose
their plasticizing effect and serve as binders.
116 Dental Materials Vol. 11

The formed teeth are then placed on ceramic

firing plates and heated to 800 ! C to volatilize
the organic components. The tooth is finally
fired at 1200 – 1350 ! C for 8 – 30 min, de-
pending on the manufacturer. Today, the vacu-
um-firing technique, introduced in 1949 by
GATZKA,is used primarily. This produces teeth
essentially free of pores, which is beneficial in
terms of strength and polishability of the teeth
and – by increasing the transparency – particu-
larly desirable in terms of aesthetic effects. In
this procedure, the furnace is evacuated to ap-
proximately 1 kPa. When the tooth surfaces
have become sintered, firing is continued at
atmospheric pressure; firing is complete when
the tooth surfaces are smooth while the tooth
contours are still unchanged. After soldering of
the retentions and the required quality checks,
the teeth are collected in sets according to color
and shape (Fig. 8).

3.1.3. Quality Requirements

Quality requirements are defined in ISO Standard

22112 (Dentistry – Artificial teeth for dental
prostheses). Porosity, color matching with the
shade guide, and dimensional stability are par-
ticularly stressed. Additional requirements are
tissue compatibility of the material, and obser-
vance of laws and regulations relating to protec-
tion from radiation. As a result, uranium salts, Figure 8. Cross section of a ceramic tooth and embedding in
formerly added to achieve fluorescence, are no denture base a) Precious-metal shell; b) Soldered gold-coated
longer used. pin; c) Core material; d) Back material; e) Dentin material;
f) Translucent material; g) Enamel material; h) Solder

3.2. Dental Ceramic Fused to Metal
Restorative Materials
In the past, partial dental restorations such as
crowns and bridges were fabricated entirely of
precious metal. Today, standard practice in-
volves casting the framework in metal and ve-
neering this with a ceramic layer. After insertion,
such a prosthesis can hardly be distinguished
from natural teeth.
The first attempts of this sort were made in
1728 by FAUCHARD, who attempted to enamel a
gold denture base. However, only in 1962, was
WEINSTEIN, an American, able to develop frits
that achieved sufficient adhesion between metal
and ceramic [24]. The bonding material pro-
duced is related to enamel. The metal provides
sufficient tensile strength, while the ceramic,
glaze-like veneer affords great abrasion resis-
tance, good tissue compatibility, and an esthetic
appearance.
In the past, mechanical retention of the ce-
ramic layer on the rough metal surface was
thought to be a prerequisite for good adhesion
between the two components. Today, more sig-
nificance is attributed to adhesion through chem-
ical bonding between the materials. Bond forma-
tion generally is ascribed to the presence of easily
oxidized components, such as tin and indium, in
the alloy (see Chap. 2). Presumably, the metal
Vol. 11
oxide layer between the metal and the ceramic,
enriched through a so-called oxide firing step,
provides the chemical bridge between the com-
ponents [25].
3.2.1. Thermal Expansion
The durability of the bond between the metal and
the ceramic depends particularly on the thermal
expansion of the components [26]. If the differ-
ence in this parameter is too great, the ceramic
inevitably will split away from the metal during
cooling. Under optimal condition, the ceramic
shrinks a little less than the metal during cooling;
i.e., the ceramic has a smaller coefficient of
thermal expansion than the metal. It is then under
slight compressive strain, which avoids tensile
strain that is absorbed less well by the ceramic.
Ordinarily, metals have a higher coefficient of
thermal expansion than glasses; the values of
metals used for casting partial dentures are in
the range of 130 – 150 & 10%7 K%1 between 25
and 500 ! C. Glasses with sufficient chemical
resistance, however, have a significantly lower
coefficient of thermal expansion. The required
high coefficient is attained through the precipita-
tion of a finely divided, dendritic form of leucite
(K2O ' Al2O3 ' 4 SiO2) as a crystalline phase in
the glass during firing [27]. Leucite is trans-
formed from the tetragonal to the cubic form in
the range from room temperature to 620 ! C. This
transformation is accompanied by a 5 % increase
in volume and thus is associated with a high
coefficient of thermal expansion. A concentra-
tion of 20 – 30 % of leucite suffices to provide an
adequate coefficient of thermal expansion to the
ceramic. In theory, any frit that will precipitate
the required amount of leucite through appropri-
ate temperature handling suffices [28]. In prac-
tice, however, several frits of different composi-
tion are used, which permit better control of the
properties of the ceramic and a broadening of the
melting range; this simplifies subsequent firing of
the ceramic to the bridge framework.
3.2.2. Raw Materials
Orthoclase (potassium feldspar) is the most im-
portant raw material for a ceramic that is to be
Dental Materials 117
fused to metal. To make a frit that easily segre-
gates leucite, the potassium content must be
increased, e.g., by adding potassium carbonate,
K2CO3. Some manufacturers prefer to replace
natural feldspar with a mixture of other raw
materials, e.g., quartz flour, alumina, and potas-
sium carbonate. Furthermore, the addition of flux
powders, such as alkalis, alkaline earths, or boric
acid, is necessary to lower the fusion range. The
ceramic must be able to be applied at a tempera-
ture significantly below the softening tempera-
ture of the metal. Firing temperatures between
900 and 980 ! C are customary, but temperatures
as low as 750 ! C are becoming increasingly
common. The attainable decrease in the firing
temperature is limited by the increasing chemical
solubility of the ceramic.
3.2.3. Fabrication
The raw materials are first sintered into frits. The
composition of ceramic materials varies greatly
among manufacturers. This is caused, in part, by
the practice of mixing several different frits. The
main constituents of most of the relevant ceramic
materials are present in these following ranges
(mass fractions in percent):
SiO2 58 – 66
Al2O3 15 – 17
K2O 10 – 14
Na2O 5 – 8
Li2O 0 – 1
CaO 0 – 2
B2O3 0 – 3
A ceramic of this sort is made into ready-to-
use powders by adding opacifiers and pigments to
the frit, so that the final veneer corresponds in
color to the shade guides provided. Every veneer
requires three different powders: the opaque,
dentin, and enamel powders. The opaque ceramic
provides adhesion and simultaneously prevents
the metal from showing. To meet this function, it
contains up to 12 % of opacifiers such as TiO2,
SnO2, CeO2, ZrO2, or ZrSiO4. Dentin and enamel
powders make a toothlike appearance possible
through their coordinated shades and trans-
lucence.
118 Dental Materials
The dental technician mixes the ceramic
powders to a creamy mass using water or a
special modeling liquid. Each of the three ce-
ramic layers is applied and fired separately.
Appropriate distribution of grain size of the
ceramic powders assures sufficient contour sta-
bility and condensability of the ceramic pastes.
The grain size is in the range of 2 – 80 mm, with
a maximum between 20 and 30 mm. Each firing
lasts about 5 min. The vacuum-firing procedure,
described for tooth firing, has been widely
adopted. If the veneer must be ground later for
adjustment, glazing and refiring provide the
necessary shiny appearance. Unpigmented,
finely ground glass frits are used as glazes. They
contain sufficient flux and can be fired at lower
temperatures than those required for veneering.
Strongly pigmented glazes are used to provide
specific colors. For example, tooth necks can be
accentuated with color, and superficial anoma-
lies, such as enamel tears and white spots, can be
copied. Figure 9 shows a cross section of a
crown.
3.2.4. Quality Requirements
The requirements and testing procedures are
defined in the standard ISO 9693. Important
Figure 9. Cross section of a ceramic-fused-to-metal crown
a) Metal substructure (0.2 – 0.4 mm); b) Opaque layer
(0.2 mm); c) Dentin layer (0.6 mm); d) Enamel
Vol. 11
properties that must be checked constantly by
the manufacturer include thermal expansion,
adhesion to the metal, bending strength, firing
shrinkage, chemical durability, and transparency
and color of the fired ceramic materials.
3.2.5. Ceramic Fused to Titanium
Since about 1985, titanium has been used to a
small but increasing extent as a framework ma-
terial. Titanium has a lower thermal expansion
(92&10%7 K %1) than the traditional ‘‘ceramic
alloys’’. Therefore, the ceramic does not require
leucite to enhance its thermal expansion. The
firing temperature of the ceramic must be below
850 ! C, due to the high reactivity of titanium.
The veneer ceramic consists predominantly of a
leucite-free glass with an increased content of
alkali metal oxide and boric acid.
3.3. Dental Ceramics for Fixed
Restorations
3.3.1. Jacket Crowns
Long before the combination of metal and ce-
ramic was accepted, damaged teeth were re-
paired exclusively with ceramic materials. The
first success was achieved by H. LAND, who
introduced his jacket crowns in 1895 in the
United States. In Europe they became popular
only after 1918.
The following technique is used to fabricate a
jacket crown: A model is made of a die of the
prepared tooth. The model is covered with plati-
num foil; the foil serves as a base for the layers of
ceramic to be placed on it. The foil is removed
after the crown has been completed. As with
ceramic-fused-to-metal restorations, several
layers of ceramic, each with a specific transpar-
ency and shade, are fired. The core material is
covered with a dentin layer and then with an
enamel layer.
The demands made on the ceramic’s physical
properties are different from those required of
ceramic powders for application to metal. Be-
cause no metal base is present, the thermal
expansion of the ceramic does not have to be
increased, and the firing temperature does not
Vol. 11
have to be reduced below 1000 ! C. Nor need the
core material be extremely opaque. However, the
absence of a support for the crown, otherwise
provided by the metal framework, must be com-
pensated by increased strength, at least of the
core material. The flexural strength of this mate-
rial should be at least 100 MPa, whereas 50 MPa
is sufficient for the opaque material in the metal –
ceramic technique.
Jacket crowns were fabricated in the past
from ceramic powders quite similar to those
used for teeth. This required that they had to be
fired at temperatures no lower than 1250 ! C.
Today, ceramics are available which, through
the addition of boric acid and other fluxes, can
be fired at temperatures below 1100 ! C. The
necessary increase in bending strength of the
core material is achieved by adding as much as
50 % alumina, usually in the form of carborun-
dum [29]. Prerequisites to the increased flexur-
al strength elicited by the carborundum are
good binding with the surrounding glass matrix
and a controlled difference in thermal expan-
sion between the carborundum and the glass
phase.
Because of the better mechanical properties of
metal – ceramic crowns and because of their
more readily attainable exactness of fit, they have
largely replaced jacket crowns. But for patients
with allergic reactions to precious metals, jacket
crowns still find some use. Additionally, the lack
of the opaque metal layer allows for a more
natural appearance of the restoration.
3.3.2. Newer Developments
While the importance of traditional jacket
crowns approaches zero, extensive efforts have
been made to replace the metal frame by newly
developed high-strength ceramic. Suitable ce-
ramic materials, superior to the jacket crown
material regarding their strength are readily
available. Glass ceramics, for example, have
flexural strengths up to 300 MPa, and oxide
ceramics such as Al2O3 and ZrO2 even up to
1000 MPa. While some glass ceramics have a
tooth-like appearance, oxide ceramics can serve
only as core materials because of their opacity
and have to be veneered with more transparent
ceramics. There are no generally accepted re-
Dental Materials 119
quirements for the strength of ceramics for
dental restorations. The standard ISO 6872 re-
quires a minimum flexural strength of 100 MPa
for ceramic materials used for the fabrication of
the supporting structure of crowns, veneers,
inlays, and onlays. However, ceramics for
crowning posterior teeth are only acceptable if
they considerably exceed this minimum, and
materials for bridges are expected to have flex-
ural strengths above 300 MPa. Besides the di-
mensions of the restoration and the expected
masticatory pressure, the durability also de-
pends on the manner in which it is fixed to the
prepared tooth. The main problem lies in
manufacturing dental restorations from these
ceramic materials at an acceptable price. The
fact that each restoration has its individual
dimensions which must be observed exactly
exacerbates the problem.
There are several methods for shaping the
ceramic material.
Sintering of ceramic powder has the problem
that shrinkage during the sintering process means
that the shape before and after firing differ con-
siderably. In the case of metal – ceramic and
jacket crowns, the inner surface of the restora-
tion, which has to fit exactly to the prepared tooth,
is determined by the metal frame or the platinum
foil. During the firing process, the ceramic pow-
der shrinks towards the metallic base. The form,
which the dental technicians build up with the
ceramic powder slip, must be oversized to com-
pensate for the shrinkage.
Normally, glass ceramic is produced by cast-
ing of the glass melt into the desired form,
followed by a tempering process, in which the
glass partly crystallizes. Distribution, quantity,
and size of the crystals are responsible for the
quality and the properties of the material. But if
the glass ceramic is sintered together from fine
particles, it is hardly possible to achieve an
optimal crystallization process, and the result-
ing material is inferior. Thus, for the production
of glass ceramic restorations dense ingots are
used, which are cast or pressed in a prepared
form.
Dentsply introduced the first glass ceramic
dental system Dicor in 1984. It was developed
jointly with Corning Glass Works. Its basis is a
mica – glass ceramic [31]. The tooth crown was
cast of a special glass at 1370 ! C. A centrifugal
casting procedure similar to that used for casting
120 Dental Materials
metal denture restorations was used. In the sub-
sequent ceramic firing (14 h at 1070 ! C), approx-
imately 55 % of the glass crystallizes. The struc-
ture of the resulting translucent glass ceramic is
characterized by platelike, interlaced crystals of a
fluoride-containing mica with the formula
K2Mg5Si8O20F4. These crystals, approximately
1 mm in size, should lend strength to the material
and retard crazing. A colored glaze is fired onto
the structure to provide the desired shade [32].
The long–term success of this material was not
sufficient; therefore it has been withdrawn from
the market.
In 1990, Ivoclar introduced their Empress
system [33]. This is also a glass ceramic system,
but with some important differences compared to
Dicor. The ingots are not cast but pressed into the
form by a special hot-pressing device. For this
reason, they have to be heated up only to the
plastic state, and the reinforcing crystals present
in the ingots do not dissolve during the hot-
pressing process. This has the advantage that the
time-consuming subsequent ceramic firing is not
necessary. The crystal phase in Empress is leu-
cite, but in contrast to metal – ceramics the
crystallization process is optimized to give a
flexural strength of about 150 MPa. Similar to
Dicor, a colored glaze gives the desired shade.
Similar systems from other manufactures are
nowadays common.
Another way to overcome the problems asso-
ciated with the sintering shrinkage is represented
by In-Ceram, a product marketed by Vita Zahn-
fabrik since 1989 [34]. The model of the prepared
tooth is duplicated with a special gypsum. An
alumina powder slip is applied to this die and
fired. Firing has to be timed in such a way that the
alumina does not shrink and a porous, partially
sintered preform is created. This preform is
infiltrated with a glass melt in a second firing
step. The resulting dense core has a flexural
strength of more than 400 MPa. Therefore, this
material is useful not only for inlays and crowns,
but also for bridges. A toothlike appearance can
be achieved by veneering the core with a more
transparent ceramic.
In 1988, the first CAD/CAM system for
manufacturing dental restorations was offered
by Siemens. This CEREC-System was devel-
oped by M€ oRMANN and BRANDESTINI. It was suit-
able for the production of inlays only, but today,
systems are available for the production of
Vol. 11
crowns and even bridges [35]. All these systems
use industrially produced dense ceramic blocks
as starting materials, they are therefore not con-
fronted with the problem of shrinkage. The pro-
cess can be divided into three steps:
1. Three-dimensional scanning of the surface
of the prepared cavity or tooth stump by an
optical or mechanical device and transmis-
sion of the data to a computer. Scanning can
be performed either intra-orally or extra-
orally after manufacture of a model from an
impression. Instead of the cavity or the
stump, a preformed model of the desired
restoration can be used for the scanning
process.
2. Design of the restoration using the three-
dimensional computer model derived from
the scanning device. The operator can either
complete or change the restoration on the
screen. The outer form with the occlusal
surface can be designed with the assistance
of different tooth forms stored in the
computer’s database.
3. Fabrication of the restoration from the ceram-
ic block by a computer-controlled precision
milling machine.
Many types of ceramic are applicable for this
purpose, but ceramics with a glass-matrix are
preferred because of their toothlike appearance
and ease of grinding. The strength of these cera-
mics is sufficient for inlays and crowns, but for
bridges oxide-ceramics have to be chosen. Most
CAD/CAM systems can also be used for the
milling of metal preforms.
The CAD/CAM systems are expensive but
advantageous in that they allow the production
and insertion of restorations at the chairside
during a single visit.
CAD/CAM systems are also used to produce
frameworks for full ceramic bridges even for the
posterior region. Yttrium–stabilized zirconium
oxide ceramic is mainly used for this purpose.
Beside the main constituent zirconium oxide the
ceramic contains 5 % yttrium oxide and a small
amount of aluminum oxide. The main impurity is
hafnium oxide, which is contained in an amount
of approximately 2 %. The addition of yttrium
stabilizes the tetragonal high–temperature phase
of zirconium oxide down to room temperature.
Under the stress of a propagating crack the stable
Vol. 11 Dental Materials 121

monoclinic phase is produced, associated with . Neutralization reaction

expansion. The pressure from this expansion
stops further growth of the crack. This gives this
type of material its high strength and durability.
Originally, frameworks of zirconium oxide
ceramic were made from dense sintered material.
Because of the rigidity of the material the milling
process took a long time. Nowadays, mainly
presintered material is used. It has a chalklike
consistency and can be easily milled. To get a
fitting restoration the computer calculates an
oversized framework to be milled by taking into
account the firing shrinkage. After dense sinter-
ing of the material the framework is veneered
with a special veneering ceramic which is adjust-
ed to the low expansion coefficient of zirconium
oxide.
4. Cements
In dentistry the term ‘‘cement’’ is often used with
two different meanings. Dentists use ‘‘cement’’
for all luting materials for the fixation of crowns,
bridges, inlays, or onlay, even if the material is
resin-based. Chemically speaking, the term ‘‘ce-
ment’’ describes dental materials that contain
reactive fillers as one component of the setting
system. Only these materials are treated in this
chapter.
These cements can be classified according to
their type of setting reaction:
. Complex formation reaction
4.1. Cements Setting by Neutralization
Reaction
The development of amalgam, gold alloys, and
dental porcelain in the 1800s led to the search
for luting and more esthetic restorative materi-
als. Cements composed of calcium oxide and
phosphoric acid, magnesium oxide and solu-
tions of magnesium chloride (magnesium oxy-
chloride cement), or zinc oxide and zinc chlo-
ride solutions were developed. The first dental
cement with satisfactory properties and rela-
tively low pulp irritation was zinc phosphate
cement. The most important properties of ce-
ments setting by neutralization reaction are
listed in Table 6.
4.1.1. Zinc Phosphate Cements
Zinc phosphate cement (phosphate cement) was
introduced in 1879 [93]. The powder contains
zinc oxide and small amounts of magnesium
oxide. The liquid is an aqueous solution of
orthophosphoric acid (ca. 50 – 60 %) and alumi-
num phosphate. Both components may contain
minor amounts of additives to improve various
characteristics. During setting, the oxides are
neutralized by phosphoric acid. Set cements

Table 6. Properties of cements setting by neutralization reaction

Zinc
Zinc Silicate polycarboxylate Resin-modified Polyacid-modified
Property phosphatecements cements cements Glass ionomers glass ionomers composites

Strength low medium low high higher highest

Wear resistance low low low high medium high
Solubility medium high low very low low very low
Shrinkage no no no no low high
Swelling no no no no high high
Bond mechanical mechanical dynamic, dynamic, dynamic, with bonding
interlocking interlocking chemical bond chemical chemical bond systems
bond
Fluoride release addition of high addition of high high low
fluorides zfluorides
Pulp sensitivity medium high very low medium medium medium
Biocompatibility under discussion under discussion good very good under discussion under discussion
(H3PO4) (H3PO4) (residual (residual
monomers; monomers)
HEMA)
Translucency low medium low medium high high
Esthetics low medium low medium good very good
122 Dental Materials
consist of unchanged zinc oxide particles embed-
ded in an amorphous matrix of zinc phosphate
and zinc aluminophosphate [94]. Due to the
relatively low strength and the opaque appear-
ance, zinc phosphate cements are used exclusive-
ly as luting materials for restorations.
Trade Names: Fleck’s cement (Mizzy); Har-
vard Cement (Richter & Hoffmann).
4.1.2. Silicate Cements
Replacing the zinc oxide of zinc phosphate
cements by ion-leachable glasses gives the sili-
cate cements, first developed in 1902 [95].
Glasses are melted from silica, alumina, sodium
fluoride, cryolite, and calcium sources such as
calcium fluoride, calcium oxide, calcium car-
bonate, or calcium phosphate [94]. The liquid is
similar to that used with zinc phosphate ce-
ments. In the setting reaction, the glass is at-
tacked by acid, and metal ions are released and
precipitated as phosphates. Unconsumed glass
particles surrounded by silica gel are embedded
in the phosphate matrix. Due to the fluoride
content of the glass, silicate cements release
fluoride. Strength and esthetics are better than
those of zinc phosphate cements, but solubility
is higher [94]. Old silicate cements led to some
extent to pulp necrosis, an effect that was ex-
plained by the relatively high content of arsenic
impurities in their glasses. But even cements
with practically arsenic free glasses led to pulp
sensitivity [96]. Possibly the slow increase in pH
leading to a prolonged contact of the pulp with
an acidic environment can explain these findings
[94], [96]. The major use of silicate cements is in
anterior restorations.
Trade Name: Silicap (Vivadent).
4.1.3. Silicophosphate Cements
Silicophosphate cements (stone cements) are a
combination of zinc phosphate and silicate ce-
ments. The powder contains both zinc oxide and
ion-leachable glass. Their properties are in be-
tween those of zinc phosphate and silicate ce-
ments [94]. They are used as filling materials,
like silicate cements.
Trade Name: Drala Steinzement (Detax).
Vol. 11
4.1.4. Zinc Polycarboxylate Cements
Zinc polycarboxylate cements were developed
by D. C. SMITH in 1964 and became commer-
cially available in 1968 [93]. The phosphoric
acid of phosphate cements was replaced by an
aqueous solution of polyacrylic acid (20 –
60 %). Different additives to the powder
(e.g., fluorides) are used to improve cement
properties. Some products contain dried poly-
acrylic acid in the powder and are mixed only
with water. The major new feature of these
cements was their chemical adhesion to tooth
tissue [93]. This property can be explained by
the fact that the carboxylic groups of the poly-
acid react not only with the zinc ions released
from the powder (setting reaction), but also with
calcium ions of the tooth structure [94]. Zinc
polycarboxylate cements have relatively low
mechanical strength but are well tolerated by
the pulp. For that reason they are used mainly as
luting materials for metallic restorations and
base materials.
Trade Names: Durelon (ESPE); Poly F Plus
(Dentsply).
4.1.5. Glass Ionomers
History. A. D. Wilson investigated the use
of ion-leachable glasses with polyacrylic acid.
By increasing the basicity of the glasses, systems
with acceptable reactivity were obtained in 1969
[97]. That class of materials was named glass
ionomer (glass þ ionic polymer) or glass poly-
alkenoate. The first glass ionomer ASPA I (alu-
minum silicate polyacrylate) was used clinically
in 1970 by J. W. MCLEAN. Due to a short working
time and a very slow setting, the workability was
restricted [98].
Composition. All glass ionomers contain
three essential components: an ion-leachable
glass, a polycarboxylic acid, and water.
The first glasses were calcium aluminum
fluorosilicate glasses (with small amounts of
sodium and phosphorus), melted from the same
raw materials as the glasses for silicate ce-
ments. A typical composition (G 200) is: SiO2
30.1 %, Al2O3 19.9 %, AlF3 2.6 %, CaF2
34.5 %, NaF 3.7 %, AlPO4 10.0 % [2]. After
introduction of the sandwich technique (1985),
Vol. 11
in which dentin is replaced by glass ionomer,
and enamel by composite resins, the need for
radio-opaque glass ionomers became evident
[98]. Modern glasses for glass ionomers contain
heavy elements such as strontium, barium, or
lanthanum. For the reactivity of glasses the
content of aluminum and the formation of a
glass matrix containing Si–O–Al bonds is im-
portant [99].
For extended use in dentistry an adjusted
working and setting time is needed. Since these
requirements are only partially realizable with
the glass structure, the setting characteristic has
to be adjusted by different techniques. Tempera-
ture treatment of the glass powders prolongs the
working time [98], as does the reduction of
reactive ions on the particle surface by a pretreat-
ment with dilute acids [100]. Addition of tartaric
acid as chelating agent prolongs the working time
and accelerates the setting reaction [101]. Most
modern glass ionomers contain tartaric acid as a
setting modifier.
In the first glass ionomers, an aqueous solu-
tion of polyacrylic acid was used. Many com-
mercially available products still contain such
solutions, even though they tend to form gels at
lower temperatures. Copolymers of acrylic and
itaconic acid [98] or of acrylic and maleic acid
[102] are used to overcome this problem and to
increase reactivity. In some products the high
ratio of maleic acid in the copolymer leads to a
higher degree of cross-linking in the material,
resulting in high mechanical strength. The use
of polyvinylphosphonic acid [103]or copoly-
mers of acrylic and vinylphosphonic acid
[104] has also been reported. The polycar-
boxylic acids used in glass ionomer formula-
tions have a molecular mass in the range of
10 000 – 100 000 and are used in concentra-
tions of about 20 – 60 % (depending on the
different products). Depending on the indication
the powder : liquid ratio can vary in a wide
range of about 1.5 : 1 to 4 : 1. All glass ionomers
contain water, which is the reaction medium
and the only liquid component for paste
formation.
Setting Reaction. After the attack of the
polyacid on the glass, cross-linking of polycar-
boxylate with metal ions released by the glass
takes place. A calcium aluminum polycarbox-
ylate matrix is formed, in which glass particles
Dental Materials 123
covered by silica gel and water molecules are
embedded. As a result of ion hydration, the
content of evaporable water decreases with time
[105], while the cross-linking reaction still
slowly continues. Both effects lead to an in-
crease in mechanical strength and Young’s
modulus [106] and reduced wear [107] in the
course of time.
Further Developments. In a search for im-
proved wear resistance the cermet (ceramic met-
al) ionomers were developed in 1985 [108]. In
these materials silver is sintered with the glass
particles. In other products silver is added as a
powder component.
By the use of dried polyacid in the powder
setting time was prolonged. An improvement in
handling characteristics was obtained by the
introduction of capsules containing predosed
components which are mixed mechanically.
Recently, highly viscous glass ionomers were
developed. These materials have high strength,
high wear resistance, and low solubility
[109–113].
Properties. Glass ionomers adhere chemi-
cally to the tooth structure by the same mechan-
isms as zinc polycarboxylate cements. Due to the
possibility of reformation of broken bonds during
the remodeling of dentin, the bond has a dynamic
character. In a humid environment neither
shrinkage nor swelling is observed. Fluoride
release [114–116] and recharge (e.g., from tooth-
pastes) [117] explain why secondary caries are
only rarely observed near glass ionomer fillings.
Fluoride and calcium release promote dentin
remineralization [118]. The very good biocom-
patibility of glass ionomers, demonstrated in
many tests [119], led to their use as bone cements
and bone replacement materials in orthopedic
and ear – nose – throat surgery with good re-
sults [120–123].
Uses. Beside the major use as filling, luting,
and base or core buildup materials [98], further
indications are endodontic filling [124], fissure
sealant [125], orthodontic luting material [126],
filling material for open furcations [127], and
retrograde root-filling material [128].
Trade Names: Ketac-Fil Plus (ESPE), Ke-
tac-Molar (ESPE), Fuji II (GC), Fuji IX (GC)
(filling materials); Ketac-Cem (ESPE), Fuji I
124 Dental Materials
(GC) (luting materials); Ketac-Silver (ESPE),
Miracle Mix (GC); HiDense (Shofu) (Cermets);
Ketac-Bond (ESPE) (base material); Ketac-
Endo (ESPE), Endion (Voco) (root-filling
materials).
4.1.6. Resin-Modified Glass Ionomers
In an attempt to combine the advantages of glass
ionomers with those of composites, monomers
and initiators were added to glass ionomers.
Thus, parallel to the glass ionomer reaction a
polymerization reaction can be started by photo-
chemical or redox initiation [129]. Methacry-
lated polycarboxylic acids are also used [130].
Often these materials are called light-curing glass
ionomers; the general term resin-modified glass
ionomer cements has been proposed for this class
of materials [131]. An interpenetrating network
of ion-cross-linked polycarboxylate and poly
(meth)acrylates is formed. To obtain compatibil-
ity of water-based glass ionomers and resins, all
materials contain hydroxyethylmethacrylate and
other hydrophylic monomers [93]. Due to the
hydrophilicity, a relatively high swelling is ob-
served. For this reason resin-modified glass io-
nomer cements are not recommended for cemen-
tation of all-ceramic restorations (cracking of
such restorations was observed) [132–134]. Res-
in-modified glass ionomers have higher strength
and better esthetics than conventional glass io-
nomers but a relatively low wear resistance.
Depending on the amount of resins in the struc-
ture, these materials can be self-adhesive. Due to
the ease of handling they are largely used in
pediatric dentistry.
Trade Names: Photac-Fil Quick (ESPE), Fuji
II LC (GC), Vitremer (3M) (filling materials);
Fuji Plus (GC), Vitremer Luting (3M) (luting
materials)
4.1.7. Polyacid-Modified Composites
Conventional and resin-modified glass ionomers
contain all three essential components of a glass
ionomer, which react spontaneously when they
come into contact. In search of light curing ‘‘one-
component-glass ionomers’’, water-free systems
were formulated. The glass ionomer reaction
takes place only on water absorption in the oral
Vol. 11
environment [135], [136]. These materials are
known as polyacid-modified composites [131] or
compomers (composite ionomers). These mate-
rials are composite resins containing ion-leach-
able glass fillers, polymerizable acids, polycar-
boxylic acids, and hydrophilic monomers that are
compatible with the acids and facilitate water
absorption for the glass ionomer reaction [93].
An important property is the ease of handling.
Strength and esthetics are better than those of
resin-modified glass ionomers and comparable to
those of composites. However, they have no self-
adhesion and only low fluoride release compared
to glass ionomers. They shrink comparably to
composites and show the same tendency to swell
as resin-modified glass ionomers [132–134].
Resin-modified glass ionomers and polyacid-
modified composites are often referred to by the
collective term ‘‘glass ionomer composite hy-
brids’’ (or simply hybrids). For both classes the
most important indications are in fillings, the
luting of metallic restorations, or as a liner or
base [94].
Trade Names: Dyract (Dentsply), Compo-
glass (Vivadent),Hytac (ESPE) (filling materi-
als); Dyract Cem (Dentsply) (luting material).
4.2. Cements Based on Complex
Formation
These cements harden by the reaction of a metal
oxide, hydroxide or salt with a chelating agent.
Chelates form a matrix in which the inorganic
particles are embedded. These materials gener-
ally have low mechanical strengths and therefore
their use is limited to temporary fillings or lut-
ings, pulp capping materials or root fillings.
4.2.1. Zinc Oxide – Eugenol Cements
Zinc oxide – eugenol cements (ZOE cements)
contain zinc oxide and eugenol (the principal
component of oil of cloves) as essential compo-
nents. In two-paste systems, zinc oxide is sus-
pended in a vegetable or mineral oil, and eugenol
is thickened with resins. Small amounts of water
or acetic acid are added to initiate and accelerate
the reaction. The strength of these materials is
low, and their solubility is high compared to other
Vol. 11
cements. Depending on the powder/liquid ratio
or paste formulation, temporary restorations,
luting cements, or root canal sealers can be
prepared. Similar systems are used as impression
materials [94]. In some formulations part of the
eugenol is replaced by o-ethoxybenzoic acid.
These EBA cements are stronger. They are used
for the same indications as ZOE cements [94].
Due to the phenolic character of eugenol, the use
of certain resin-based luting materials after tem-
porary cementation with ZOE or EBA cements is
problematic (inhibition of polymerization by
phenols).
Trade Names: Temp Bond (Kerr), Scutabond
NF (ESPE).
4.2.2. Calcium Hydroxide Cement
First attempts to use calcium hydroxide in den-
tistry are dated from the late 1700s. Calcium
hydroxide has an antimicrobial effect and in-
duces the formation of secondary dentin. The
calcium hydroxide has been used in pulp capping
since 1859 [137]. Cements contain salicylate
chelating agents that react with calcium hydrox-
ide (e.g., methyl salicylate or butanedioldisali-
cylate) [138], [139].
Trade Names: Dycal (Dentsply), Alkaliner
(ESPE), Life (Kerr).
4.2.3. Other Chelating Cements
Various chelating agents are used in dentistry,
especially together with zinc oxide. Root canal
filling materials containing a 1,3-diketone and
eugenol-free temporary cements containing liq-
uid carboxylic acids are known.
Trade Names: Diaket (ESPE) (root filling
material);Temp Bond NE (Kerr), Freegenol
(GC), Procem (ESPE) (temporary cements).
4.3. Standards
The international standards for dental cements
are:
. ISO 3107, Dentistry – Zinc oxide/eugenol
and zinc oxide/non eugenol cements
. ISO 6876, Dental root canal sealing materials
Dental Materials 125
. ISO 9917-1, Dentistry – Water based ce-
ments – Part 1 Powder/liquid acid base
cements
. ISO 9917–2, Dentistry – Water based ce-
ments – Part 2 Light activated cements
5. Synthetic Resins
Synthetic resins are of great significance in den-
tistry. Polymers of the polymethacrylate group
have been in use since around 1934, and they are
still used today [36].
5.1. Denture Base Resins
The first organic base material for dentures was
hard rubber. Pink India rubber was vulcanized in
a water-filled autoclave at ca. 140 ! C. This den-
ture base material was used in combination with
porcelain teeth. The dental prostheses produced
in this way were functional, but not esthetically
pleasing. The India rubber procedure is of only
historical interest today.
The basic process of denture fabrication has
remained unchanged. A stone (gypsum) model
of the jaw is prepared from an impression of the
patient’s oral cavity. The original shape of the
denture base is molded in wax on the stone
model. The artificial teeth, either of porcelain
but today mainly of resin, are mounted on this
wax rim. The wax denture on the stone model is
then invested with gypsum in the lower half of a
denture flask. Subsequently, the other half of the
flask, open on the upper side, is attached and the
wax model is embedded completely. The gyp-
sum on top of the upper half of the mold is
planed by pressing with a lid. After the plaster
has set, the two halves are separated and the wax
is removed by melting. The artificial teeth re-
main fixed in the upper half of the flask. In this
way, a precisely fitting cavity is obtained in
which raw, unvulcanized rubber or the resin
mixture to be polymerized is pressed and
hardened.
Insulation of the stone plays a decisive role in
this process, because the resin must be kept
separate from the plaster. Initially, dental tech-
nicians used ductile tinfoil, which could be
adapted with perfect precision to the teeth on
the free plaster surface of the model. Tinfoil also
seals the doughy mass to be polymerized from the
126 Dental Materials
steam that can evolve from hot plaster. More
conveniently, a coating consisting of a ca. 3 %
solution of sodium alginate in water can be
applied to the plaster surface. It reacts with the
plaster surface to give a water-insoluble calcium
alginate film.
The decisive breakthrough in denture base
resins was the development of poly(methyl meth-
acrylate) by R€ oHM. ROTH, a dental technician,
mixed ground poly(methyl methacrylate) with
the methyl methacrylate monomer; this gave a
dough that could be used to make a functional and
aesthetically satisfactory dental prosthesis, as
described above [37]. The polymer – monomer
mixture solved two problems of methyl methac-
rylate polymerization simultaneously: (1) the
pure monomer shrinks by ca. 20 % during poly-
merization and (2) it simultaneously releases a
large amount of heat (56.6 kJ/mol).
Poly(methyl methacrylate) [9011-14-7] has a
dominant position in dental resins; it meets best
the following requirements of a denture material:
. Absence of taste or odor, even after long
periods of wear
. Good tissue compatibility
. Good mechanical properties
. Exact reproduction of details of the model
. Dimensional stability
. Low water sorption
. Color stability
. Good aesthetic appearance
. Simple manipulation (no need for expensive
equipment)
. Good reparability
. Ease of cleaning
Methacrylates are available as powder and
liquid. The polymer powder, today usually bead
polymer, is mixed with the liquid monomer in a
weight ratio of (2.5 – 3):1. After a certain swell-
ing time, doughs are obtained which can easily
be manipulated by pressing, pouring, or
molding.
Mineral pigments are the principal coloring
agents used; organic dyes are less important. To
avoid formation of stress cracks and improve
mechanical properties, the liquid monomer gen-
erally contains up to 10 % of a cross-linking
agent. Ethylene glycol dimethacrylate [97-90-
5] is preferred. Depending on the polymerization
initiator used, four types of materials can be
Vol. 11
distinguished: heat-, cold-, light-, and micro-
wave-cured polymers.
5.1.1. Heat-Cured Polymers
The procedure developed by ROTH is called the
‘‘Paladon technique’’ in dental laboratory tech-
nology. In heat-cured polymers, 0.1 – 0.5 % di-
benzoyl peroxide [94-36-0] is generally used as
the free-radical initiator.
After the resin dough has been added to the
insulated plaster form and pressed, the form is
placed in a hot water bath. Dibenzoyl peroxide
decomposes between 80 and 100 ! C and initiates
the radical chain reaction. If heating is too rapid,
polymerization proceeds too vigorously and a
porous product is formed due to boiling of the
monomer (bp 100.2 ! C at 101.3 kPa). Therefore,
the initial heating process should be held at 70 –
75 ! C for 30 min; then the water bath is allowed
to boil for an additional 30 min.
The resin can be added to the hollow mold by
injection or by packing the negative mold and
applying pressure with a pneumatic press. In the
packing and pressing procedure, excess resin is
placed in the denture flask and the two molds are
joined under pressure; excess material is
squeezed out between the casts. The flask is then
opened, and squeezed out excess material is cut
off. The closed flask is then placed in the water
bath. Better fit can be obtained by using the
injection technique [38]; in this case, the resin
is injected under high pressure into the closed
flask. The flask is then placed in the water bath
and held under pressure until polymerization is
complete.
Trade names: Paladon 65 (Heraeus Kulzer,
Germany); SR 3/60, SR Ivocap (Ivoclar, Liech-
tenstein); Lucitone (Dentsply, USA).
5.1.2. Cold-Cured Polymers
In addition to the heat-cured polymers described
above, cold-cured polymers (also called autopo-
lymers) have increased in significance [36]. In
cold-cured polymers, the polymerization is initi-
ated by a two-component redox system, one
component of which is in the powder and the
other in the liquid. Such systems are usually
composed of tertiary amines, e.g., N,N-dimeth-
Vol. 11
yl-p-toluidine [99-97-8] (1 – 2 %), and perox-
ides, particularly dibenzoyl peroxide (0.5 –
2 %) which has been used worldwide since about
1940 [39]. The addition of UV stabilizers is
customary to reduce discoloration.
When the components of the redox system are
combined, numerous radicals form which acti-
vate polymerization. However, the formation of
inactive byproducts leads to a yellow-brown
discoloration of the resin. Initiator systems that
do not produce discoloration were developed in
1956 [40]; they consist of a 5-substituted barbi-
turic acid combined with dibenzoyl peroxide or
heavy-metal salts. The color stability of cold-
cured polymers having this type of initiator
system is so high that the quality of the polymer
reaches that of heat-cured materials.
Cold-cured polymers are manipulated like the
heat-cured polymers, but the ratio of monomer to
polymer is higher (10 : 4 to 10 : 7), and polymeri-
zation takes place in the closed flask at room
temperature in 10 – 30 min. If no injection pres-
sure is used, i.e., in the completion of cast
dentures with resin (partial dentures) and in the
fabrication of complete cast dentures, polymeri-
zation is carried out in a pressure chamber at
0.2 – 0.3 MPa and 45 – 55 ! C to avoid porosity
of the product.
Cold-cured polymers are preferred today for
repairing fractured prostheses and for relining
poorly fitting ones. The cold-cured resins are also
used almost exclusively for the completion of
cast partial dentures.
For complete dentures, cold-cured polymers
are injected. While heat-cured polymers show
certain strain after cooling, which arises from
differences in expansion coefficients between
plaster and resin, cold-cured resins polymerize
practically free of strain. This results in a better fit
of prostheses fabricated from cold-cured resins.
Trade names: Palapress, Paladur (Heraeus
Kulzer, Germany); SR 3/60 Quick (Ivoclar,
Liechtenstein), Degupress (Degussa-H€ uls,
Germany).
5.1.3. Light-Cured Polymers
The first denture resin that was polymerized by
the action of light from a halogen source was
introduced in 1984 (Triad, Dentsply). The resin
material is supplied in a ready-to-use form which
Dental Materials 127
eliminates the need for mixing in the dental
laboratory.
Instead of methyl methacrylate, diesters of
methacrylic acid with high molecular mass diols
similar to bis-GMA (see Section 5.6) or high
molecular mass urethane dimethacrylates are
used as monomer.
The handling technique has been adjusted
because complete investment in plaster is no
longer possible, since the light must have access
to the resin from all sides. For this reason, for
example, pontics are provided in prefabricated
standard sizes. A more detailed description of
light curing is given in Section 5.6.2 on resin-
based filling materials.
Trade name: Triad VLC, Eclipse (Dentsply,
USA).
5.1.4. Microwave-Cured Polymers
The reaction of microwave-cured polymers is
almost the same as for heat-cured materials. The
main difference is that the flask is not placed in a
water bath and heated to boiling temperature.
Instead, the water contained in the gypsum in the
flask is boiled by microwave energy. Since metal
flasks are impermeable to microwaves, flasks for
microwave-cured polymers are made from fiber-
reinforced polyester. The initiator system must
be adjusted to the polymerization process. There-
fore only materials specifically designed for mi-
crowave curing can be used for this polymeriza-
tion procedure.
Trade name: Acron MC (GC, Japan).
5.1.5. Other Denture Resins
Soft resins are used as liners of dentures. In the
past, plasticized acrylic or methacrylic acid es-
ters or esters of higher alcohols were used;
however, they are not sufficiently durable. If
made of silicones, the liners have better durabili-
ty but insufficient bonding to the denture base
material.
Many attempts have been made to replace
methyl methacrylate as the denture base material
by other plastics [41], [42]. Polyamides and
polyurethanes, practically indestructible resins
in the fabrication of dental prostheses, have failed
because of their insufficient rigidity and their
128 Dental Materials
excessive water sorption. At one time, polycar-
bonates (e.g., Thermpont, Andoran, and Copo-
dan) appeared to be alternative resins because of
their high impact strength. However, their di-
mensional stability did not meet clinical require-
ments [41]. The high sensitivity of these materi-
als to the steam evolved during injection into the
mold, was responsible for alterations in shape
and color. Furthermore, polycarbonates are sen-
sitive to alkali which is present in many denture
cleansers and leads to the formation of strain,
tears, and denture fractures. The special injec-
tion techniques required and the associated ex-
pensive devices have also contributed to the
elimination of polycarbonates from the denture
base market.
Resins based on poly(vinyl chloride) [9002-
86-2] appear to have a better chance for use as
denture materials. Copolymers of vinyl chlo-
ride, vinyl acetate, and methyl methacrylates
(e.g., Luxene and Virlene) are used because of
their constancy of shape, low water sorption,
and high fracture resistance. They can only be
handled in licensed laboratories and require
relatively complicated and expensive special
apparatus; their market share has, therefore,
remained minor.
5.2. Acrylic Teeth [43]
Most artificial teeth set up in a denture base resin
are acrylic teeth, made from poly(methyl meth-
acrylate) and methyl methacrylate. The early
problems of poor shade composition, shade du-
rability, crazing resistance, and particularly,
abrasion resistance have been solved. Today,
resin teeth can replicate natural teeth perfectly.
The resin tooth is built up from cervical, dentin,
and incisal resins, each of which is colored to
correspond to the appropriate tooth shade.
The layers are pressed into metal molds, one
after the other, and heat-polymerized under pres-
sure. To give greater hardness to the outmost
(incisal) layer for greater abrasion resistance, ca.
10 % of a cross-linking agent, preferably ethyl-
ene glycol dimethacrylate [97-90-5], is added.
The cervical material is not or only weakly cross-
linked, because it then absorbs the monomer of
the denture base resin dough more readily, which
provides for better bonding of the acrylic tooth to
the denture base.
Vol. 11
Despite its high abrasion resistance, poly
(methyl methacrylate) is not entirely satisfactory
for teeth in the posterior region. The mechanical
properties and the wear resistance of the resin can
be increased enormously when it is filled with
30 – 60 % of very small (mean grain size
0.04 mm) particles of hydrophobic (fumed) silica
(e.g., Aerosil, Degussa).
Trade names: SR-Orthosit, SR-Vivodent PE
(Ivoclar, Liechtenstein) Vitapan (Vita Zahnfab-
rik, Germany).
5.3. Crown and Bridge Veneer Resins
[44]
Resins are also used to veneer the visible parts of
metal crowns or bridges. Today, polymers of
high molecular mass methacrylic acid diesters
are used almost exclusively for this purpose and
for jacket crowns. The abrasion resistance of the
methacrylates can be increased by adding inor-
ganic fillers such as very fine grained silica, and
fine grained glass or quartz (particle size
< 1 mm)
5.3.1. Heat-Cured Resins
Heat-cured resins provide better results than
cold-cured polymers for crowns and bridges.
They are available as combinations of powder
and liquid or as ready-to-use pastes. The resin
pastes are molded directly on the metal frame-
work by the dental technician and are then poly-
merized in a pressure vessel at approximately
0.6 MPa and 110 ! C. Steam, water, or glycerol is
used as the heat-transfer medium.
Trade names: SR-Chromasit (Ivoclar, Liech-
tenstein); Biodent KþB Paste (Dentsply,
Germany); Vita Zeta (Vita Zahnfabrik, Germany).
5.3.2. Light-Cured Resins
A breakthrough, particularly in processing, oc-
curred when light-cured crown and bridge ve-
neer resins were introduced [45]. These materi-
als consist of ready-to-use single-paste resins,
which eliminates the need for mixing. Polymer-
ization is induced by irradiation with light
Vol. 11
(wavelength 300 – 500 nm). An aromatic ke-
tone or camphoroquinone is employed as photo-
initiator; tertiary amines are frequently used as
reaction promoters. Light-initiated polymeriza-
tion can provide resins that are fully equal in
quality to heat-cured ones.
Trade names: Signum þ (Heraeus-Kulzer,
Germany); Sinfony (Espe, Germany); Cristobal
þ (Dentsply, USA).
5.4. Resin – Metal Bonding
The question of adhesion between metal and
resin is of great significance for denture resins
and for crown and bridge veneer resins. Unfor-
tunately, without special bonding processes,
gaps form between metal and resin in cast
prostheses after short periods of use. Bacteria
and food debris can settle in these gaps, leading
to discoloration at the metal – resin interface.
The same problem arises in crowns and bridges.
Formerly, the resin could be held to the metal
framework only with mechanical devices (metal
beads or wires), which may be visible through
the resin.
In 1984, the Silicoater technique was devel-
oped, which solved the problem of adhesion
between metal and resin for all precious and
nonprecious alloys. In this procedure, a silane
is pyrolyzed in a flame and the products are
deposited on the metal framework, where an
SiOxC layer of 0.1 mm thickness forms. On this
surface, another silane, such as 3-methacrylox-
ypropyltrimethoxysilane [2530-85-0], can sim-
ply be painted. If the methacrylate monomer is
then applied, it reacts with the silane. The metal-
to-resin bond achieved in this manner is stronger
than the self-tear resistance of the resin. The bond
remains stable in the oral milieu [47], [48].
Another process of silane coupling between
metal and resin is the Rocatec technique. In this
process, introduced in 1989, the surface energy
of the metal is increased by two-step sandblast-
ing with aluminum oxide. The first step uses
pure aluminum oxide, and the second step with
aluminum oxide coated with a special glass, part
of which remains on the metal surface after
impact. A silane is then applied to the treated
surface.
Other systems apply hydrophobic fluorinated
methacrylates to the surface (Sebond-MKV), use
Dental Materials 129
a molecule containing an acidic group (SR-Iso-
sit-Spectra-Link) or use tin plating and oxidation
of the tin layer on the surface (OVS). Another
method is bonding with 4-methacryl-oxyethyl-
trimellitone-hydrid (4-META).
Trade names: Silicoater (Heraeus-Kulzer,
Germany). Rocatec (Espe, Germany); Sebond-
MKV (Sch€utz Dental, Germany); SR-Isosit-
Spectra-Link (Ivoclar, Liechtenstein)
5.5. Resins for Orthodontics
Orthodontic treatment is used to correct the
position of teeth. For removable orthodontic
devices, cold-cured polymers, such as those
described in Section 5.1.2, are used. For fixed
orthodontic appliances, resins very similar in
chemical composition to those used in cold-
cured restorative materials are employed as
adhesives.
Trade names: Orthocryl (Dentaurum,
Germany); Super C Ortho (Amco, USA).
5.6. Restorative Resins
In the past, only silicate restorations and expen-
sive fired porcelain inlays were available to
provide ‘‘invisible’’ tooth restoration. Silicate
cement fillings have insufficient durability be-
cause their surfaces wash out and they do not
esthetically satisfy.
Soon after their discovery, cold-cured poly
(methyl methacrylate) resins (Section 5.1.2)
were also used for restorative fillings. However,
the presence of amine – peroxide catalysts in
the resins leads to a bright yellow discoloration
after service periods of only a few months.
Similarly, the abrasion resistance of the resto-
ration is not sufficient. In addition, the high
concentration of unconverted monomer remain-
ing in the resin can provoke pulp irritation.
Therefore, these resins have been replaced by
the new filler resins described in the following
paragraphs.
BOWEN transferred the structural principle of
an epoxy resin to a methacrylate material and
thus gave the latter the excellent material prop-
erties of filled epoxies [36]. The key chemical in
this method is the so-called Bowen monomer
(bis-GMA)
130 Dental Materials
which is made from bisphenol A di(2,3-epoxy-
propyl) ether [1675-54-3] and acrylic acid [79-
10-7]: BOWEN also proposed using a mixture of
70 % ground quartz glass (average particle size
approximately 15 mm) and 30 % of bis-GMA
[36], [49] . Not only is the composite made in
this way much more rigid and harder than
polymers of methyl methacrylate, but it also
shrinks less during polymerization because of
the greater molecular mass per double bond.
Today monomer mixtures of bis-GMA and
triethylene glycol dimethacrylate [109-16-0], as
well as other dimethacrylates which act as dilu-
ents and certain urethane dimethacrylates, are
used. In addition, the high content of inorganic
fillers greatly decreases the thermal expansion
coefficient and thus approaches that of the
natural tooth.
The important problem of matrix-to-filler
bonding is solved by treating the inorganic filler
material with special silanes [50], [51], e.g.:
The silanol groups of the hydrolyzed silane
react with the hydroxyl groups of the silica
filler, and its methacryl groups enable copoly-
merization with the matrix resins to occur,
thus providing a chemical bond between matrix
and filler.
The structure and particle size of the inorganic
filler material have also been modified. The
relatively coarse-grained fillers of the first
Vol. 11
composite generations (especially quartz with
a particle size of 15 – 30 mm) did not permit
glaze polishing of the external surface of the
restoration. The use of fumed silica with a parti-
cle size of 0.01 – 0.04 mm led to restorative
materials whose surfaces were homogeneous and
amenable to glaze polishing. These ‘‘micro-
filled’’ composites contain about 50 vol % fillers.
In a more recent development, glass particles
(< 1 mm; barium or strontium silicate glass) are
mixed with the fumed silica. Such composites,
called hybrids, are characterized by particularly
good mechanical properties, homogeneous
surfaces, and good polishability. These materials
contain ca. 10 wt % fumed silica and ca. 70 %
glass.
Composite restorative materials are no longer
limited to the anterior region. Nowadays they
have the required strength and abrasion resis-
tance for use on occlusal surfaces.
5.6.1. Paste – Paste Systems
The composites whose chemical composition is
described in the previous section have been
available as two-paste systems: base paste and
catalyst paste [36], [50], [51]. Nowadays there
are only a few materials of this kind available on
the market.
The tooth-colored base paste contains a ter-
tiary amine (1 – 2 %), and the catalyst paste
contains dibenzoyl peroxide (1 – 1.5 %). The
tertiary amine usually is N,N-bis(2-hydro-
xyethyl)-p-toluidine [3077-12-1]; it does not
have as great a tendency for discoloration as the
N,N-dimethyl-p-toluidine used earlier. However,
UV stabilizers must still be added. The catalyst
pastes have a strictly limited shelf life of approx-
imately one year and must be stored in a
refrigerator.
Before placement, the base and catalyst pastes
are mixed in a 1 : 1 ratio. Depending on the
particular product, the working time ranges from
1 to 2 min and the setting time from 3 to 5 min.
Disadvantages of the paste – paste system are
the severely limited shelf life of the peroxide
paste and the still-unsatisfactory color stability.
Furthermore, air bubbles are generated in the
pastes during mixing which severely affect the
quality of the restoration.
Vol. 11
5.6.2. Light-Cured Polymers
Light-cured polymers do not have the disadvan-
tages of the paste – paste systems described in
the previous section. The light-cured composites
are almost identical in composition to those
materials described in Section 5.6. However,
they consist of only one component that contains
a photoinitiator system.
The advantages of light-cured composites
over the paste – paste systems are
* Immediate readiness for use
* Fewer air bubbles because mixing is not
required
* Prolonged working time
* Better color stability
* Much longer shelf lives (three years)
* No need for cool storage
* Much higher reaction rate
The first radiation-cured composites were po-
lymerized with UV radiation (320 – 440 nm) in
the presence of an aromatic ketone initiator such
as 1,2-diphenyl-2,2-dimethoxyethanone [24650-
42-8]. At an irradiation time of 20 s, a maximum
depth of cure of only 1.5 mm was attainable.
Nowadays, visible light (380 – 500 nm) is used
with camphoroquinone [10373-78-1] as initiator
and certain aliphatic and aromatic amines as
polymerization promoters, and only common
halogen lamps (150 – 250 W) or blue LED
lights are required. In addition, the risk of UV
radiation to the dentist’s and patient’s eyes dis-
appeared. The most important advantage of po-
lymerization with visible light, however, is the
much greater cure depth attained. Depending on
the composite and the light source, curing depths
of 4 – 8 mm can be attained after 20 – 40 s
irradiation time. Fiberoptics conduct the light to
the site at which radiation is required.
Trade names: Charisma, Soltaire 2 (Heraeus-
Kulzer, Germany); Artemis, Tetric Ceram (Vi-
vadent, Liechtenstein); Prisma TPH, Surefil
(Dentsply, USA); Beautifil (Shofu, Japan);
Clearfil posterior (Kuraray, Japan); Prodigy
(Kerr, USA); Filtek (3M Espe, USA).
5.6.3. Ormocer-Based Filling Materials
In this type of polymer-based filling material, the
main component of the monomer matrix is an
Dental Materials 131
organically-modified-ceramic (ormocer). This is
a cross-linked silicone oligomer bearing meth-
acrylate groups. Dimethacrylates are used as
diluents. Initiators and fillers are like in the
light-cured polymers (Section 5.6.2). Advan-
tages of this type of material are:
. Lower polymerization shrinkage because of
the size of the oligomer molecule
. Lower dissolution rate of residual monomers
because of the hydrophobic nature of the mol-
ecule, and a higher probability of each mono-
mer molecule being incorporated in the poly-
mer network because of the multifunctionality
. Higher abrasion resistance compared to mate-
rials with the same type and size of filler
particles
Trade names: Definite (Dentsply De Trey,
Germany);Admira (Voco, Germany).
5.6.4. Sealant Resins
Fissures of the posterior teeth are potential sites
at which carious lesions can arise. However,
when these fissures are sealed with thin layers
of bis-GMA or related compounds, the occlusal
surfaces can largely be protected from caries. The
sealant resins, like restorative resins, are avail-
able as cold-cured and light-cured systems.
Trade names: Estiseal F (Heraeus-Kulzer,
Germany); Delton (Dentsply, USA).
5.6.5. Resin – Tooth Bonding
Adhesion of the resin to the tooth is very impor-
tant because otherwise restorations have short
lifetimes, and marginal gaps are formed between
the restorative resin and the tooth [49], [51], [52].
These gaps can be sites of secondary caries. In
general, no bonding occurs between tooth and
resin, and the dentist must provide mechanical
anchorage to ensure retention. However, when
mechanical retention is used, a relatively large
amount of sound tooth tissue is lost.
The acid-etch technique has been used to
provide bonding of enamel to composite resins.
The dental enamel surface was first roughened
with an approximately 35 % solution of phospho-
ric acid so that microretentions result. A thin
132 Dental Materials
layer of resin of the bis-GMA type was then
applied to the etched surface; the monomer pe-
netrates the pores etched into the enamel and is
firmly anchored there. Finally, the restorative
resin was applied, and a mechanical bond formed
between dental enamel and resin.
Adhesion to dentin can not so easily be
achieved. It took a while until it was realized
that chemical bonding is not the way to solve the
problem. With modern materials a smear layer
that is formed on the dentin surface during cavity
preparation is dissolved in an acid. Part of the
inorganic material of the dentin is dissolved, too.
Collagen fibers extending into sound dentin re-
main on the surface. The dissolved material is
washed away or remains in the adhesive. The
adhesive penetrates the collagen and a part of the
dentin tubuli to form a hybrid layer. The meth-
acrylate groups of the monomers in the adhesive
provide chemical bonding to the filling material.
Since moisture is always present at the dentin,
surface monomers in the adhesive have to be
hydrophilic.
Trade names: Scotchbond (3M Espe, USA);
Clearfil bond (Kuraray, Japan); Dentin Adh€asit
(Ivoclar, Liechtenstein); Syntac (Vivadent,
Liechtenstein) Prime & Bond NT (Dentsply,
USA);
5.6.6. Toxicology
The toxicology of restorative resins is an impor-
tant international issue, especially because of the
relatively high pulp toxicity of methyl methac-
rylate. For this reason, new monomers with high
molecular mass have been developed, e.g., bis-
GMA (LD50 14.15 mL/kg) which is not orally
toxic and does not irritate skin or mucous
membranes.
Studies on the biocompatibility of restorative
resins have increased enormously in the past few
years. A series of important components of re-
storative resins has been examined for tissue
compatibility, and none of the substances exam-
ined caused irritation [46].
5.7. Standards
The following international standards on poly-
mer based materials apply:
Vol. 11
. ISO 1567: Dentistry – Denture Base Polymers
. ISO 4049: Dentistry – Polymer-based filling,
restorative and luting materials
. ISO 6874: Dentistry – Polymer--Based Pit and
Fissure Sealants
. ISO 6876: Dental Root Canal Sealing
Materials
. ISO 7491: Dental Materials – Determination of
Color Stability
. ISO 10139–1: Dentistry – Soft lining materials
for removable dentures — Part 1: Materials for
short-term use
. ISO 10139–2: Dentistry – Soft lining materials
for removable dentures – Part 2: Materials for
long-term use
. ISO 10477: Dentistry – Polymer-Based Crown
and Bridge Materials
. ISO 22112 Dentistry – Artificial teeth for
dental prostheses
6. Impression Materials [53–61]
According to their handling (chemoplastic or
thermoplastic) and their properties after setting
(elastic or hard, reversible or irreversible),
impression materials can be grouped as follows:
Chemoplastic
Elastic, irreversible
alginate
elastomers
Hard, irreversible
impression gypsum
ZOE paste
polymer
Thermoplastic
Elastic, reversible
Hydrocolloid
Hard, reversible
impression compound
wax – resin
gutta-percha
The oldest known impression material is plas-
ter of paris (DWINELLE 1840). Dental compound
(STENT 1840) and gutta-percha (1850) were de-
veloped for use as impression materials in the
mid-1800s. Hydrocolloids (agar) were intro-
duced in 1927 (POLLER), zinc oxide and eugenol
pastes in 1935 (KELLY); alginates in 1940
Vol. 11
(WILDING); polysulfides and condensation sili-
cone resins in 1955; polyether resin in 1964
(ESPE); and addition silicone resins in 1976.
The principal requirements for impression
materials are:
. Biocompatibility for patient and user
. Physical and chemical properties in accor-
dance with the purpose of impression taking
(precision of the dies, recording of the func-
tion): Flowability during impression taking,
detail reproduction, mechanical strength, di-
mensional stability of the impression, compat-
ibility with the die material
. Efficient workability to optimal quality (lot
consistency, storability, ease of dosing
and mixing), hygienic aspects (disinfectabil-
ity), ergonomically favorable methodology,
economy
The dentist needs a large choice of impression
materials, because they fulfill the requirements to
different degrees. For each task a certain impres-
sion material is best suited. The choice of an
impression material is mainly governed by the
required precision of the die (documentation,
type of dental restoration), the object to be repli-
cated (shape and condition), and the method of
impression taking. When equally good results
can be obtained with different impression mate-
rials, ergonomic and economic aspects are
decisive.
6.1. Elastic Materials
An important advantage of elastic materials is
that it is possible to remove them from the object
from which the impression is taken without
breakage or extreme deformation, even when
they fill undercuts.
6.1.1. Alginates
Alginates (see also ! Polysaccharides, Section
3.4.1.) are derived from alginic acid, a polyuronic
acid composed of up to 750 units of D-mano-
nuronic acid and L-guluronic acid 1,4-glycosi-
dicly linked. It is contained in the marine algae in
the amount of 40 % (dry substance). It is almost
Dental Materials 133
insoluble in water but has a high ability to swell
by the absorption of water.
Dental alginates are powder mixtures with the
following composition: sodium alginate (10 –
20 wt %), calcium sulfate (10 wt %), trisodium
phosphate (1 – 4 wt %), diatomite (70 – 80
wt %), color and flavor (1 – 2 wt %). Mixing
with water gives a plastic mass which sets by
chemical reaction to give an elastic hydrogel.
Monovalent soluble salts of alginic acid (Na, K,
NH4 alginate) are precipitated as sparingly solu-
ble Ca salts. Since 1980 no lead compounds are
contained in alginate, and low-dust and no-dust
versions are available. The reaction is prolonged
to a practical duration by a retarder (trisodium
phosphate) which initially reacts with the Ca
ions. Fast- and normal-setting preparations are
available. The filler (diatomite) influences the
plasticity of the mixture as well as the strength
and elasticity of the impression. The plasticity of
the mixture can be influenced by the powder/
liquid ratio, and the working time by the water
temperature. Dosing is performed manually, and
mixing manually or in a mixer. The hydrogel
ages (syneresis) and is sensitive to environmental
conditions. Storage in air leads to a significant
shrinkage of the impression. Disinfection is pos-
sible if well-proven recommendations are fol-
lowed. The die must be manufactured as soon as
possible, preferably 15 min after removal of the
impression from the mouth and not later then
60 min after removal if stored in a humidor.
Plastic deformations result from pulling over
strongly curved parts of the impression. Thin
bridges of the impression material tear off. Detail
reproduction requires pressure during impression
taking and is not as good as with reversible
hydrocolloids or elastomers.
Handling is simple and cheap. Alginates are
used in many ways: to obtain dies for documenta-
tion, for therapy planning, removable dentures
and removable orthodontic devices. They are not
suited for fixed restorations (crowns and bridges).
A 3 % aqueous solution of alginate is used to
produce insulating layer on gypsum dies in dental
polymer technology.
6.1.2. Elastomers
Silicones. Impression silicones can be dif-
ferentiated into condensation cross-linked sili-
134 Dental Materials Vol. 11

cones (C-silicones) and addition cross-linked
silicones (A-silicones).
In the case of C-silicones, organic polysila-
nols and polydimethylsilanediols are condensed
to give macromolecules by cross-linking agents
(tri- and tetrafunctional alkoxysilanes) and ac-
celerators (e.g., tin octanoate and dibutyltin di-
laurate) with cleavage of volatile byproducts
(alcohols). Fillers (10 – 80 wt %) are used to
adjust the consistency: extra fine, fine, medium,
heavy, and putty. Dosing and mixing of the
base paste and hardener (as liquid or paste) are
performed manually. The addition of colorants
makes homogeneous mixing easier and
allows materials of different consistency to be
distinguished when combinations of materials
are used.
In the case of A-Silicones, polyvinylsiloxanes
and siloxanes with terminal SiH groups are
additively coupled by a platinum(0) divinylte-
tramethyldisiloxane complex (Karstedt cata-
lyst). Reactive oligomers are formed as discrete
intermediates by transfer of H atoms to give
dimethylene bridges without formation of by-
products (hydrosilylation). The polymerization
reaction can be disturbed by catalyst poisons
(local anesthetics, astringents, traces of sulfur
from vulcanized latex gloves, accelerators and
cross-linking agents of C-silicones). The consis-
tency can be adjusted from low viscosity to
putty by fillers (40 – 70 wt %) and softening
agents or paraffin oil (5 – 10 wt %). The pro-
ducts consists of a base paste and a catalyst
paste, which are
. Dosed and mixed manually
. Pressed out of a double cartridge by a static
mixer (homogeneous mixing)
. Dosed and homogeneously mixed by a ma-
chine with a dynamic mixer
Stability of the flowable silicones during ap-
plication results from their thixotropy (reversible
sol – gel transformation).
By addition of small amounts of nonionic
tensides, which lower the interfacial tension with
respect to water, the wettability of the hydropho-
bic A-silicones is enhanced. During impression
taking, A-silicones with added tensides remain
mainly hydrophobic, since the tenside micelles
align only during contact with the moist impres-
sion object. However, contact to the hydrophilic
gypsum during die production is enhanced, and
this avoids voids (bubbles) on fine edges of the
die. This can be achieved by the treatment of
nonhydrophilic silicone with a wetting liquid
(tenside in ca. 40 wt % isopropyl alcohol).
A comparison of C- and A-silicones is given
in Table 7.
A-silicones can be used for all kinds of im-
pressions in dentistry because of excellent detail
reproduction, high elasticity, and superior di-
mensional stability. They are neutral in taste and
odor. They are especially suitable where high
precision is needed (fixed restorations). In cases
where other, cheaper impression materials fulfil
the requirements for precision, A-silicones are
not used.
For silicones different impression methods
exist. The highest precision is achieved with a
combination of a high-viscosity material
(putty) with a low-viscosity material (double-
mixing impression, corrective impression, sand-
wich impression). Pressure during application
and a dry impression object are important re-
quirements for a successful impression of the

Table 7. Differences between condensation cross-linking silicones (C-silicones) and addition cross-linking silicones (A-silicones)

Property C-silicones A-silicones

Flowability/plasticity depends on consistency depends on consistency

Detail reproduction shift of details on shrinkage high
Plastic/elastic transition slow easier to recognize
Resistance to deformation depends on consistency depends on consistency
Residual plastic deformation higher very low, even under high compression
Change in volume contraction, depending on consistency, very low contraction
thickness of layer, and storage time
Storage of the impression limited by shrinkage indefinite, several die casts possible
Die material galvanic die production limited usable for all types
Disinfection dimensional changes possible without problems
Costs low higher
Vol. 11
prepared tooth substances. For functional im-
pressions (full dentures) slowly reacting mate-
rials are advantageous.
Further uses of A-silicones are:
. Evaluation of the positional jaw relation of the
patient (materials with a high Shore hardness)
. Duplication of dies in dental technology with
low viscosity materials
. Rebasing of dentures with a soft A-silicone
prosthetic material
. Soft A-silicone material in maxillofacial
prosthetics.
Polyethers. A poly(ethylene oxide)/poly
(tetramethylene oxide) copolymer with terminal
aziridino groups (content in the base paste ca.
60 wt %) are linked additively by an organic
sulfonium fluoroborate as starter (content in the
reactor paste ca. 30 wt %). The consistency of the
pastes is adjusted by fillers and softening agents
(triglycerides). Mechanical mixing is the method
of choice. Cooling of the pastes results in sub-
stantial increases in viscosity and makes mixing
difficult. Before use pastes stored in the refriger-
ator have to be brought to room temperature.
Detail reproduction, plastic/elastic transition,
permanent deformation, and dimensional stabil-
ity are the same as those of A-silicones. Resis-
tance to deformation during removal of the im-
pression from the teeth and from the die is higher.
Polyethers are hydrophilic. They can be stored in
air indefinitely. In aqueous media they exhibit a
small time-dependant swelling. The time avail-
able for disinfection is limited. Short-term taste
disturbance may occur with some patients. The
main use is for fixed restorations. Mono-phase
impressions and one-time two-phase impressions
with individual impression trays are preferred.
The die material is gypsum. Galvanic die fabri-
cation by silver plating is possible; copper plating
is not recommended. A special polyether mate-
rial for evaluation of the positional jaw relation is
available.
Polysulfides. Polysulfide oligomers with
terminal and side-chain SH groups are three-
dimensionally linked at the SH groups by lead
dioxide or manganese dioxide. An elastomer is
created by polycondensation. The base paste
consists of 50 – 90 wt % polysulfide oligomer
and, depending on the consistency, 10 – 50 wt %
Dental Materials 135
filler (TiO2) and softening agents (neutral oils).
The reaction paste normally consists of 77 wt %
PbO2, 3 wt % sulfur, and 20 wt % filler, and
softening agents. Newer products contain organ-
ic peroxides instead of PbO2. Common are one-
time impressions with two different consisten-
cies and individual impression trays made of
resin material. Handling, indication and proper-
ties are, at their best, comparable to those of C-
silicones. The materials are sticky, biocompati-
bility is limited (Pb content), and taste and odor
are unpleasant. The market share of this impres-
sion material is very small nowadays.
Agar Hydro Gels. consisting of 8 – 15 wt
% agar (a heteropolysaccharide from brown
algae) and 75 wt % water are converted by heat
to a flowable hydro sol and set again by cooling.
Viscosity, plasticity, and elasticity are reversibly
dependent on the temperature. Addition of glyc-
erol (7 wt %) and borax (0.2 wt %) enhance
elasticity and strength; fillers (7 wt % kaolin)
affect the consistency. Potassium sulfate
(0.1 wt %) compensates for the negative influ-
ence of borax on the setting reaction of gypsum.
Antiseptic additives (thymol) prevent microbial
contamination.
Hydrocolloid materials are distributed in
tubes (tray material) or in bars (syringe material).
They have to be conditioned by stepwise heat
treatment (water bath with three tanks): liquefac-
tion of the gel to a sol in boiling water, tempering
for storage (62 – 69 ! C); cooling to impression-
taking temperature (45 – 45 ! C). Low-viscosity
hydrocolloid is placed on the impression object
from a syringe, and then high-viscosity material
is applied on top with an impression tray. Special
impression trays are necessary that provide me-
chanical retention for the impression material
and are equipped with channels for water
cooling.
Detail reproduction of the hydrophilic mate-
rial is very good, even under low pressure. Per-
manent plastic deformation is higher than with
elastomers, and tear resistance is much lower.
The field of use is impressions for fixed restora-
tions (inlays, crowns, bridges). Results equal to
those of elastomers are reached with correct
handling. Disinfection is possible only with short
contact time. Hydrocolloid impressions can not
be stored; immediate casting of a die (gypsum) is
necessary.
136 Dental Materials
6.2. Rigid Materials
6.2.1. Plaster of Paris
A powder of CaSO4 b-hemihydrate (90 wt %),
fillers (alumina, CaCO3, diatomite; 7 wt %), ac-
celerators (K2SO4, NaCl; 2 wt %), color, and
flavor is mixed with water (1.5 to 2 parts of
powder, 1 part of water) and hardens to an
irreversible rigid impression within 3 – 5 min.
Flowability and plasticity can be satisfactorily
adjusted by means of the water content and
depend on the working temperature. The reaction
is exothermic. Plaster expands slightly (max.
0.15 % linear). Detail reproduction is very good
as long as no small parts of the impression break
off and get lost. In the case of undercuts, the
hardened material must be broken and put to-
gether again. Plaster impressions can be stored
indefinitely. The material for die casting is also
gypsum. Before pouring in the die gypsum, the
impression must be disinfected, watered, and
treated with a release agent. The separation of
impression and die gypsum is difficult, and the
surface of the die can be damaged during this
procedure.
Plaster of Paris is used for functional and
anatomic impression taking of the edentulous
jaw and fixation impression of restorations. It is
rarely used for impressions since the introduction
of alginate and elastomers. The procedure is
unpleasant for the patient. Another use is fixation
during determination of the positional jaw
relation.
6.2.2. Zinc Oxide – Eugenol Pastes
The reactive components ZnO and eugenol
(80 – 96 wt %) are supplied as two pastes, which
are adjusted in consistency by oils (olive oil,
mineral oil) and fillers (talc, kaolin, rosin, vase-
line). Zinc acetate and magnesium chloride are
used as accelerators for the formation of zinc
eugenolate. Addition of a few drops of water
during mixing enhances setting. Irritation of
tissue by eugenol is possible. Impressions are
taken from the wet mucosa with individual im-
pression trays (functional impression with thin
layers of paste; unwanted high-detail reproduc-
tion to avoid micromechanical influences on the
mucosa by the prosthesis since the details espe-
Vol. 11
cially those of the oral mucosa change rapidly).
During removal from undercuts, plastic defor-
mation of the impression occurs. Impressions can
be disinfected and stored for a long time. The die
material is gypsum. After setting of the die
gypsum, the paste can be softened by immersion
in water (70 ! C) and pulled off. Zinc oxide pastes
are rarely used nowadays (compression impres-
sion of the mucosa).
6.2.3. Resins
Self-hardening methyl methacrylate/poly(meth-
yl methacrylate) systems are no longer used
today for biological and methodological reasons.
Polymeric materials for temporary rebasing of
dentures can be used as impression materials to
give a working model for a new denture. These
materials consist of a polymer bead powder of
higher acrylates [poly(ethyl methacrylate)],
which is swelled for a few minutes in a mixture
of phthalate ester and alcohol to give first a
flowable and then a stable gel, without a setting
reaction taking place. The mass reacts on short
term loading with rebound (elasticity), and on
long term loading with flow (plasticity).
6.2.4. Thermoplastic Impression
Materials
Thermoplastic impression materials were for-
merly composed of natural materials (copal,
shellac, colophonium, mastics, sandarac resin,
carnauba wax, raw rubber). Today mainly syn-
thetic resins, waxes, and fatty acids (stearic,
palmitic, and oil acids) are used. Added to this
are fillers and colors. The masses are reversibly
plastified in a water bath or by a flame. They can
be disinfected. Gypsum is used as die material.
Thermoplastic materials belong to the oldest
impression materials. Today their market share
is low.
Thermoplastic impression compounds consist
of resin, fatty acid, and filler in a ratio of 2/1/3.
The usual filler is magnesium silicate (talc). The
necessary plasticity for impression taking is
reached at 50 – 45 ! C. Hardening takes place
above 37 ! C. At room temperature the materials
remain rigid, even under pressure. Today these
materials are used in dentistry only as accessories
Vol. 11
during impression taking (individualization of
impression trays).
Wax/resin materials contain 70 – 80 wt %
synthetic resins, 15 – 25 wt % hard paraffin, par-
affin oil, and fillers. Some products contain metal
powders to enhance heat capacity. At mouth
temperature the materials are flowable under the
pressure from the soft tissues of the mouth (func-
tional impression), and rigid at room temperature
and pressureless storage.
Gutta-percha is the trans isomer of natural
rubber. Impression materials contain 60 wt %
gutta-percha, resins (25 wt %), and fillers
(15 wt %). Gutta-percha is occasionally used for
special impression tasks for removable prosthe-
ses and in maxillofacial prosthetics.
7. Dental Waxes
Waxes are used in rather large quantities in
various dental laboratory and clinical proce-
dures. Different types of waxes are required for
various applications. The differences relate
chiefly to softening behavior and hardness, and
the characteristics desired are usually obtained
by blending natural and synthetic waxes. Waxes
are not chemically uniform materials. They are
defined only by their similar properties.
Natural waxes are obtained either from ani-
mals, mostly insects, or from minerals. In the
dental literature, the following natural compo-
nents are often cited: paraffin, ceresin, carnauba
wax, candelilla wax, and beeswax.
Synthetic waxes, waxlike materials, and ad-
ditives are often added to the natural waxes.
Among these, the most important synthetic
waxes are polyethylene wax, polyoxyethylene
glycol wax, and esters of long-chain aliphatic
alcohols and organic acids.
Various additives, e.g., resins, rosin, dammar,
myricyl palmitate, or stearates, are added to
special-purpose waxes. Coloring agents, usually
fat-soluble dyes, are dissolved in dental waxes to
differentiate the various types and to approxi-
mate the natural color of the gingiva and the
teeth.
Most of the waxes and waxlike substances can
be melted together to form mixtures that do not
separate when cooled. In this way, any special
dental wax required for specific dental laboratory
and clinical applications can be made.
Dental Materials 137
Dental waxes are generally used after being
heated to a softened or liquid state. Below the
melting point, a solid – solid change occurs in
the crystal lattice; a wax should be molded above
this temperature to avoid internal stress which
can result in distortions of the pattern. The ad-
vantages of waxes include easy workability,
good polishability, broad softening range, low
viscosity when melted, hydrophobic behavior,
and clean burnout. Among the disadvantages of
waxes are high thermal expansion, formation of
internal stresses, solid – solid transition, and low
hardness at room temperature.
Some dental waxes are used as material for
patterns in the lost-wax technique. This tech-
nique, also called the indirect technique, involves
fabrication of a wax pattern, embedding it in an
investment, burnout of the wax, and casting a
molten alloy in the hollow space. Inlays, crowns,
bridges, and the metal framework of partial
dentures are constructed in this manner. Other
types of waxes are used for bite registration,
construction of trial baseplates for complete
dentures, and temporary connection of fragments
of a broken denture before a repair procedure.
Many types of dental wax are marketed. Their
names indicate the uses for which they are
intended:
* modeling wax
* casting wax, burnout wax, inlay wax
* carding wax, setup wax
* bite registration wax
* blockout wax
* baseplate wax
* correction wax
* sticky wax, adhesive wax.
Because of their particular importance, dental
inlay casting wax and baseplate wax are treated
in more detail in the following paragraphs.
Dental Inlay Casting Wax. Inlay wax is
used to produce cast inlays. It is available in two
slightly different types: type I for direct modeling
in the mouth and type II for indirect modeling on
the die. Both wax qualities must (1) burn out
without residue, (2) have minimum thermal con-
traction, (3) be carved without chipping and
flaking, and (4) be intensely colored. Type I must
not solidify at 37 ! C but should flow easily at
43 ! C, whereas type II must still not soften at
138 Dental Materials
34 ! C and should flow easily at 40 ! C. Inlay
waxes contain a larger fraction of hard waxes,
such as carnauba wax, than the related baseplate
waxes.
Dental Baseplate Wax (Modeling Wax).
Baseplate wax is preferred in the production of
dentures to shape the denture base that is later
made from resin. The waxes are mixtures of
paraffin and beeswax with minor additions of
carnauba wax. The modeling waxes are classified
into three types which differ slightly in their
softening range and hardness. The following
requirements must be fulfilled: easy removal
with boiling detergent solution, low thermal
contraction, easy trimming and carving, and
glossy surface after gentle flaming.
8. Other Model and Die Materials
The most important model material is dental
stone (model gypsum); this is treated in detail
in Chapter 9. In this chapter, only model materi-
als other than gypsum are treated briefly; these
materials, however, are much less important than
gypsum.
Die Cements. The composition of die ce-
ments is similar to that of the silicophosphate and
stone cements described in Chapter 4. As a result
of their poor physical properties, these materials
are rarely used today.
Only small amounts of powder and liquid
(acid) can be mixed to form a thick, homoge-
neous, plastic mix. For this reason, only small
models or single tooth dies can be fabricated. The
advantages of die cements are their high rigidity
and good scratch resistance. Their disadvantages
are poor flow rate, contraction during setting and
storage, and the fact that they can be used only
with compound impression materials.
Resins. Various resins which cure at room
temperature are used as binders for chemically
inert fillers. Methyl methacrylates, polyesters,
epoxies, and ethylenimine resins are available
commercially. Very fine quartz powder and met-
al powders are used as fillers; their chief function
is to reduce shrinkage during setting. The mate-
rials are available as powder and liquid or as two-
paste systems.
Vol. 11
The materials are rarely used because of their
disadvantages. Resins are very rigid and provide
good reproduction of details. However, they
require a long setting time, some products are
sticky after mixing is complete, they are not
compatible with all impression materials, and
they contract during setting.
Metallic Materials. The amalgams used as
die materials are identical with the silver amal-
gams described in Chapter 2. They cannot be
used with elastic impressions because they must
be placed by plugging. Hardness and absence of
shrinkage are good; detail reproduction is satis-
factory. Their use is restricted to small models or
dies.
Electrolytic plating of the impressions with
copper or silver and, more rarely, with nickel
produces very good models and dies. However,
plaster, alginate, and hydrocolloid impression
materials cannot be electroplated. The impres-
sion, made conductive by dusting with metal or
graphite powder (dental compound), is sus-
pended in an aqueous electrolyte as the cathode.
The main components of the electrolyte are
copper sulfate or silver cyanide, respectively.
Pure copper or silver is used as the anode.
Appropriate selection of the bath and the electri-
cal current leads to development of a thin, but
smooth and homogeneous, coating of the impres-
sion. Detail reproduction, precision, and rigidity
of the models are very good. To prevent defor-
mation during manipulation, dental stone is cast
into the plated impression. The only disadvan-
tage is the time required for the plating procedure
(up to 10 h).
9. Dental Gypsum Products
Gypsum materials have a wide spectrum of use in
dentistry. In addition to their use as model ma-
terials, they also serve as impression plasters
(Section 6.1.1), as a component of alginate im-
pression materials (Section 6.2.2), and as a com-
ponent of investment materials (Chap. 10). His-
tory, raw materials, phases of the CaSO4– H2O
system, natural and byproduct gypsum, and pro-
duction of calcium sulfate hemihydrate are de-
scribed elsewhere (! Calcium Sulfate) [62].
Dental gypsum products are classified by inter-
national standards:
Vol. 11
Type 1: Impression plaster
Type 2: Dental plaster
Type 3: Dental stone
Type 4: Dental stone, high strength
Use as Model Material. A dental impres-
sion is a negative reproduction of the teeth and
the oral tissues. By pouring a suitable model
material into this negative form, the dental tech-
nician obtains a positive cast of the form and
relationship of the teeth and oral tissues. Dental
stone and high-strength dental stone are ideally
suited for high-precision mastercasts. Dental
plasters are suitable for study, repair, and refer-
ence casts.
Requirements. The requirements for such
a material depend on the purpose for which it
is used: type 2 dental plaster should be easy to
manipulate and show a smooth surface; type 3
dental stone and type 4 dental stone, high
strength should be easy to manipulate, be
compatible with common impression materials,
have a very good fluidity in the plastic phase
thus needing a short time for vibration, and
have a short setting time (max. 30 min). On
the other hand, the setting time must be long
enough to facilitate pouring of the impression
[62–64].
In addition to the requirements mentioned
above, the final model should show the finest
details; have a smooth surface without pores;
have sufficient strength, hardness, and wear re-
sistance; and have a constant volume (small
expansion is better than even minimal shrinkage)
[63], [64].
The requirements for hardness, compressive
strength, and the maximum linear setting expan-
sion are different for all four types of gypsum.
None of the model materials of type 2 – 4 can
fulfill perfectly all the requirements mentioned.
Dental stone high strength fulfills them best and
is therefore the most common model material for
casts used for the construction of inlays, crowns,
bridges and removable partial or full dentures
[63], [64].
Chemical Composition. Calcium sulfate
hemihydrate occurs in two phases: a and b (for
more details, see ! Calcium Sulfate). The com-
position of dental gypsum products are as
follows:
Dental Materials 139
. Type 1 impression plaster (see Section 6.2.1).
. Type 2 dental plaster consists of b-CaSO4
hemihydrate and modifiers.
. Type 3 dental stone consists of a-CaSO4 hemi-
hydrate crystals with a small specific surface
and modifiers.
. Type 4 dental stone high strength consists of an
a-CaSO4 hemihydrate that has been dehy-
drated in an autoclave with special solutions
[65]. This type also contains modifiers, added
by the manufacturer to obtain the properties of
the final product required by national and
international specifications.
Typical ionic additives are potassium sulfate,
potassium citrate and sodium potassium tartrate.
Water-soluble melanine resins are used as non-
ionic additives to increase the fluidity of the
water – hemihydrate mixture. All these modi-
fiers influence the setting expansion, the setting
time, the hardness of the dental stone, and the
morphology of the dihydrate crystals. Potassium-
containing additives can produce crystals of syn-
genite (potassium calcium sulfate), which can
appear as efflorescences on the surface of dental
casts [66–68].
The setting time [69–72] can be shortened by
(1) addition of inorganic acids and their salts,
such as calcium sulfate dihydrate, 3 % sodium
sulfate; 2.5 % sodium chloride, or 2 – 3 % po-
tassium sulfate; (2) intensive and extended spa-
tulation (excessive spatulation destroys the crys-
tal structure and decreases strength); and (3) low
water-to-powder ratio.
The setting time can be prolonged by (1)
addition of organic acids and their salts as well
as the presence of organic colloids such as dried
blood or gelatin; (2) addition of salts of phos-
phoric and boric acids; (3) addition of more than
3 % of sodium chloride; (4) presence of nitrate or
citrate;and (5) high water-to-powder ratio [62].
The setting reaction does not completely con-
vert the calcium sulfate hemihydrate to dihy-
drate. Residual hemihydrate is present in the
structure of fully set casts [66].
Physical Properties. The strength of hard-
ened calcium sulfate dihydrate is directly propor-
tional to its density; therefore, the strength de-
pends on the ratio of water to hemihydrate powder
and on the porosity of the hardened plaster or
stone. Dental a-CaSO4 hemihydrates (stones)
140 Dental Materials Vol. 11

need small amounts of water for mixing and
fluidizing and therefore have a high density and
great strength; however, they are brittle. The
strength of calcium sulfate dihydrate also depends
on the humidity of the atmosphere during storage.
The hardness of rehydrated type 3 dental
stone and type 4 dental stone high strength in-
creases with the time of storage. Chemically
produced gypsum reaches its final hardness after
4 d, whereas natural gypsum needs 6 d. Due to
sedimentation, the hardness of a cast is greater on
the bottom than on the surface, where more pores
are located [62], [73–75].
The hardness can also be influenced by con-
tact with some impression materials. Contact
with hydrocolloids, condensation-cured sili-
cones, and polyethers lowers the hardness. This
tendency can be reduced if the impression with
the mixed hemihydrate is stored at 95 % R.H. for
30 min or during the entire setting period [62].
Volume Change. The absolute volume of a
mixture of CaSO4 hemihydrate and water first
decreases when CaSO4 dihydrate is formed. The
contraction can only be measured for a short time
after mixing [71], [76–79]. As soon as the rehy-
drated gypsum hardens, expansion starts. The
thermal expansion during setting is reversible,
but the setting expansion is almost irreversible.
This setting expansion is influenced by (1) the
water-to-powder ratio: the lower the water con-
tent, the greater is the expansion; (2) the presence
of chemicals: for example, potassium sulfate
lowers the expansion but also the strength; (3)
the climate: storage of a model of type 4 dental
stone high strength after the removal of the
impression at 23 ! C and 50 % relative humidity
results in a contraction of about 0.05 % of its
highest setting expansion within 7 d (Figs. 10
and 11); and (4) spatulation: high intensity and
long time of spatulation of the water – hemihy-

Figure 10. Measurement of dimensional change of dental stone

A: In a closed extensometer at 23 ! C
B: With side plates removed (23 ! C, 50 % relative humidity) 2 h after start of mixing
C: Immersion in water bath for 5 min after 24 h a) Dial gauge; b) Movable front plate; c) Removable side plates;
d) Polytetrafluoroethylene (PTFE) sheet
Vol. 11 Dental Materials 141

[64]. The material of the surface of the extensom-

eter in contact with the water – dihydrate mixture
can influence the setting expansion [97].

Quality Standards. The Technical Com-

mittee 106 of the ISO has published ISO Standard
6873 (1998) Dental Gypsum Products. This stan-
dard also specifies the corresponding test
methods.
Table 8 shows the ISO requirements for
four different types of dental gypsum products.
Table 9 compares the results obtained for various
commercial products.

Storage and Packaging. Types 3 and 4

Figure 11. Dimensional change of dental stone model (at
23 ! C and 50 % rel. humidity) as a function of storage
conditions [62], [76]
A: Storage in a closed extensometer
B: Storage at 23 ! C and 50 % relative humidity
C: Immersion in water bath for 5 min and subsequent stor-
age as in B
For experimental conditions of A, B, C, see Figure 10.
drate mixture increase the expansion of type 3
and type 4 dental stone.
The results of the setting expansion depend on
the method and time of measurement (Figs. 10
and 11). The dental gypsum products are mea-
sured in an extensometer with a length of 100 mm
stones should be packed and stored in protective,
moistureproof, and sealed containers. Each con-
tainer must at least be marked clearly with the
following information: name and/or trademark
of the manufacturer, type, lot number, date of
packaging, and date beyond which the material
should not be used without retesting when stored
under the recommended conditions: ca. 23 ! C
and not more than 50 % relative humidity.
Trade names: Type 2: Snow White Plaster
No. 1 (Kerr); Alabaster (Dr. B€ohme); Laboratory
Plaster (Whip Mix).
Type 3: Castone, R & R Lab Stone (Dentsply);
Coecal Buff, White (Coe Lab.); Octa-Mol

Table 8. Requirements and limits for types 1 – 4 dental gypsum products according to ISO Standard 6873. Working time and setting time are
measured from the first contact of hemihydrate and water; the setting time must be within ( 20 % of the time given by the manufacturer

Setting time, Compressive

Pouring min Setting strength, N/mm2
Testing time, min expansion, %
Type consistency, mm min. min. max. max. min. max.

1 80 ( 4 1.25 2.5 5.0 0.15 4.0 8.0

2 75 ( 4 2.5 6.0 30.0 0.30 9.0
3 30 ( 3 3.0 6.0 30.0 0.20 20.0
4 30 ( 3 3.0 6.0 30.0 0.15 35.0

Table 9. Physical properties of some commercial type 4 dental stones, high strength

Linear setting Compressive

Water-to-powder expansion, % strength, N/mm2 Hardness, N/mm2
Product ratio, cm3/g (ISO 6873) (ISO 6873) (DIN 13 911) (1976)

Begodur 0.23 0.13 40 160

Fujirock 0.20 0.10 40 240
Geostone 0.23 0.10 35 190
Gilstone 0.23 0.13 43 185
Silky Rock 0.22 0.11 40 190
Tewestone 0.23 0.10 43 200
Vel-Mix Stone 0.23 0.14 40 185
142 Dental Materials
(Heraeus-Kulzer); Modelit (Dr. B€ohme); Micro-
stone, Quickstone (Whip Mix).
Type 4: Duralit (DeguDent); Duroc (Dents-
ply); Begodur (Bego); Octa-Stone (Heraeus-
Kulzer); Gilstone (Giulini); Silky-Rock (Whip
Mix); Super-Cal Dental Stone (Coe Lab.); Te-
westone (Kettenbach); Vel-Mix (Kerr).
10. Dental Investments
An investment is generally a powder mixture
which can be mixed with a liquid to give a
flowable paste that sets in a given time. The
refractory material allows heating above
1100 ! C. These properties make the material
suitable as a mold material for alloy casting.
In dental technology a model is made from an
impression that reproduces the teeth. The wax
pattern (or resin, adapter cap) is shaped on this
model. The pattern is removed from the model
and provided with sprues on a base former and a
casting ring. The mixed investment material is
then poured into the casting ring. After hardening
of the investment, the mold is heated to burn out
the wax model. The casting mold is brought to the
final temperature required by the particular alloy.
After casting the object is divested and is ready to
be worked on.
Classification. Investments can be classi-
fied according to the nature of the bonding mate-
rial (gypsum- or phosphate-bonded) or the pur-
pose for which they are produced (Co – Cr
castings, precious metal castings, soldering of
metallic parts, ceramic pressure technique).
Requirements. Investment casting materi-
als should fulfill the following requirements:
. Expansion control: diluting the liquid compo-
nent of phosphate-bonded investment materi-
als with distilled water allows the expansion of
an investment to be controlled in a way that the
contraction of the particular casting alloy is
compensated
. A suitable setting time
. Creamy consistency during investment
. Production of a smooth surface and reproduc-
tion of fine details
. No cracking during heating and on impinge-
ment of the molten alloy
Vol. 11
. Compatibility with the alloys
. Keeping the high thermal expansion during the
entire time of casting and reversible thermal
expansion on cooling
. Easy removal from the cast object
. A possible additional requirement is suitability
for the rapid-burnout method.
Chemical Composition. Casting invest-
ment materials consist of bonding and refractory
materials. The refractory materials such as silica,
usually quartz or cristobalite or a mixture thereof
are responsible for the thermal expansion.
a-Cristobalite changes reversibly into b-cristo-
balite, and a-quartz into b-quartz. These two
crystal structure transformations result in the
reversible thermal expansion of an investment.
Standard investments need time for these trans-
formations to take place without formation of
cracks; hence, holding times at 270 and 573 ! C
are needed during the heating process.
Gypsum-Bonded Investments. The bond-
ing material is a-calcium sulfate hemihydrate
CaSO4 ' 0.5 H2O, which is converted to calcium
sulfate dihydrate CaSO4 ' 2 H2O by mixing with
water. The excess water is vaporized during
initial heating to about 100 ! C, and above this
temperature water of crystallization is driven out
of the investment. After reaching a temperature
of 150 ! C, gypsum-bonded investments either
show a slight thermal contraction or remain
unchanged up to 225 ! C. At higher temperatures,
the presence of silica dominates the thermal
expansion. Gypsum-bonded investments should
not be heated to temperatures exceeding 700 ! C.
Beyond that point, gypsum decomposes in the
presence of silica to liberate sulfur dioxide, which
causes porosity and corrosion of the casting.
2 CaSO4 ! 2 CaOþ2 SO2 þO2
Expansion control of gypsum bonded invest-
ments is achieved by varying the mixing ratio
with water.
Phosphate-Bonded Investments. High-
temperature investments require a bonding ma-
terial other than gypsum. This bonding material
consists of magnesium ammonium phosphate or
a soluble acid phosphate such as ammonium
dihydrogenphosphate and a metal oxide such as
Vol. 11
magnesia. These materials are mixed with an
aqueous silica sol. The following simplified
chemical reaction occurs during setting at room
temperature and gives the investment the green
strength before heating:
ðNH4 ÞH2 PO4 þMgOþ5 H2 O ! MgNH4 PO4 '6 H2 O
The next reaction takes place during heating,
water and ammonia are evolved above 200 and
300 ! C, respectively.
2 ðMgNH4 PO4 '6 H2 OÞ ! Mg2 P2 O7 þ13 H2 Oþ2 NH3
The silica-catalyzed decomposition into mag-
nesium diphosphate increases the strength and
hardness of the phosphate-bonded investment.
By heating above 1000 ! C with MgO surplus the
following reaction takes place:
Mg2 P2 O7 þMgO ! Mg3 ðPO4 Þ2
Physical Properties. The most important
physical property of a dental investment material
is expansion. The expansion is the sum of setting
and thermal expansions and is responsible for the
outstanding accuracy of dental restorations.
Setting Expansion. The setting of the phos-
phate-bonded investments is accompanied by the
evolution of heat. At the end of the reaction
process, the temperature reaches a maximum of
55 – 80 ! C. This temperature increase affects
the setting expansion. A standardized method
for measurement of the setting expansion is
presently under discussion. The setting expan-
sion constitutes about 30 – 50 % of the thermal
expansion and is caused by the reaction of the
bonder. The bonder transformation separates the
quartz and cristobalite grains and the result is an
increase in volume. This process is intensified by
mixing the powder with a special liquid and
causes aqueous silica particles to crystallize to
long needles.
The setting expansion of gypsum-bonded in-
vestments is based on the same principles as for
gypsum products in Chapter 9.
Thermal Expansion. When dental alloys
are cast, they contract on cooling. For this reason,
thermal expansion is very important for dental
Dental Materials 143
investments and should compensate for the
shrinkage of the casting alloys; however, the two
materials have different thermal contraction
curves. The thermal expansion of the investment
materials depends on their composition and, in
the case of phosphate-bonded investments, on the
dilution of the liquid component and the particle
size of the silica. The thermal expansion curves
for quartz and cristobalite are very much differ-
ent. Moreover, both silica modifications show a
phase transition, each at a different temperature:
quartz at 573 ! C and cristobalite at 200 –
270 ! C. All modifications of silica show a break
in their expansion curves. Therefore, the thermal
expansion curves for investment materials are
very complicated.
Setting time of phosphate bonded investment
materials is dependent on the reaction time of the
two bonding materials and consequently on their
mixing ratio and their grain size. Gypsum-bond-
ed investment materials include small amounts of
chemical additives which influence the setting
time.
Hardness. All dental investments need en-
ough hardness to resist the high temperatures and
the casting impact.
Quality Standards. The classification and
requirements for investment materials together
with the corresponding test methods are de-
scribed in the standards ISO 9694 (Dental Phos-
phate-Bonded Casting Investments, 1996) and
ISO 7490 (Dental Gypsum-Bonded Casting In-
vestments 2000).
Application. In general, the instructions of
the manufacturer should be strictly followed for
optimum results. Gypsum-bonded investment
materials should not come into contact with
phosphate-bonded investment materials. For
gypsum- and phosphate-bonded investment ma-
terials, the use of separate mixing bowls and
spatulas is necessary. Standard investment ma-
terials need preheating with holding times to
withstand the quartz and cristobalite phase tran-
sitions without cracking. Rapid-burnout invest-
ment materials can be preheated in an oven at the
final temperature. Exact ratios of the bonding and
the silica materials and the use of special liquid
components are the reasons for these robust
properties. The advantages are that they do not
144 Dental Materials
require preheating in a controlled oven, have
shorter heating times, and save energy.
References
1 J. F. Bates, A. G. Knapton: ‘‘Metals and Alloys in
Dentistry,’’ Int. Met. Rev. 22 (1977) no. 3, 39 – 60.
2 G. Tammann, Z. Anorg. Allg. Chem. 107 (1919) 1 – 240.
3 H. Knosp, M. Nawaz, M. St€umke, Gold Bull. 14 (1981)
no. 2, 57 – 64.
4 R. M. German, Int. Met. Rev. 27 (1982) no. 5, 260 – 288.
5 R. L. Bertolotti, J. Am. Dent. Assoc. 108 (1984) no. 6,
959 – 966.
6 J. R. Kelly, T. C. Rose, J. Prosthet. Dent. 49 (1983)
no. 3, 363 – 370.
7 Cobalt, Monograph, edited by centre d’information du
cobalt, Bruxelles 1960.
8 H. Newesely, Naturwissenschaften 70 (1983) 324 –331.
9 W. Wagner, P. Tetsch: Deutscher Zahn€ arzte-Kalender
1986, Hanser Verlag, M€unchen 1986, pp. 45 – 58.
10 P. J. Branemark, G. A. Zarb, T. Albrektsson: Tissue
Integrated Prostheses Osseointegration in Clinical Den-
tistry, Quintessenz-Verlag, Berlin 1985.
11 J. Wirz: Deutscher Zahn€ arzte-Kalender, Hanser Verlag,
M€ unchen, 1983, pp. 52 – 66.
12 R. V. Williams, C. E. Ingersoll, Phillip Journal f€ ur
restaurative Zahnmedizin 1 (1984) 33 – 39.
13 W. I. Ferrier: Gold Foil Operations, University of
Washington Press, Seattle 1959.
14 K. Dreyer Jørgensen: Amalgame in der Zahnheilkunde,
Hanser Verlag, M€unchen-Wien 1977.
15 D. B. K. Innes, W. V. Youdelis, J. Can. Dent. Assoc. 29
(1963) 587 – 593.
16 Special Metals Corp., US 3 980 472, 1975 (K. Asgar,
S. H. Reichman).
17 Sybron Corporation, US 3 985 558, 1975 (H. H.
Simpson).
18 R. Kropp, H. Haußelt, Quintessenz 34 (1983) 1027 –
1031.
19 A. Knappwost, E. Gura, D. Fuhrmann, A. Enginalev,
ZWR 94 (1985) 131 – 139.
20 E. Lugscheider, G. Jangg: Z. Metallkd. 62 (1971) 548 –
551.
21 P. A. Steinberg, K. H. Schmitz: Grundriß der Dental-
Keramik, Verlag Neuer Merkur, M€unchen 1968.
22 Ch. Hahn, D. Rothemund: ‘‘Dentalkeramik,’’ in: Hand-
buch der Keramik, Verlag Schmidt GmbH, Freiburg
i. Br. 1977 and 1981, Gruppe II L, pp. 1 – 12.
23 J. W. McLean (ed.): Dental-Keramik, Quintessenz Ver-
lags-GmbH, Berlin 1984.
24 Permadent Products Corporation, US 3 052 982
(¼ DE 1 441 336), 1962 (M. Weinstein, S. Katz,
A. B. Weinstein).
25 J. Jach, A. Joshi, D. Sengupta, Semicond. Insul. 5 (1980)
111 – 122.
26 P. Dorsch, Dental Labor XXXI (1983) 1237 – 1242.
Vol. 11
27 K. Krumbholz, Quintessenz Zahntech. 9 (1983) 1175 –
1179.
28 Johnson & Johnson Dental Products Company, EP-
A 0 124 298, 1984 (C. Panzera).
29 J. W. McLean, T. H. Hughes, Br. Dent. J. 119 (1965) .
30 J. Schmidseder, ‘‘Hi-Ceram,’’ Phillip Journal f€ ur res-
taurative Zahnmedizin 3 (1986) 226.
31 Corning Glass Works, US 3 839 055, 1974 (D. G.
Grossmann).
32 Dentsply International Inc., EP-A 0 154 137, 1985 (J. J.
Blair, R. C. Shue).
33 A. Wohlwend, P. Sch€arer, ‘‘Die Empress-Technik. Ein
neues Verfahren zur Herstellung von vollkeramischen
Kronen, Inlays und Facetten,’’ Quintessenz Zahntech. 16
(1990) 996.
34 H. Claus, ‘‘Vita In-Ceram, ein neues Verfahren zur
Herstellung oxid-keramischer Ger€uste f€ur Kronen und
Br€ucken,’’ Quintessenz Zahntech. 16 (1990) 35.
35 J. Becker, D. Heidemann, ‘‘Entwicklungsstand und Pro-
bleme des Einsatzes von CAD/CAM-Systemen,’’ Dtsch.
Zahnaerztl. Z. 48 (1993) 611.
36 A. Groß, Chem. Uns. Z. 13 (1979) 142.
37 Kulzer & Co GmbH, DE 737 058, 1983.
38 W. Westermann, H. Meiners, Zahn€ arztl. Welt 84 (1975)
531.
39 Degussa, DE 975 072, 1941 (A. E. Czapp, E. Schnebel,
A. G€olz).
40 H. Bredereck, et al., Chem. Ber. 87 (1954) 129; 88 (1955)
438; 89 (1956) 731.
41 H. Marx: ‘‘Prothesenkunststoffe und ihre Verarbeitungs-
verfahren,’’ in Fortschritte in der zahn€
arztlichen Prothe-
tik und Werkstoffkunde, vol. 1, Hanser Verlag, M€unchen
1980, pp. 344 – 356.
42 A. Schmidt, ‘‘Die Geschichte der Methacrylate in der
Stomatologie,’’ Zahntechnik (DDR) 19 (1978) 436.
43 H. Marx: ‘‘Kunststoffz€ahne,’’ in Fortschritte in der
zahn€arztlichen Prothetik und Werkstoffkunde, vol. 1,
Hanser Verlag, M€unchen 1980, pp. 358 – 360.
44 H. Marx: Fortschritte in der zahn€ arztlichen Prothetik
und Werkstoffkunde, vol. 1, 1980, H. Marx: ‘‘Verblen-
dkunststoffe und ihre Verarbeitungsverfahren,’’ in For-
tschritte in der zahn€arztlichen Prothetik und Werkstoff-
kunde, vol. 1, vol. 2, Hanser Verlag, M€unchen 1980,
1984; pp. 362 – 367 (vol. 1); pp. 252 –259 (vol. 2).
45 M. Hofmann, J. Hofmann, ‘‘Eine neue Kunststoffver-
blendtechnik,’’ Quintessenz Zahntechnik 7 (1981) 1101.
46 H. R. Stanley, R. L. Bowen, J. Folio, ‘‘Compatibility of
various materials with oral tissues’’ II: ‘‘Pulp responses
to composite ingredients,’’ J. Dent. Res. 58 (1979)
1507.
47 R. Musil, H.-J. Tiller, ‘‘Die molekulare Kopplung der
Kunststoff-Verblendung an die Legierungsoberfl€ache,’’
dentallabor 32 (1984) 1155.
48 Kulzer, US 4 600 390, 1986 (R. G€obel, R. Musil, H.-J.
Tiller, St. Oppowsky, A. Schmidt, R. Janda). Bard Ltd.,
DE 3 403 874, 1986 (D. E. Cross).
49 M. Atsuta, A. K. Abell, D. T. Turner, N. Nakabayashi,
M. Takeyama, ‘‘A new coupling agent for composite
Vol. 11
materials 4-methacryloxyethyltrimellitic anhydride,’’
J. Biomed. Mater. Res. 16 (1982) 619.
50 H. W. R. Schaefer, ‘‘Fortschritte auf dem Gebiet der
Kunststoff-F€ullungen-F€ullungsmaterialien mit feinsttei-
ligem Siliciumdioxid als anorganischem F€ullstoff,’’
Quintessenz 32 (1981) 1.
51 H. Newesely, ‘‘Zemente, Composites, Adh€asive und
Kleber,’’ in Fortschritte in der zahn€arztlichen Prothetik
und Werkstoffkunde, vol. 1, Hanser-Verlag, M€unchen
vol. 1, 1981, pp. 392 – 411. H. Newesely, R. Janda:
vol. 2, 1984, pp. 284 – 303.
52 R. L. Bowen, US 3 066 112, 1962; US 3 179 623,
1965; 3 194 783, 3 194 784, 1965.
53 J. Anderson et al.: Applied Dental Materials, Blackwell
Science Ltd., Oxford 1998.
54 R. G. Craig: Restorative Dental Materials, 10th ed.,
C. V. Mosby Co., St. Louis 1996.
55 E. H. Greener, J. K. Harcourt, E. P. Lautenschlager:
Materials Science in Dentistry, Williams & Wilkins Co.,
Baltimore 1972.
56 F. J. Harty, D. H. Roberts: Restorative procedures for the
Practicing Dentist, J. Wright and Sons Ltd., Bristol
1974.
57 K. K€ orber, K. Ludwig: Zahn€ arztliche Werkstoffkunde
und Technologie, 2nd ed., Thieme-Verlag, Stuttgart
1993.
58 R. W. Phillips: Skinner’s Science of Dental Materials,
9th ed., Saunders, Philadelphia 1991.
59 J. Viohl: ‘‘Abformwerkstoffe,’’ in K. Eichner, H. F.
Kappert (eds.): Zahn€ arztliche Werkstoffe und ihre Ver-
arbeitung, 6th ed., vol. 1, H€uthig Verlag, Heidelberg
1996.
60 B. W€ ostmann: ‘‘Abformmaterialien,’’ in H. Meiners,
K. M. Lehmann (eds.): Klinische Materialkunde f€ ur
Zahn€ arzte, Hanser Verlag, M€unchen – Wien 1998.
61 Deutsches Institut f€ur Normung e.V. (ed.): DIN-
Taschenbuch 267 Zahnheilkunde; Werkstoffe. Normen,
Gesetze, Richtlinien, 1st ed., Beuth Verlag, Berlin –
Wien – Z€ urich 1997.
62 G. Franz: Dentalgipse, Hanser Verlag, M€unchenWien
1981.
63 Deutsches Institut f€ur Normung (DIN): DIN 13 911
(Dental Gypsum).
64 International Organization for Standardization (ISO):
ISO 6 873 (Dental Gypsum Products).
65 G. Giulini, DE 1 157 128, 1968.
66 U. Sondermann, K. M. Lehmann (eds.): Dentalgipse
und ihre Anwendung, Philipps Universit€at, Marburg
1998.
67 J. Wolf, U. Sondermann, K. M. Lehmann: ‘‘Der Nach-
weis verschiedener Kristallphasen an Gipsoberfl€achen
mittels R€ontgendiffraktometrie,’’ Interdiszipl. J. Proth.
Zahnheilk. 1 (1998) 175 – 178.
68 K. M. Lehmann, J. Wolf: ‘‘Der Einfluß von Stellmitteln
auf das Abbinden eines a-Calciumsulfat-Subhydrates,’’
Interdiszipl. J. Proth. Zahnheilk. 1 (1998) 425 – 430.
69 K. Dreyer Jørgensen, A. S. Posner, J. Dent. Res. 38
(1959) 491.
Dental Materials 145
70 G. Franz: ‘‘Gips,’’ in K. Eichner (ed.): Zahn€ arztliche
Werkstoffe und ihre Verarbeitung, 4th ed., H€uthig Ver-
lag, Heidelberg 1981.
71 J. K. Harcourt, E. P. Lautenschlager, J. Dent. Res. 49
(1970) no. 3, 502.
72 D. C. Smith, J. Dent. Res 41 (1962) 1256.
73 W. Finger, Zahn€ arztl. Welt 81 (1972) 747.
74 F. A. Peyton, J. P. Leibold, G. Ridgley, J. Prosthet. Dent.
2 (1952) 381.
75 H.-J. Rehberg, G. Becherer, Dtsch. zahn€ arztl. Z. 9 (1954)
488.
76 G. Franz: Untersuchungen u€ber das Dimensionsverhal-
ten zahn€arztlicher Hartgipse, Hanser Verlag, M€unchen-
Wien 1978.
77 D. B. Mahler, Int. Dent. J. 5 (1955) 241.
78 H. Marx, Dtsch. Zahn€ arztl. Z. 31 (1976) 694.
79 H. H. van’t Hoff, E. E. Armstrong, S. Hinrichsen,
F. Weigert, G. Just, Z. Phys. Chem. Stoechiom. Ver-
wandschaftsl. 45 (1903) 257.
80 S. Halbach, Human & Experimental Toxicology 13
(1994) 496 – 501.
81 M. Walter, P. D. Reppel, K. B€oning, W. B. Freesmeyer,
J. Oral Rehabil. 26 (1999) 91 – 96.
82 A. H. Sherif, Egypt Dent. J 41 (1995) 1067 – 1076.
83 B. S. Vence, J Prothet. Dent. 77 (1997) 444 – 449.
84 L. Pr€obster, J. Geis-Gerstorfer, A. Simonis, J. Setz,
H. Weber, Dent. Labor (M€ unchen) 39 (1991)
1073 – 1078.
85 P. Rammelsberg, R. van Kaldenkerken, P. Pospiech,
Dtsch Zahn€ arztl Z. 53 (1998) 844 – 848.
86 E. Wagner: Werkstoffkunde der Dental-Edelmetalle-
gierungen, Verlag Neuer Merkur, Munich 1980.
87 E. M. Wise: Palladium Recovery and Uses, Academic
Press, New York 1968.
88 Degussa AG, DE 11 83 247, 1962 (Wagner).
89 Degussa AG, DE 15 33 233, 1966 (Wagner).
90 Degussa AG, DE 27 55 913, 1977 (Knosp).
91 W. Groll, Thesis, Universit€at Erlangen, 1987.
92 E. Schmid, Thesis, Universit€at Stuttgart, 1987.
93 D. C. Smith, Biomaterials 19 (1988) 467 – 478.
94 K. J. Anusavice: Phillips’ Science of Dental Materials,
10th ed., W. B. Saunders Comp., Philadelphia PA, 1996,
p. 525 ff.
95 DE 174 558, 1903 (P. Steenbock).
96 K. Falck: Einf€ uhrung in die Werkstoffkunde f€ ur
Zahn€ arzte, Carl Hanser Verlag, M€unchen 1948.
97 NRDC, DE 2 061 513, (Priority GB: 1969) (A. D. Wil-
son, B. E. Kent).
98 A. D. Wilson, J. W. McLean: Glasionomerzement,
Quintessenz Verlags-GmbH, Berlin 1988.
99 R. G. Hill, A. D. Wilson, Glass Technol. 29 (1988)
150 – 158.
100 ESPE, EP 0 023 013, (Priority: 1979, DE) (W. Schmitt,
R. Purrmann, P. Jochum, O. Gasser).
101 S. Crisp, A. D. Wilson, J. Dent. Res. 55 (1976) 1023 –
1031.
102 ESPE, EP 0 024 056, (Priority: 1979, DE) (W. Schmitt,
R. Purrmann, P. Jochum, O. Gasser).
146 Dental Materials
103 NRDC, EP 0 340 016, (Priority: 1988, GB) (A. D.
Wilson, J. Ellis).
104 Albright & Wilson, GB 2 291 060, (1994) (C. E.
Wilde, M. J. Williams).
105 A. D. Wilson, J. M. Paddon, S. Crisp, J. Dent. Res. 58
(1979) 1065 – 1071.
106 R. G. Hill, J. Mater. Sci. 28 (1993) 3851 – 3858.
107 A. J. de Gee, R. N. B. van Duinen, A. Werner, C. L.
Davidson, J. Dent. Res. 75 (1996) 1613 – 1619.
108 ESPE, DE 3 248 357, 1982 (J. W. McLean, O. Gasser).
109 R. Hickel, Dtsch. Zahn€ arztl. Z. 52 (1997) 572 – 585.
110 R. Frankenberger, J. Sindel, N. Kr€amer, Quintess. Int. 28
(1997) 667 – 676.
111 R. Guggenberger, R. May, K.-P. Stefan, Biomaterials 19
(1998) 479 – 483.
112 N. Kr€amer, M. Pelka, P. Kautetzky, J. Sindel, A.
Petschelt, Deutsch. Zahn€ arztl. Z. 52 (1997) 186 – 189.
113 K.-P. Stefan, J. Dent. Res. 77 (1998) Special Issue B, 688
(Abstract Nr. 454).
114 L. Forsten, Scand. J. Dent. Res. 98 (1990) 179 – 185.
115 A. Stassinakis, J. Gujer, B. Hugo, P. Hotz, Acta Med.
Dent. Helv. 1 (1996) 244 – 249.
116 E. Glockmann, C. Gehroldt, K. Triemer, Dtsch.
Zahn€ arztl. Z. 52 (1997) 668 – 672.
117 L. Forsten, Scand. J. Dent. Res. 99 (1991) 241 – 245.
118 H. Ngo, V. Marino, G. J. Mount, J. Dent. Res. 77 (1998)
Special Issue B, 641 (Abstract Nr. 75).
119 G. Schmalz, K.-A. Hiller, F. D€orter-Aslan, J. Mat. Sci.:
Mat. In Med. 5 (1994) 43 – 51.
120 L. M. Jonck, C. J. Grobbelaar, H. Strating, Clin. Mater. 4
(1989) 85 – 107.
121 L. M. Jonck, C. J. Grobbelaar, H. Strating, Clin. Mater. 4
(1989) 201 – 224.
122 G. Geyer, J. Helms, Adv. Biomater. 10 (1990) 529 – 535.
123 I. M. Brook, P. V. Hatton, Biomaterials 19 (1998) 565 –
571.
124 ESPE, EP 0 469 573, (Priority: 1990, DE) (O. Gasser,
R. Guggenberger).
125 J. W. McLean, A. D. Wilson, Br. Dent. J. 136 (1974)
269 – 276.
126 H. W. Seeholzer, Schweiz. Monatsschr. Zahnmed. 97
(1987) 344 – 347.
127 C. H€uskens, C. Matter-Gr€utter, F. Lutz, Schweiz. Mon-
atsschr. Zahnmed. 105 (1995) 216 – 221.
Vol. 11
128 F. Khoury, H. J. Staehle, Dtsch. Z. Mund Kiefer Ge-
sichtschir. 11 (1987) 351 – 355.
129 R. Mathis, I. L. Ferracane, J. Dent. Res. 66 (1987) 113
(Abstr. 51).
130 3M, US 5 130 347, 1991 (S. B. Mitra).
131 J. W. McLean, J. W. Nicholson, A. D. Wilson, Quiness.
Int. 25 (1994) 587 – 589.
132 M. B. Miller, Phillip J. 14 (1997) 385 – 386.
133 The Dental Advisor 14 (1997) Juni, 2.
134 J. Sindel, N. Kr€amer, R. Frankenberger, S. Bischoff,
J. Dent. Res. 77 (1998) Special Issue B, 928 (Abstract
2375).
135 Ernst M€uhlbauer KG, EP 0 219 058, (Priority: 1985,
DE) (J. Engelbrecht).
136 Dentsply, EP 0 621 028, (Priority: 1993, US) (C.-T.
Hunag, P. Hammersfahr).
137 H. J. Staehle: Calciumhydroxide in der Zahnheilkunde,
Carl Hanser Verlag, M€unchen 1990.
138 Hoechst, DE 1 006 125, 1954 (O. Fuchs, G. Wegner).
139 ESPE, EP 0 094 049, (Priority: 1982, DE) (P. Jochum,
O. Gasser).
Further Reading
J. F. McCabe, A. W. G. Walls (eds.): Applied Dental Materi-
als, 9th ed., Blackwell, Oxford 2008.
W. J. O’Brien: Dental Materials and Their Selection, 4th ed.,
Quintessence Pub. Co., Hanover Park IL 2008.
J. M. Powers, R. L. Sakaguchi, R. G. Craig: Craig’s Restor-
ative Dental Materials, 12th ed., Mosby, St. Louis MO
2006.
J. M. Powers, J. C. Wataha: Dental Materials, 9th ed., Mosby,
St. Louis, MO 2008.
J. A. Tesk, J. M. Antonucci, C. M. Carey, F. C. Eichmiller, J.
R. Kelly, N. W. Rupp, R. W. Waterstrat, A. C. Fraker, L.
C. Chow, L. A. George, G. E. Schumacher, J. W. Stans-
bury, E. E. Parry: Dental Materials, ‘‘Kirk Othmer Ency-
clopedia of Chemical Technology’’, 5th edition, vol. 8, p.
274–354, John Wiley & Sons, Hoboken, NJ, 2004,
online: DOI: 10.1002/0471238961.0405142020051911.
a01.pub2.