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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


preventive purposes (sealants for developmental
Dental materials are used for the replacement of pits and grooves in the biting surfaces of teeth and
destroyed or lost structures (hard tooth substance, athletic mouth guards to reduce forces applied to
teeth, soft tissues of the mouth, tissues of the head) teeth during contact sports).
and for the restoration of disturbed functions According to their handling dental material
(masticatory, phonetic, esthetic, physiognomic) can be grouped in the following way:
of the orofacial organ. They are involved in the
morphological, physiological, and psychological . Direct restorative materials, which are pro-
reconstitution of the patient (curative effect). At cessed in the mouth
the same time they prevent structural decay and . Indirect restorative materials, which are fabri-
functional failure (preventive effect). Their use cated outside the mouth
takes into account biological and technical as-
pects. This is documented by the large number of 1.1. Direct Materials
international standards (ISO). There is a require-
ment for chemical biocompatibility (lack of tox- Pure Gold. Gold foil can be formed into
icity, allergenicity, mutagenicity, cancerogeni- solid gold of nearly theoretical density by me-
city), functional biocompatibility (strength, chanically condensing it directly into a retentive
environmental resistance), and technical func- cavity preparation. By means of small-diameter
tionality (handling, ergonomics, economy). Some condenser tips, the gold is work-hardened to have
dental materials are incorporated permanently or properties comparable to a 90 % gold – 10 %
temporarily in the orofacial organ; legally, they copper cast alloy. Electrolytically produced pow-
are similar to medicinal products. Other materials dered gold containing 0.5 % calcium may be
are used for the production of tooth restorations substituted for gold foil. These restorations have
and do not come into contact with the patient’s low mechanical properties and are restricted to
tissues. From the standpoint of industrial hygiene small non-stress-bearing applications in posteri-
they must be completely harmless to the user or teeth because of aesthetics.
(dentist, dental technician, dental assistant).
There are may uses for dental materials: Silver Amalgam. Silver amalgam is sup-
plied as a powder consisting mainly of silver,
. Reconstruction of decayed tooth structure with a balancing amount of tin, copper, and
(enamel, dentin) by fillings and crowns minor elements. These amalgams are classified
. Replacement of missing teeth by partial or full as low-copper (< 6 %) and high-copper (13 –
dentures 30 %) types. The powder is mixed with mercury
. Surgical prostheses and epitheses in orofacial to form a plastic mass which is condensed into a
prosthetics retentive cavity preparation. The surface is
Vol. 11 Dental Materials 97

carved shortly after placement; depending on the polymer acid react; a similar reaction may occur
product, the surface may be finished and polished between the calcium from the tooth and the
immediately or at a second appointment. Amal- polymer acid to form an adhesive bond. Finishing
gam is used in posterior teeth because of its gray is delayed for 24 h because of the slow comple-
appearance and is successful in stress-bearing tion of the reaction. This method is most success-
restorations. In badly decayed teeth, amalgam ful for cervical restoration; its functions are to
may be retained by threaded metallic pins placed restore the contour of the tooth, thus increasing
into dentin, which extend into the amalgam. It periodontal health, and to reduce the sensitivity
can be used to build up the crown of a tooth (a of the tooth.
core) on which a cast restoration is placed. Composites have been used in posterior teeth,
but the lack of wear resistance has restricted their
Polymers and Composites. Difunctional application to situations in which aesthetics is
oligomers and monomers, usually mixed with essential. Composites with higher filler content
fillers, are used to fill developmental pits and and wear resistance have been developed, and
fissures in the occlusal surfaces of enamel to restoration of posterior teeth with composites has
prevent caries. Before placement, the enamel is increased.
etched with acid, rinsed, and dried. Etching Agents are available to bond enamel and
provides for mechanical retention of the sealant. dentin with composites. The bonding agents are
The sealants are formulated to be polymerized in organic compounds with a variety of functional
situ by a chemical-activated or light-activated groups. They are applied to the cavity preparation
free-radical mechanism. The treatment is most before the composite, but the adhesive bond is
successful on the teeth of children soon after weak.
eruption. Composites are used as cores in severely
Anterior teeth with small to moderate frac- broken-down teeth and, in combination with the
tures or decay can be restored with composites. acid-etch technique, as veneers on severely dis-
They contain an inorganic filler of various parti- colored or deformed anterior teeth.
cle sizes, as well as difunctional acrylate oligo-
mers and monomers. Composites are today only Cements. Cements are classed as luting ce-
rarely available as two pastes for the chemically ments (attaching a cast gold restoration to a tooth)
activated type and mostly as a single paste for the or base cements (support for an amalgam resto-
light-activated type. After cavity preparation, an ration). Chemically, they are classified as (1) zinc
adhesive is applied on enamel and dentin and phosphate, (2) zinc oxide – eugenol and mod-
polymerized. The peripheral enamel is etched ifications, (3) zinc polyacrylate, (4) glass iono-
with acid, rinsed, and dried. Equal volumes of the mer, or (5) resin and composite cements. The
chemically activated type are mixed, syringed or applications of cements are listed in Table 1.
packed into the preparation, and allowed to po- Zinc phosphate cement is supplied as a pow-
lymerize. For the light-activated type, the paste is der (mainly ZnO) and a liquid (mainly H3PO4 in
placed into the cavity preparation and polymer- water). The ratio of powder to liquid is higher for
ized by exposure to light. Setting occurs prompt- a base than for a luting cement. The acid – base
ly, and final finishing to proper contour is done. reaction is exothermic, and the cement is mixed
When the proper shade is used, the boundary on a cool glass slab to control the temperature.
between the restoration and the tooth is difficult The mix is then placed on the restoration and
to detect. tooth, and the excess is forced out when the
Cervical caries or eroded areas of teeth are restoration is seated. A base cement is stiffer
generally restored with glass ionomers. They and is packed into the bottom of the cavity
consist of a powder and a liquid (an acid-soluble preparation and contoured. It is acidic when
glass and an aqueous solution of polyacrylic placed, and the pulp is protected with a varnish
acids). The exposed dentin is cleaned, and an on the dentin. Cements have low thermal con-
adhesive is applied. Any peripheral enamel is ductivity and high stiffness and strength; they
etched with acid. The components are spatulated provide thermal insulation for the pulp and me-
to a thick paste and packed into the prepared area. chanical support for the restoration. Zinc phos-
Leached metal ions from the powder and the 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 Dental Materials 99

Auxiliary Materials). After the investment has must be done carefully so that minimal damage to
hardened, it is heated to remove the wax and to the wrought metal occurs.
expand the mold. Molten alloy is forced into the Stainless steel is also employed in the manu-
space occupied by the pattern, usually by cen- facture of small tapered files and reamers used to
trifugal force. The investment and metal are then clean out the root canals of infected teeth during
cooled, and the restoration is finished. endodontic treatment.
Gold casting alloys are of types 1 to 4 with Preformed wrought shell crowns of stainless
increasing copper and other non-noble metal steel, nickel – chromium, or tin- and aluminum-
content. Type 1 is soft and used for non-stress- based alloys are used for semipermanent and
bearing restorations; type 2 is stronger and used temporary restoration of children’s primary
for simple posterior stress-bearing restorations; teeth. They are supplied in a multitude of sizes
type 3 is still harder and stronger, and is used for for different teeth. The best size is selected,
complex posterior crown and bridge restorations; trimmed, and adapted to the correct shape. It is
and type 4, the strongest, can be used in remov- then cemented with a permanent or temporary
able partial dentures. Types 3 and 4 contain cement.
enough copper for their as-cast hardness to be Feldspathic, aluminous, and crystallizable
increased by heat treatment. glass ceramics are used for the preparation of
The price of gold has increased the use of full anterior crowns. In the first two, the crowns
palladium – silver, cobalt – chromium, and are built up on a die of the prepared tooth covered
nickel – chromium alloys for crowns and with platinum foil. Ceramic powder is mixed
bridges. They are generally harder and stronger with water, and the slurry is painted on the
than type 3 gold alloys. They have higher melting matrix. Water is removed by vibration, blotting,
points than gold alloys and must be cast in high- baking, and firing. The crown is built up initially
temperature investments. with more opaque ceramics; then more translu-
Removable partial denture frameworks are cent ceramics are used toward the surface. Char-
almost always cast from nickel – chromium, acterization results in a restoration that matches
cobalt – chromium or cobalt – chromium – the appearance of natural teeth. Aluminous cera-
nickel alloys because of their lower cost and mics have alumina added to the feldspar to im-
higher stiffness (about twice that of gold alloys). prove resistance to fracture.
Partial denture frameworks are so large that free- Ceramic crowns are retained with a dental
standing patterns distort during investing. Pat- cement. Because they are brittle and lack high
terns are formed on refractory investment models strength, ceramic crowns are used mainly on
of the upper or lower teeth. The pattern and the anterior teeth where appearance is primary.
model are then invested to produce the mold used Ceramics are used to manufacture artificial
in the casting process. Plastic base and artificial teeth for dentures. These teeth are held in position
teeth (Section Auxiliary Materials) are attached by acrylic polymers and by mechanical retention
to the framework to produce the denture. These of pins in anterior, and diatoric holes in posterior,
alloys have higher melting points and hardness, teeth. The teeth are available in a variety of
and lower density, than gold alloys and are more shades, sizes, types, and shapes.
difficult to finish.
Ceramics and Metal – Ceramic Combi-
Wrought Metals. Wrought wires of 18 – 8 nations. A thin metal coping is cast to fit the
stainless steel, cobalt – chromium – nickel, tooth. Special ceramics that bond to the metal are
nickel – titanium, and titanium – molybdenum applied to the outside surface. The completed
are used in orthodontics in biomechanical de- crown has a strong metallic substructure covered
vices to move teeth by the application of forces. with an aesthetic outer layer. These combinations
After treatment, these appliances are removed. have superior strength compared to ceramic re-
The stiffness of 18 – 8 stainless steel and co- storations and can be used for posterior as well as
balt – chromium – nickel is the highest, fol- anterior crowns and bridges.
lowed by titanium – molybdenum and then Metals that have been used are gold-, nickel-,
nickel – titanium. Fabrication of the appliances and palladium-based alloys. Feldspathic cera-
often involves soldering or spot-welding, which mics with matching thermal expansion properties
100 Dental Materials Vol. 11

are essential. They are also retained in the mouth artificial teeth are supported by a wax denture
with dental cements. base. Pressure is maintained on the mold until the
Full ceramic crowns and small bridges can be monomer has polymerized. The flask is then
made using press ceramics. In this process a removed from the appliance and the plastic base
ceramic pellet is heated to a soft stage and pressed is finished. A pour processing technique is some-
into a form inside of an investment material times used, in which a mixture of polymer and
similar to casting a metal crown. The material monomer is poured into the sectional mold.
is a glass ceramic reinforced by leucite crystals. The tissue-bearing surface of a denture may be
Another way to produce full ceramic crowns made of a soft polymer such as plasticized acrylic
and small bridges is to use aluminum oxide or an or a silicone rubber for patients who have special
aluminum oxide/zirconium oxide ceramic to problems wearing dentures.
build up the crown on a refractory die, loosely The facial surfaces of anterior metallic crown
sinter it so that it does not shrink, and infiltrate it copings may be coated with tooth-colored ac-
with a glass. For a more toothlike appearance it rylics for aesthetic reasons. The polymer is mixed
must be veneered with a veneering ceramic like a or delivered as a paste with diacrylate monomers
metal framework. having a low vapor pressure. They can be pro-
CAD/CAM techniques can also be used to cessed in an oven or cured by light or microwaves
prepare full ceramic restorations. When this without investing because of the low volatility of
technique is used to prepare frameworks from the monomers. Acrylic denture teeth are also
aluminum oxide or yttrium-stabilized zirconium manufactured by means of dough molding. They
oxide, even wide-span bridges can be made out of are available in a wide range of shades, types, and
full ceramic. The framework must be veneered geometries. They are softer and less wear resistant
with a veneering ceramic which has a thermal than ceramic teeth but can be chemically bonded
expansion coefficient that fits to the framework. to the acrylic denture base. Temporary restora-
Since milling of a framework out of densely tions are made directly in the mouth from
sintered zirconium oxide ceramic is time- polymer – monomer mixes, with the aid of an
consuming a computer technique is used to pre- impression. They are then retained with a tempo-
calculate sinter shrinkage and produce an en- rary cement until the permanent restoration is
larged framework out of presintered material. made.
The enlarged framework is then dense sintered Athletic mouth protectors are made by form-
to a fitting framework. ing in a vacuum, a sheet (3 mm) of polyethyl-
Ceramics are today only rarely used to manu- ene – poly(vinyl acetate) copolymer over a mod-
facture artificial teeth for dentures. These teeth el of the athlete’s upper teeth. After cooling, the
are held in position by acrylic polymers and by excess is cut away with scissors and the edges are
mechanical retention of pins in anterior, and flame-polished. When worn, these protectors
diatoric holes in posterior, teeth. The teeth are nearly eliminate oral injuries in contact sports.
available in a variety of shades, sizes, types, and
shapes.
1.3. Auxiliary Materials
Polymers. Acrylic polymers and copoly-
mers are used for partial and complete denture Impression Materials. Since diagnostic
bases, soft and hard denture liners, artificial and therapeutic measures in the oral cavity are
denture teeth, crown and bridge facings, and restricted, a working model must be created out-
temporary materials. They are usually processed side the mouth. This is done by physically trans-
by a dough-molding technique, and free-radical ferring information from the patient to the dental
polymerization is initiated either by heat or by a laboratory by a two-step inversion process:
chemical. Shrinkage is controlled by mixing
three parts of polymer and one part of monomer 1. Impression taking: a plastic material is
(usually methyl methacrylate) to form a dough. brought into contact with the object to be
The mixture is packed or pressed into a sectional reproduced and removed as an impression
mold formed by the lost-wax technique. The (negative) after hardening by cooling or
mold is formed by investing a denture where the chemical reaction
Vol. 11 Dental Materials 101

2. Model production: the impression is filled the thermal expansion and stress relaxation prop-
with a die material to give a model (positive) erties of the wax are taken into consideration.
Denture bases are prepared from softer waxes,
The model must correspond to the shape and which keep the artificial teeth in the correct
dimensions of the morphological situation in the relationship before the base is invested and pro-
mouth and, if necessary, give an instantaneous cessed in acrylic plastic.
picture of functional sequences. Impression and
die materials form an integrated whole. For the Dental Casting. The lost-wax technique in
application of the impression material to the combination with centrifugal casting is the most
object to be reproduced, rigid impression trays common way to make dental castings. The free-
are necessary. They are available prefabricated standing wax pattern or the wax pattern on a
from metal or resin or custom made in the dental refractory investment model is invested in a ring
laboratory from light-polymerizable filler-con- by using gypsum-, phosphate-, or silicate-bonded
taining polymers (composite materials). investment. The latter two are used with high-
melting alloys. In addition to the binder, the
Models and Dies. Models and dies are usu- investment consists of silica materials. It is mixed
ally made from one of three types of gypsum with water or special liquids and poured around
material and, less frequently, from plastics (usu- the pattern in the ring. After setting, the wax or
ally epoxy) and metals (electroformed silver or plastic pattern is burned out (480 – 980 ! C, de-
copper). Gypsum materials are compatible with pending on the technique). The alloy is melted
all impression materials, whereas epoxies are and then cast into the mold. The shrinkage of the
compatible with some rubber impressions. Den- wax pattern during mold formation and of the
tal compound and addition silicones are compat- alloy on cooling is compensated for by careful
ible with copper forming, whereas most rubbers control of the setting and thermal expansion of
are compatible with silver forming. the investment.
Plaster, stone, and improved stone gypsum
products are supplied as powders that are mixed
with water to a heavy slurry which is vibrated into 2. Metals
impressions. The strength, accuracy, and cost
increase from plaster to improved stone. 2.1. Introduction
Epoxy materials are supplied as an epoxide
paste and a liquid amine catalyst. The fluid mix is Metals and alloys are widely used materials in
poured into the rubber impression. They set modern dentistry. In restorative dentistry metallic
slowly compared to gypsum materials. materials are used for fillings for periodontal and
Electroforming of rubber impressions is done endodontic treatment; prosthetic dentistry uses
by painting the impression with finely divided metals for crowns and bridges, partial dentures
metal powder; this surface is then made the and implant suprastructures; and for orthodontic
cathode in an electroplating system. Pure copper treatment, the elastic and shape-memory effects
or silver is used as the anode, and electroforming of metals and alloys are utilized. Finally in dental
is carried out by using the appropriate electrolyte implantology, titanium metal is almost exclusive-
and direct current (d.c.). Plating is continued until ly used for its osseointegration capabilities.
more than 1 mm has been deposited; the remain- Depending on the specific application, the
ing space is then filled with acrylic plastic or required physical properties and processing
improved stone. characteristics vary widely. For instance, an
amalgam filling material must first be a plastic
Pattern Materials. Patterns to be used in mass, which allows the dentist to pack it into the
the lost-wax technique are most often made from dental cavity; it must then harden so that the
wax and occasionally from acrylic plastics, sup- filling can be contoured with a sharp instrument
plied as a powder and a liquid. Inlay, crown, and shortly after placement; finally, it must harden
bridge patterns are made from harder waxes rapidly, so the patient can chew an hour or two
which are built up in increments on the model after the filling has been placed. Root canal posts
or die. Accurate wax patterns are possible when and implants must be made of rigid, strong
102 Dental Materials Vol. 11

materials with a high elastic limit. They are 2.2. Metallic Materials for Fillings
mostly prefabricated because of requirements
for precision, surface properties, and strength. 2.2.1. Pure Gold
Other requirements for certain applications (in-
dications) may be a certain coefficient of ther- In the past, the filling of tooth cavities by cold-
mal expansion or melting range if the metal weldable pure gold was rather popular. Today
framework is to be veneered with a tooth-col- this technique is less important, because it is time
ored ceramic material. consuming and inconvenient to the patient.
General requirements for all dental materials Gold for fillings is available in different
result from the requirements to be met by a shapes: gold foil of 1 mm thickness or rolled into
finished dental restoration in the oral cavity and cylinders (Gold Cylinder, Williams Gold Ltd.);
from interactions with the biological and chemi- electrolytically deposited mat gold in strips par-
cal processes of the patient. The quality of the tially wrapped in gold foil; and gold powder
restoration, which ultimately guarantees long- encased in gold foil (Williams Gold Ltd.); par-
term success in the mouth, is determined not tially sintered chemically deposited gold powder
only by the material but also by the quality of [12], [13]. One type contains a small addition of
its dental and technical processing. These three calcium to improve work hardening (Electraloy
areas – medicine, processing technology, and RV, Williams Gold Ltd.). The pieces must be
materials science – cannot be regarded indepen- annealed and allowed to cool; they are then
dently of each other. inserted immediately into the cavity and con-
The most important medical requirements on densed by malleting with hand instruments or
dental alloys are: electric condensers [13]. Direct plastic gold fill-
ings are advisable only for small cavities on the
. Corrosion and tarnish resistance in the mouth occlusal surfaces or near the neck of the tooth.
. Biocompatibility Larger fillings with two or more surfaces must be
. Esthetics made by the inlay casting technique.

No material should be introduced into the oral


cavity that can corrode under the sometimes- 2.2.2. Silver Amalgams
aggressive conditions that prevail there, that is,
dissolve with the formation of considerable Amalgams are alloys of mercury with other
amounts of metal ions. Tarnished layers, which metals. Silver amalgams were introduced to den-
can develop by the reaction of metal ions with tistry at the beginning of the last century. The
constituents of the saliva, are also undesirable dentist mixes an alloy powder with mercury to
because they lead to esthetically unsatisfactory obtain a plastic mass. This plastic amalgam is
results. then packed into the prepared tooth cavity. It
The requirement for a good biocompatibility begins to harden after a few minutes; the surface
of a material is closely related with the require- can be shaped by carving after 10 min or less; and
ment for corrosion resistance. This means that after 1 – 2 d, the amalgam is completely hard-
materials which come into contact with the body ened, and can be polished.
of the processor or of the patient must not cause
any harm to health. When a new alloy is formu- Properties. Today many different types of
lated, a high corrosion resistance must be en- alloys are available for amalgams. They consist
sured, which in addition to the composition can of finely divided Ag – Sn – Cu alloys, some-
be improved further by a homogeneous, fine- times with small additions of zinc, mercury,
grain microstructure. An appropriate processing indium, or noble metals. They are distinguished
procedure in the laboratory also plays an impor- by the following criteria
tant role here. However, since even highly cor-
rosion resistant alloys release minimal amounts
of ions into solution, elements that have a proven
Silver content: >65 % or 40 – 60 %
high allergenic or toxic potential, such as Cd, Be, Copper content: 10 – 30 % or <6 %
Pb, and Ni, must not be used.
Vol. 11 Dental Materials 103
Grain size: <150 mm or <60 mm
Shape: cut filings or atomized spherical particles
polished fillings than the conventional low-cop-
Number of alloys: single alloy or particles from different alloys per amalgams.
Some of the cut alloys are preamalgamated to
accelerate the wetting and reaction with mercury.
Until around 1970, only alloys with high silver For this purpose, the alloy powder is treated with
content and low copper content were used. These a mercury salt solution, which precipitates mer-
conventional alloys mainly consist of the inter- cury at the surface of the particles. Zinc is also
metallic phase Ag3Sn (g), which reacts with added as a deoxidizer; it slightly increases the
mercury to form two new intermetallic phases strength of the amalgam but, if contaminated
(g 1 and g 2): with moisture, has the disadvantage of producing
hydrogen, which causes delayed expansion or
Ag3 SnðgÞþHg ! Ag3 Hg4 ðg 1 ÞþSn8 Hgðg 2 ÞþAg3 Sn blisters.

An excess of Ag3Sn remains in the hardened Production. Filings are produced by cutting
amalgam; its g 2 phase is the weakest and most annealed ingots of alloy (10 – 20 kg) in a ma-
prone to corrosion. Corrosion products are tin chine with a rotating milling cylinder and water
oxides and tin oxide chlorides. The mercury from cooling. They are ground, sieved, annealed under
the corroding g 2 phase diffuses back into the protective gas, etched with acid or preamalga-
amalgam and causes mercuroscopic expansion mated (see above), rinsed, and dried (Fig. 1).
[14] which damages the margins of the filling. Spherical alloy particles are produced directly
Since 1965, alloys with higher copper content from the melt by pouring it through a hole in the
have been developed. Instead of Sn8Hg, the bottom of the crucible and atomizing the melt
mercury-free phase Cu6Sn5 (h0 ) is formed, which stream with high-pressure nitrogen. The atom-
is less prone to corrosion; it has the additional ized droplets solidify while falling or are
advantage of making the matrix phase Ag3Hg4 quenched in water, forming small spheres or
more creep resistant. irregular particles. The powder is sieved and
The first amalgams that were free of the g 2 annealed in a reducing atmosphere or etched
phase were the dispersion-type alloys, which with acid.
contain about 30 % of spheres (< 35 mm) of the Cut filings or atomized particles are either
Ag – Cu eutectic (28 % Cu) in addition to the used as a single-alloy powder or mixed according
conventional Ag3Sn filings [15]. The initial re- to different manufacturing prescriptions. By an-
action with mercury is similar to that of the nealing, the rate of reaction with mercury (setting
conventional alloys, which is followed by time, working time for the dentist) and the setting
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 Figure 1. Remission electron microscopy (REM) photo-
yield much more stable margins and brighter graph of Luxalloy-non-gamma 2
104 Dental Materials Vol. 11

expansion of the alloy can be influenced and following disadvantages: elevated corrosion, dis-
optimized. coloration, and metallic taste. Allergic reactions
to mercury in amalgam fillings are observed only
Standards. Amalgams were the first dental in very rare cases.
materials to be standardized. The following in-
ternational standards exist: ISO 24234 (Dentist-
ry – Mercury and Alloys for Dental Amalgam). 2.2.3. Copper Amalgams

Handling. In earlier times, the alloy powder In former times, copper amalgams were used in
and mercury were mixed in a glass mortar with childrens’ temporary teeth. They were supplied
pestle. Today, electric mixing devices produce in the form of tablets with about 35 % copper and
the amalgam paste in 6 – 30 s. The recom- 65 % mercury. They had to be plasticized by
mended ratio of mercury to alloy depends on the heating above 128 ! C, and they hardened on
type of particles. The range is 0.9 – 1.2:1, with cooling to form the phase Cu7Hg6 [20]. The
less mercury used for spherical powders and heating process is a dangerous source of mercury
more for filings. An excess is expressed by the vapor. The corrosion resistance of copper amal-
dentist during compression into the cavity. Ratio, gams is poor.
mixing frequency, and mixing time influence the
properties of the amalgam before and after hard-
ening. A low ratio causes a dry amalgam paste 2.2.4. Gallium Alloys
and porosities in the filling. An extended mixing
time may change the setting expansion into a Gallium has a melting temperature of 30 ! C. A
contraction. eutectic alloy with indium and tin is liquid at
room temperature and can be used to form a paste
Toxicology and Occupational Health. The similar to the amalgam paste. When it is mixed
mercury release from amalgam into water or with an alloy similar in composition to an amal-
saliva was found to be very low: 2.4 – 3.8 mg/ gam alloy with silver, copper and tin and in one
cm2 during the first day from fresh amalgam and case 9 % palladium, it hardens in the same way.
0.1 – 0.3 mg/cm3 per day from completely hard- Since the vapor pressure of liquid gallium at
ened amalgam. Tooth brushing twice a day in- mouth temperature is close to that of solid iron
creases this amount to 0.5 – 0.8 mg/cm2 per day. at this temperature, evaporation of gallium is of
The daily uptake of mercury from normal food is no concern.
7 – 12 mg, and can be as high as 40 – 50 mg with The problem with this type of filling material
one meal of fish [18]. The daily dose from is that gallium is not as noble as mercury. This
amalgam fillings is below 10 mg [80]. means corrosion rates are higher than those for
Spilled mercury and amalgam waste can be a amalgam. The alloy tends to undergo dark dis-
source of mercury vapor and therefore hazardous coloration in the mouth and the corrosion rate of
for the dentist and his staff. Spillage must be gallium from this type of alloy is two orders of
avoided by using modern dispensing and mixing magnitude higher than that of mercury from
devices, and by keeping wastes in closed boxes amalgam. Therefore biocompatibility of this type
under thiosulfate solution. By this means, the of alloy is by no means better than that of
mercury concentration in dental offices can be amalgam.
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- 2.3. Metallic Materials for Prosthetic
take of mercury by breathing through the mouth Restorations
was found to be less than 0.1 mg/m3 for an
amalgam surface of 1 cm2 [19]. Contact between The wide span of qualities required in materials
amalgam fillings and gold restorations in the for restorative devices has led to a variety of
mouth should be avoided, because the different metallic dental materials. Castings are used for
potentials of these materials can lead to the rebuilding partly damaged teeth (inlays, onlays,
Vol. 11 Dental Materials 105

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
Figure 2. Corrosion resistance of binary gold and palladium
becoming increasingly popular. alloys
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- The more positive the potential, the more
rial and the technique of application, the sub- corrosion-resistant the element. Due to their very
strate alloys must have very specific properties. high values, precious metals are not attacked by
Since the ceramic veneer is fired onto the metallic hydrogen ions. As shown in Figure 2, the high
dental framework, alloys suitable for this electrochemical potential of gold and palladium
technique must fulfill specific requirements con- is retained in binary alloys provided the Au or Pd
cerning thermal expansion, melting range, and content exceeds 50 atom % in all phases of the
bonding characteristics to the ceramic material. alloy.
Alloys for this porcelainfused-to-metal tech- Gold has a melting point of 1063 ! C and a
nique are usually referred to as PFM alloys or coefficient of thermal expansion of ca.
simply porcelain alloys. Metallic dental restora- 14.6 & 10%6 K%1 and therefore offers ideal
tions are usually manufactured by a specific properties as a dental material. The warm yellow
dental casting technique. Other means of color is highly esteemed due to its positive
manufacturing inlays, crowns, and bridges are influence on the esthetics in the oral cavity. The
milling, sintering, or electroforming [81–83]. 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.
2.3.1. Precious Metal Casting Alloys In comparison with gold, palladium has a
lower density and a lower price, so that material
Due to their high corrosion resistance, precious costs for restorations with palladium-base alloys
metals are well suited for use in the oral cavity, are considerably lower. Palladium, however, is
where the metals come in contact with saliva, white. Since the coefficient of thermal expansion
which contains hydrogen ions Hþ (pH value of up and melting point are outside the range required
to 3) and oxygen. for ceramic alloys, considerable amounts of al-
A measure for the stability of a metal is its loying elements have to be used to meet the
electrochemical standard potential (relative to requirement profile for PFM alloys.
the standard hydrogen electrode): Platinum is used as alloying element, espe-
cially in high-gold alloys, to increase the strength
and to raise the melting point. Ruthenium and
Al % 1.7 Co % 0.3 iridium are used as additives for grain refinement.
Ti % 1.6 Cu þ 0.4 Tables 2 and 3 give an overview of the various
Zn % 0.8 Hg þ 0.8 base systems used as dental alloys with their
Cr % 07 Ag þ 0.8
Fe % 0.4 Pd þ 1.0
main alloying elements. A differentiation is
Ni % 0.3 Au þ 1.4 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 Dental Materials 107

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 Figure 4. Microstructure of Degulor M in the hardened and
Au – Ag – Cu have been used for the soft states A) Hardened, soft þ 15 min/400 ! C/air; B) Soft,
manufacturing of dental restorations since the 15 min/750 ! C/Ar, H2O
introduction of the casting technique. The Au –
Ag – Cu ternary system is shown in Figure 3. creased. Table 2 lists the composition and Ta-
While a complete miscibility of the components ble 3 the properties of Degulor alloys for various
is possible in the Au – Cu and Au – Ag systems indications, together with a selection of other
over the entire range of concentration, the solu- DeguDent alloys.
bility of silver in copper and of copper in silver is In the past high-gold alloys based on Au –
only limited. With decreasing temperature, this Ag – Cu could be veneered with resin materials
solubility gap increasingly extends in the direc- based on poly(methyl methacrylate) (PMMA) to
tion of the gold corner. Alloys with a composition give the restoration a tooth-colored appearance.
in the range of the solubility gap can be hardened Esthetically higher grade restorations, however,
by heat treatment [86]. During this process, pre- could only be obtained by veneering with ceram-
cipitates that are rich in copper or silver are ic materials that are fused to the alloy at ca.
formed and increase the hardness and strength 980 ! C. Since the solidus temperature of the
of the alloy. Figure 4 shows the structure of the alloys based on Au – Ag – Cu lies below this
Degulor M alloy in the soft and hardened temperature, these alloys could not be used for
condition. this purpose. Newly developed low-fusing (hy-
By means of slight variations in the silver and drothermal) ceramic materials allow for ceramic
copper contents, the extent of precipitate and thus veneering of this type of alloys.
the mechanical properties of these alloys can be Since the difference between the firing tem-
varied. Consequently, it is possible to design perature of the ceramic and the solidus tempera-
optimum alloys for the various clinical indica- ture of the alloy should be at least 100 ! C, the
tions. A further improvement of these alloys is solidus temperature of such an alloy must be
achieved by adding platinum and iridium. Due to raised above the melting point of gold (1063 ! C).
the grain-refining effect of these elements, den- Therefore, platinum and palladium are used as
dritic solidification and thus an inhomogeneous alloying elements (Fig. 5). However, the addi-
element concentration within the grain (segrega- tion is limited by the requirement for a maximum
tion) can be avoided. The fine-grain microstruc- liquidus temperature of 1300 ! C.
ture also leads to an improved corrosion and Palladium as an alloying element can be used
tarnish resistance; ductility and strength are in- very effectively to raise the melting range
108 Dental Materials 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
Figure 5. Ternary Au – Pt – Pd phase diagram with iso- been known since the mid-1950s. By lowering
therms of the solubility gap and some liquidus temperatures the Cu content to 4.4 % and removing the Pd the
veneering characteristics and color were opti-
because, in contrast to platinum, it widens the mized (see Tables 2 and 3).
melting range considerably less. A very wide
melting range increases the tendency to develop Gold-Reduced Alloys. With the sharp in-
segregations during solidification of the alloy. crease of the gold price in 1982, high-gold alloys
However, because of the unlimited miscibility of became increasingly unaffordable for many pa-
Au and Pd only a solid-solution hardening is tients and for health insurance systems, leading to
possible that does not result in an adequate an increased consumption and development of
strength of these alloys. Moreover, palladium alloys with a reduced gold content. The Au –
adversely affects the gold color. In contrast, Ag – Cu alloy base is similar to that of high-gold
platinum permits precipitate hardening at Pt alloys but the gold content is reduced to ca. 60 %
contents exceeding about 6 wt % (Fig. 5) [87]. and the silver content is increased by more than
Therefore, palladium, which raises the melting 20 %. The palladium content is ca. 5 %. Due to
range, and platinum, which increases the melting the low atomic weight of palladium compared
range and hardenability, are usually added to with gold, it can replace almost twice the amount
high-gold PFM alloys. Moreover, since alloys of gold and platinum in these alloys, so that the
with high strength are required, especially for corrosion resistance is also ensured. Due to their
Vol. 11 Dental Materials 109

Pd and lower gold content these alloys no longer and 3). The high precious metal content of this
display the intensive yellow color of the Degulor alloy (ca. 90 wt %) ensures good corrosion resis-
group alloys. Typical examples are the Stabilor tance in the mouth. The higher content of non-
alloys (Tables 2 and 3). precious elements in comparison with high-gold
Improper handling of these alloys can lead to alloys, however, can make these alloys more
porosities on the surface of dental castings. These sensitive to processing errors.
porosities can lead to the formation of so-called
aeration elements. Due to the different oxygen Palladium Alloys. Attempts to develop
contents on the surface of the alloy and inside the low-gold (or even gold-free) precious metal den-
shrinkage cavities, a difference in the electro- tal alloys date back to the 1930s, where following
chemical potential results between the two areas. the depression Ag – Pd alloys were introduced
In copper-containing alloys, copper ions go into as dental casting alloys. When manufactured
solution inside the pore, migrate out of the pore, properly, dental restorations made from these
and react with anions in the saliva to form a alloys show reasonable clinical behavior, but a
dark discoloration around the shrinkage cavity slight darkening may occur over time as a result
(tarnish). of the high silver content of these alloys and the
This potential problem provided the impetus tendency of silver to tarnish if it comes into
for the development of copper-free, gold-base contact with sulfur. Silver-base alloys that con-
alloys, based on the ternary system Au – Ag – tain up to 5 % gold are still widely used, e.g.,
Pd. In contrast to the Au – Ag – Cu system, Palliag M (see Tables 2 and 3).
however, all binary systems and the ternary In the field of PFM alloys the development of
system have no miscibility gaps. Precipitate low-gold Pd alloys dates back to the early 1970s,
hardening is therefore not possible. when Pd – Ag alloys were first introduced for
The ternary system Au – Pd – In has a solu- veneering with dental ceramics. However, due to
bility gap like the binary-edge systems Au – In the tendency of Ag-containing alloys to frequent-
and Pd – In. It should therefore be possible to ly cause greenish discolorations in the dental
achieve an increase in strength by alloying an ceramic materials available at that time, a higher
adequate amount of indium to the Au – Pd – Ag acceptance of Pd alloys for ceramic veneering
base. The range of the solid solution of In in this came only when first Ag-free versions were
ternary basis is the narrowest at medium gold developed in the late 1970s as a response to
contents, so that only little indium has to be soaring gold prices and with the introduction of
alloyed to obtain precipitate hardening. nongreening ceramic in the early 1980s (e.g.,
The C & B alloys are not suitable for ceramic Duceram).
veneering. Since there was also a demand for To obtain Pd-base alloys suitable for dental
economical alloys for ceramic veneering, it was ceramic veneering materials and for melting and
necessary to reduce the platinum content in casting with standard laboratory equipment the
addition to the gold content. Therefore, Au – Pd melting range of palladium has to be lowered by
was chosen as the base system. To achieve a at least 250 ! C, while the coefficient of thermal
noticeable cost reduction, the gold content was expansion has to be increased to a minimum of
reduced to 50 – 60 % and the palladium content 14.0 & 10%6 K%1. For this purpose, low-melting
was raised to 35 – 40 %. Due to the strong metals are used for alloying. The element with
decolorizing effect of palladium all these alloys the strongest influence in lowering the melting
are white. temperature is gallium (Fig. 6). Tin, copper, and
The high proportion of palladium results in a cobalt also lower the melting temperature signif-
considerable rise of the melting range to values icantly, whereas indium and silver have only a
far above 1400 ! C. To lower the melting range, minor effect. Silver, copper and cobalt are
elements such as indium, zinc, tin and to a slight completely soluble in palladium, whereas galli-
extent also gallium have to be alloyed to consid- um, tin, and indium have solubility limits in
erably lower the melting range. At the same time palladium of 10, 17, and 18 wt %, respectively,
the severe lattice distortions introduced by these at 700 ! C [92].
alloying elements cause strong solid-solution In contrast to high-gold alloys, in which a
hardening. A typical product is Deva 4 (Tables 2 finely dispersed second phase with a high content
110 Dental Materials 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-
Figure 6. Influence of various metals on the liquidus tem- sitive to discoloration by silver have been devel-
perature of binary Pd alloys oped (e.g., Duceram).

of precious metal is required to increase the


strength, second phases are undesired in palladi- 2.3.2. Nonprecious Metal Casting Alloys
um-base alloys. To obtain a single-phase alloy,
the amount of gallium and copper have to be Nickel-Base Alloys. Although Co – Cr and
reduced distinctly (Fig. 7). The ternary phase Ni – Cr alloys with adequate tarnish and corro-
diagram shows that with decreasing copper con- sion resistance have been available since about
tent the area of the solid solution crystal also 1930, noble-metal alloys are still the materials of
becomes wider, but even outside the two-phase choice for cast inlays, crowns, and bridges. Ef-
region the formation of a second phase is possible forts to fuse dental ceramics to nonprecious
as a result of additional alloying elements. A alloys were first successful only around 1970,
further reduction in the risk of undesired segre- when Ni – Cr alloys were used that are similar to
gation and the formation of second phases can be creep- and sag-resistant superalloys for high-
achieved by grain refinement. temperature applications such as furnaces and
Palladium and silver, similar to palladium and turbines. Chromium forms a passive layer on
copper, are completely miscible. Silver, howev- these alloys, which prevents further corrosion.
er, can be alloyed to a high degree since it does 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
Figure 7. Ternary phase diagram Pd – Cu – Ga must be specially trained. Common problems
Vol. 11 Dental Materials 111

include miscasts, poor fit, porcelain fracture, is a very reactive metal it must be cast under an
weak joints when brazed after ceramic firing, atmosphere with a very low oxygen content, and
and extended finishing time. the investment material must be chemically more
The biocompatibility of nickel alloys is an- stable than for other dental castings. The low
other point of concern. Nickel can cause allergic density is not only an advantage but also a
dermatitis. Therefore, the use of nickel-contain- disadvantage, since higher casting forces are
ing alloys is contraindicated in nickel-sensitive required to obtain void-free castings. In this
patients. Technicians must also be aware of this context the low X-ray opacity of titanium is an
potential risk. Moreover, nickel dust is consid- advantage because radiographs can be used to
ered a carcinogen. Cancer of the respiratory tract determine whether the casting is free of voids.
has been particularly well documented in persons Recently, ceramic materials for veneering
who are occupationally exposed to nickel; there- titanium have been introduced into the market
fore, precautions must be taken to avoid inhala- (e.g., Duceratin). Clinical observations have in-
tion of nickel dust during processing. Beryllium dicated that titanium veneered with these dental
is of concern mainly to the dental technician ceramic materials still has a higher risk of frac-
because it may provoke beryllosis. ture and failure of the metal – ceramic bond.
[81], [84]. However, acrylic resin veneers give
Cobalt-Base Alloys. Primarily because of better results on titanium than on precious-metal
the hazards associated with nickel and beryllium, or other nonprecious-metal dental alloys [85].
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) 2.3.3. Casting Alloys for Removable
are not useful for the CFM technique, because Dentures
they are not scale resistant, their oxides react
unfavorably with the ceramic veneer, and their Removable partial dentures are commonly cast
thermal expansion does not match that of the of suitable alloys, whereas complete dentures
common brands of dental ceramics. Special al- are now rarely made of metal; for orthodontic
loys have been developed to overcome these appliances, wires made of stainless steel or
problems. Some Co – Cr alloys are on the mar- nickel – titanium alloys are generally used. The
ket, with tungsten instead of molybdenum as a removable partial denture, which is primarily
main constituent or with titanium partially repla- supported by the mucosa, is usually held in
cing chromium. The latter alloys are especially position by clasps around the remaining natural
prone to severe oxidation at elevated temperature teeth. The clasps and the denture base are often
and must be melted and cast under vacuum. cast simultaneously as one piece of a single
Strength, melting range, and thermal expansion alloy by using a specific investment casting
of these Co – Cr CFM alloys are higher than technique. Co – Cr alloys are mainly used for
those of the Ni – Cr alloys. A completely modi- this purpose (e.g., Biosil F; Tables 4 and 5).
fied processing technique is necessary to obtain Esthetically more pleasing devices to attach a
acceptable results [5], [6], [7]. removable partial denture to natural teeth or to a
fixed partial denture are telescoping crowns or
Titanium and Titanium Alloys. Formerly, industrially prefabricated attachments (see
titanium and titanium alloys were only used for Section 2.6).
implants, but pure titanium has become increas-
ingly popular as casting alloy. Advantages of
titanium are biocompatibility, low density, and 2.4. Brazing Alloys
low thermal conductivity. A disadvantage is that
titanium undergoes a phase transformation dur- Brazing, commonly called soldering in the dental
ing cooling from solidification temperature to profession, is the operation most extensively
room temperature. The high-temperature used in dental laboratories for joining two pieces
a-phase is stabilized by impurities, especially of a metallic dental appliance together. Spot
oxygen. Contamination of the surface creates a welding is used occasionally, and laser welding
brittle surface layer called a-case. Since titanium 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, contain 60 – 80 % gold and up to 10 % platinum
rods, or ingots. Brazing is frequently conducted metals, but only trace amounts of base metals.
in electrical furnaces or by means of a gas – When the joint should not differ in color from
oxygen torch between 750 and 1150 ! C. A white parent alloys, Au – Pd – Ag brazing alloys
brazing flux dissolves or removes oxide and has are available. Although they contain up to 45 %
a positive effect in promoting rapid wetting and copper, zinc, tin, and indium, some of these have
spreading of the brazing filler metal. Because acceptable corrosion resistance if the noble metal
brazing must be conducted at temperatures that content is not less than 40 %. These white brazing
are 20 – 150! C above the liquidus temperature alloys are preferred in the fabrication of ortho-
of the filler metal without fusing the parent dontic appliances, removable partial dentures,
metal, a suitable brazing alloy has to be chosen and ceramic-veneered restorations made of
for the particular combination of metals to be base-metal casting alloys.
joined. Brazing alloys of Ag – Cu – Zn, sometimes
used for joints in removable appliances, cannot
Noble-Metal Alloys. Because brazed joints be accepted for long-term use, because of their
must be corrosion resistant in the oral environ- low corrosion resistance. Furthermore, the braz-
ment, noble-metal alloys are the filler materials ing operation itself reduces the passivation of
of choice. Brazing alloys based on the Au – some base-metal parent alloys, which can result
Ag – Cu system are called gold solders. They in mechanical breakdown of the appliance be-
usually contain 50 – 75 % gold, up to 10 % plat- cause of corrosion of the joint.
inum group metals, balance silver and copper, Alloys of Au – Ni with about 80 % gold, are
plus up to 15 % zinc and, occasionally, minor used particularly for direct brazing of a clasp wire
additions of indium or tin to lower the melting to denture bases cast from Co – Cr alloy. Fusion
range. These yellow-colored gold solders are of a high-melting Au – Ni brazing alloy to one
suitable for all joining purposes in the fabrication part of a restoration made of a base-metal alloy,
of fixed restorations, except for joining prior to prior to brazing it with a gold solder to another
firing the ceramic veneer. For this application, part made of a noble-metal alloy [1], [3], [4], is
high-melting Au – Ag alloys are used, which 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 Dental Materials 113

Base-Metal Alloys. So far the only base- of the transmucosal part has to be smooth.
metal brazing alloys commonly used in joining Roughening of the surface is done by spray
base-metal CFM alloys prior to firing the ceramic coating of titanium with titanium or by sand-
veneer are Ni – Cr – Si – B alloys, e.g., blasting or etching. The difficulty in all-cases is
BNi74CrFeSiB 980 – 1080 (ISO 3677 designa- to keep the surface free from foreign material
tion for nickel-based solder containing 14 % Cr, which may reduce biocompatibility.
4.54 % Fe, 4.5 % Si, 13 % B, and having a To enhance the healing process and to provide
working range of 980 – 1080 ! C). a bioactive surface some implants are provided
with a surface layer of hydroxyapatite or similar
calcium phosphate compounds. The problem
2.5. Metallic Materials for Implants with these layers is that the adherence to the
metal surface is too weak to withstand the shear
Since the early 1970s alloplastic implants have forces during the insertion process. Chipped-off
become increasingly important. They are used as parts from the surface may create problems
replacements for missing teeth and for retaining during the healing process.
full dentures. All implant materials must be Implants are also available completely made
highly corrosion resistant in the oral cavity as from ceramic material, mainly aluminum oxide,
well as in the bone structure. They must also be or from carbon glass or carbon fiber. The disad-
strong enough to withstand mastication forces. vantage of the carbon implants is the black color,
Implants are either supported by the jaw bone which is visible through the gum.
(subperiosteal implants) or fixed in the jaw bone A survey of materials approved in general
(endo-osseous and endodontic implants). Sub- implant surgery is given in the ISO Standard
periosteal implants are fabricated, according to Series 5832.
an impression of the jaw bone, in a dental labo- Implant systems are most successful when
ratory by using the lost-wax method with a Co – prefabricated endodontic and endo-osseous im-
Cr – Mo casting alloy. Individually shaped im- plants are provided along with the corresponding
plant frameworks are obtained, which allow a root canal and bone-cutting instruments,
prosthesis to be fixed on the posts passing respectively.
through the gum. Nowadays this kind of implant Because of the different techniques of placing
is not very popular anymore because of problems implants, various shapes of implants are avail-
with the fixation of the implant on the bone. able. Blades, screws, and hollow cylinders are
For endo-osseous and endodontic (transfixa- used mainly for endo-osseous implants [9], [10].
tion) implants, prefabricated parts of various After a root resection, endodontic implants must
alloys are available from the dental industry. be inserted through the root canal into the jaw-
They are fixed in the jawbone. Titanium and bone. The usual implant shapes are therefore
titanium-based alloys are most important be- limited to needles, pins, and screws [11].
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- 2.6. Metals and Alloys for other
patible, but because of its high density and poor Purposes
mechanical properties, it is not yet used as an
implant material on a wide basis. Wrought co- For other applications and operations in dentistry
balt-based alloys, such as Co – Cr – W – Ni and besides casting and brazing, metals and alloys are
Co – Ni – Cr – Mo, have also been used as im- used in the form of either prefabricated parts or
plant materials. Formerly, stainless steel with ca. semifinished materials.
18 % Cr, 14 % Ni, and 3 % Mo was used as
implant material, but its corrosion resistance and Root Canal Posts. Because of the severely
hence its biocompatibility are not as good as of corrosive conditions in crevices, highly corro-
other alloys [8]. sion-resistant materials must be used for root
Good incorporation of implants into the jaw canal posts which are inserted into the root of
bone requires a rough surface, while the surface a nonvital tooth as a retention for the artificial die.
114 Dental Materials Vol. 11

Some prefabricated root canal posts are made sheets, bands, wires, etc., for intraoral applica-
solely of noble metals (e.g., 80 % Pt – 20 % Ir or tion are made as well. Usually the 18 – 8 variety
60 % Au – 20 % Pd – 20 % Pt), and others from of austenitic steel is employed, whose corrosion
titanium or a titanium alloy with 6 % Al and 4 % resistance depends on proper processing, e.g.,
V. Stainless steel is not well suited for root canal heat treatment or cold working. Occasionally,
posts, even if the posts are gold plated, because of Ni – Cr and Co – Cr alloys are also used.
its low corrosion resistance. Prefabricated posts
come in different shapes and dimensions for Orthodontic Materials. Arch bars, springs,
different root sizes and purposes. and bands in orthodontic appliances are generally
made of stainless steel and are constructed and
Precision Attachments. An important ap- joined by spot welding or, occasionally, by braz-
plication of noble-metal alloys is in prefabricated ing with silver solder. Both these joining tech-
precision attachments. Various anchors, hinges, niques can reduce corrosion resistance, but this is
bar joints, etc., are available, which are based acceptable because such appliances are used
largely on the male – female principle. They are temporarily. Nickel – titanium alloys have also
used to couple different parts of a prosthesis (e.g., become popular for use in orthodontic appli-
a removable partial to a fixed partial denture) and ances. Stainless steel is also employed for pre-
to achieve fastening and accurate location of the fabricated screws and brackets in orthodontic
prosthesis. The advantage of these attachments is appliances; for matrix bands to support the filling
that the prosthesis or parts of it can be removed material packed into the tooth cavity; and for pins
for inspection and repair, for cleaning, and for to improve the retention of large amalgam or
care of the adjacent oral tissue. Depending on the resin restorations.
construction, indication, and intended joining
technique (brazing, casting onto), precision at-
tachments are made of high-melting, nonoxidiz- 3. Dental Ceramic Materials [21–23]
ing alloys (e.g., Pt with 20 % Ir or Au with 15 –
25 % Pt and 15 – 25 % Pd) or of high-strength 3.1. Ceramic Teeth
alloys based on the Au – Ag – PGM system or
the Ag – Pd – Cu system. As early as 1774, DUCHATEAUX
^ and CHEMANT
"
reported the use of ceramic powders for fabri-
Platinum Foils. A particular application of cation of teeth. FONZI, in 1808, was the first to
platinum foils (about 25 mm thick) is in the fire platinum posts into teeth as anchoring ele-
fabrication of full ceramic crowns (jacket ments. Ceramic teeth were manufactured in
crowns), in which a foil cap must conform to 1838 (ASH, England) and 1844 (S. S. WHITE,
the die onto which a particular alumina porcelain United States). Since 1950, demand for ceramic
is fired. After the firing operation, the platinum teeth has diminished continuously. Today, arti-
foil is removed, leaving a gap for cementation. ficial teeth fabricated from resin materials are
An alternative to this full ceramic crown is the preferred due to their lower price and easier
platinum-foil-reinforced ceramic crown, in processibility.
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 3.1.1. Raw Materials
fused to it, and the composite crown then cemen-
ted. Successful conditioning techniques are tin The formula for table china was the starting point
plating and oxidizing, fusing of gold bonding for the development of ceramic powders for
agents, or covering with a gold brazing alloy [1], teeth; as a rule, this porcelain is composed of
[3], [4]. 50 % kaolin, 25 % feldspar, and 25 % quartz.
Teeth made from this material, while functional-
Tools, Sheets, Bands, and Wires. Stainless ly acceptable, were faulty aesthetically because
steel is the material from which not only instru- of their excessively white opaqueness. The high
ments and tools for dentistry are fabricated, but content of kaolin is responsible for this white
Vol. 11 Dental Materials 115

opacity because of the highly refractive, highly 3.1.2. Fabrication


dispersed mullite that forms from kaolin during
firing. For this reason, the proportion of kaolin in The raw materials are crushed first in a jaw
the formula was greatly decreased or eliminated. crusher or chaser mill and then ground in ball
However, the mechanical properties of dental mills before being mixed in accordance with the
porcelain suffered as a result. prescribed formula (maximum particle size
The formulas for today’s dental porcelain 150 mm). To achieve better results, the mixtures
powders usually include more than 90 % of a are customarily fritted first. For this step, the raw
mixture of feldspar and quartz, the quartz com- materials are placed in fireclay containers and
ponent being 15 – 25 % of the mix. For this fired between 1200 and 1400 ! C until the feld-
reason, the term ‘‘porcelain tooth’’ has been spar has melted completely and the quartz has
replaced in the newer literature by ‘‘ceramic largely dissolved in the mass. The glass blocks
tooth.’’ that result from this process are again crushed and
ground to a fine powder (maximum particle size
Feldspar. Feldspar is the most important 100 mm).
raw material, in ceramic powders. High demands The starting material for tooth fabrication thus
are made on its quality: it should be largely free of prepared must now be given a color. A large
foreign phases and low in iron content because of number of differently colored ceramic powders
the danger of discoloration. Norwegian and are needed, because manufacturers offer approx-
Swedish feldspars are well suited because they imately 20 different shades of teeth. Further-
consist largely of orthoclase (K2O ' Al2O3 ' 6 more, every tooth is built up of several differently
SiO2), with the following typical composition opaque and variously shaded layers. The natural
(mass fractions in percent): 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-
SiO2 65.0
Al2O3 18.5 um-containing ZrO2. Precise control of the color
K2O 12.5 values and the transparency of the powders are
Na2O 2.5 prerequisite to achieve the desired tooth colors.
CaO 0.2 The fluorescence of natural teeth is imitated by
Fe2O3 0.02
using special fluorescing pigments or by adding
lanthanide oxides to the starting frit. The colored
powders are converted to plastic masses by use of
Quartz. The quartz used must have a similar appropriate organic additives, e.g., starch paste
purity. Quartz decreases the melting range of the or oils.
feldspar – quartz mixture and provides sufficient Shaping teeth requires much manual effort.
rigidity to the ceramic mass during firing by Two-part metal molds are generally used. The
increasing its viscosity. This assures that the labial layers of the tooth are placed in one-half
formed contours of the tooth are not lost during of the mold and the lingual layers in the other.
firing. Furthermore, the quartz content affects Posterior teeth are formed from occlusal and
several important properties of the ceramic ma- basal halves. To permit retention of the com-
terial: flexural strength, thermal expansion, re- pleted teeth in the denture base material, pre-
sistance to thermal shock, and opacity. These cious-metal shells (largely palladium) are
properties depend not only on the proportion of mounted on the back of the anterior teeth.
quartz but, significantly, on how much of the After firing, gold-plated posts are soldered to
quartz passes into the glassy phase and how much these shells. For posterior teeth, retention is
remains in the crystalline phase. provided by dovetail-shaped undercuts in the
Occasionally, minor amounts of opacity-in- base region.
ducing materials such as kaolin, mullite, or car- The filled halves of the form are pressed
borundum are added to the mixture. Addition of together for joining. When they are heated to
flux powders, such as soda or calcite, can reduce 150 – 200 ! C, the organic components lose
the melting temperature. 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 and ceramic [24]. The bonding material pro-
Restorative Materials duced is related to enamel. The metal provides
sufficient tensile strength, while the ceramic,
In the past, partial dental restorations such as glaze-like veneer affords great abrasion resis-
crowns and bridges were fabricated entirely of tance, good tissue compatibility, and an esthetic
precious metal. Today, standard practice in- appearance.
volves casting the framework in metal and ve- In the past, mechanical retention of the ce-
neering this with a ceramic layer. After insertion, ramic layer on the rough metal surface was
such a prosthesis can hardly be distinguished thought to be a prerequisite for good adhesion
from natural teeth. between the two components. Today, more sig-
The first attempts of this sort were made in nificance is attributed to adhesion through chem-
1728 by FAUCHARD, who attempted to enamel a ical bonding between the materials. Bond forma-
gold denture base. However, only in 1962, was tion generally is ascribed to the presence of easily
WEINSTEIN, an American, able to develop frits oxidized components, such as tin and indium, in
that achieved sufficient adhesion between metal the alloy (see Chap. 2). Presumably, the metal
Vol. 11 Dental Materials 117

oxide layer between the metal and the ceramic, fused to metal. To make a frit that easily segre-
enriched through a so-called oxide firing step, gates leucite, the potassium content must be
provides the chemical bridge between the com- increased, e.g., by adding potassium carbonate,
ponents [25]. K2CO3. Some manufacturers prefer to replace
natural feldspar with a mixture of other raw
materials, e.g., quartz flour, alumina, and potas-
3.2.1. Thermal Expansion sium carbonate. Furthermore, the addition of flux
powders, such as alkalis, alkaline earths, or boric
The durability of the bond between the metal and acid, is necessary to lower the fusion range. The
the ceramic depends particularly on the thermal ceramic must be able to be applied at a tempera-
expansion of the components [26]. If the differ- ture significantly below the softening tempera-
ence in this parameter is too great, the ceramic ture of the metal. Firing temperatures between
inevitably will split away from the metal during 900 and 980 ! C are customary, but temperatures
cooling. Under optimal condition, the ceramic as low as 750 ! C are becoming increasingly
shrinks a little less than the metal during cooling; common. The attainable decrease in the firing
i.e., the ceramic has a smaller coefficient of temperature is limited by the increasing chemical
thermal expansion than the metal. It is then under solubility of the ceramic.
slight compressive strain, which avoids tensile
strain that is absorbed less well by the ceramic.
Ordinarily, metals have a higher coefficient of 3.2.3. Fabrication
thermal expansion than glasses; the values of
metals used for casting partial dentures are in The raw materials are first sintered into frits. The
the range of 130 – 150 & 10%7 K%1 between 25 composition of ceramic materials varies greatly
and 500 ! C. Glasses with sufficient chemical among manufacturers. This is caused, in part, by
resistance, however, have a significantly lower the practice of mixing several different frits. The
coefficient of thermal expansion. The required main constituents of most of the relevant ceramic
high coefficient is attained through the precipita- materials are present in these following ranges
tion of a finely divided, dendritic form of leucite (mass fractions in percent):
(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
SiO2 58 – 66
the range from room temperature to 620 ! C. This Al2O3 15 – 17
transformation is accompanied by a 5 % increase K2O 10 – 14
in volume and thus is associated with a high Na2O 5 – 8
coefficient of thermal expansion. A concentra- Li2O 0 – 1
CaO 0 – 2
tion of 20 – 30 % of leucite suffices to provide an B2O3 0 – 3
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- A ceramic of this sort is made into ready-to-
tice, however, several frits of different composi- use powders by adding opacifiers and pigments to
tion are used, which permit better control of the the frit, so that the final veneer corresponds in
properties of the ceramic and a broadening of the color to the shade guides provided. Every veneer
melting range; this simplifies subsequent firing of requires three different powders: the opaque,
the ceramic to the bridge framework. 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,
3.2.2. Raw Materials SnO2, CeO2, ZrO2, or ZrSiO4. Dentin and enamel
powders make a toothlike appearance possible
Orthoclase (potassium feldspar) is the most im- through their coordinated shades and trans-
portant raw material for a ceramic that is to be lucence.
118 Dental Materials Vol. 11

The dental technician mixes the ceramic properties that must be checked constantly by
powders to a creamy mass using water or a the manufacturer include thermal expansion,
special modeling liquid. Each of the three ce- adhesion to the metal, bending strength, firing
ramic layers is applied and fired separately. shrinkage, chemical durability, and transparency
Appropriate distribution of grain size of the and color of the fired ceramic materials.
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 3.2.5. Ceramic Fused to Titanium
a maximum between 20 and 30 mm. Each firing
lasts about 5 min. The vacuum-firing procedure, Since about 1985, titanium has been used to a
described for tooth firing, has been widely small but increasing extent as a framework ma-
adopted. If the veneer must be ground later for terial. Titanium has a lower thermal expansion
adjustment, glazing and refiring provide the (92&10%7 K %1) than the traditional ‘‘ceramic
necessary shiny appearance. Unpigmented, alloys’’. Therefore, the ceramic does not require
finely ground glass frits are used as glazes. They leucite to enhance its thermal expansion. The
contain sufficient flux and can be fired at lower firing temperature of the ceramic must be below
temperatures than those required for veneering. 850 ! C, due to the high reactivity of titanium.
Strongly pigmented glazes are used to provide The veneer ceramic consists predominantly of a
specific colors. For example, tooth necks can be leucite-free glass with an increased content of
accentuated with color, and superficial anoma- alkali metal oxide and boric acid.
lies, such as enamel tears and white spots, can be
copied. Figure 9 shows a cross section of a
crown.
3.3. Dental Ceramics for Fixed
Restorations
3.2.4. Quality Requirements
3.3.1. Jacket Crowns
The requirements and testing procedures are
defined in the standard ISO 9693. Important 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
Figure 9. Cross section of a ceramic-fused-to-metal crown
a) Metal substructure (0.2 – 0.4 mm); b) Opaque layer expansion of the ceramic does not have to be
(0.2 mm); c) Dentin layer (0.6 mm); d) Enamel increased, and the firing temperature does not
Vol. 11 Dental Materials 119

have to be reduced below 1000 ! C. Nor need the quirements for the strength of ceramics for
core material be extremely opaque. However, the dental restorations. The standard ISO 6872 re-
absence of a support for the crown, otherwise quires a minimum flexural strength of 100 MPa
provided by the metal framework, must be com- for ceramic materials used for the fabrication of
pensated by increased strength, at least of the the supporting structure of crowns, veneers,
core material. The flexural strength of this mate- inlays, and onlays. However, ceramics for
rial should be at least 100 MPa, whereas 50 MPa crowning posterior teeth are only acceptable if
is sufficient for the opaque material in the metal – they considerably exceed this minimum, and
ceramic technique. materials for bridges are expected to have flex-
Jacket crowns were fabricated in the past ural strengths above 300 MPa. Besides the di-
from ceramic powders quite similar to those mensions of the restoration and the expected
used for teeth. This required that they had to be masticatory pressure, the durability also de-
fired at temperatures no lower than 1250 ! C. pends on the manner in which it is fixed to the
Today, ceramics are available which, through prepared tooth. The main problem lies in
the addition of boric acid and other fluxes, can manufacturing dental restorations from these
be fired at temperatures below 1100 ! C. The ceramic materials at an acceptable price. The
necessary increase in bending strength of the fact that each restoration has its individual
core material is achieved by adding as much as dimensions which must be observed exactly
50 % alumina, usually in the form of carborun- exacerbates the problem.
dum [29]. Prerequisites to the increased flexur- There are several methods for shaping the
al strength elicited by the carborundum are ceramic material.
good binding with the surrounding glass matrix Sintering of ceramic powder has the problem
and a controlled difference in thermal expan- that shrinkage during the sintering process means
sion between the carborundum and the glass that the shape before and after firing differ con-
phase. siderably. In the case of metal – ceramic and
Because of the better mechanical properties of jacket crowns, the inner surface of the restora-
metal – ceramic crowns and because of their tion, which has to fit exactly to the prepared tooth,
more readily attainable exactness of fit, they have is determined by the metal frame or the platinum
largely replaced jacket crowns. But for patients foil. During the firing process, the ceramic pow-
with allergic reactions to precious metals, jacket der shrinks towards the metallic base. The form,
crowns still find some use. Additionally, the lack which the dental technicians build up with the
of the opaque metal layer allows for a more ceramic powder slip, must be oversized to com-
natural appearance of the restoration. 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
3.3.2. Newer Developments glass partly crystallizes. Distribution, quantity,
and size of the crystals are responsible for the
While the importance of traditional jacket quality and the properties of the material. But if
crowns approaches zero, extensive efforts have the glass ceramic is sintered together from fine
been made to replace the metal frame by newly particles, it is hardly possible to achieve an
developed high-strength ceramic. Suitable ce- optimal crystallization process, and the result-
ramic materials, superior to the jacket crown ing material is inferior. Thus, for the production
material regarding their strength are readily of glass ceramic restorations dense ingots are
available. Glass ceramics, for example, have used, which are cast or pressed in a prepared
flexural strengths up to 300 MPa, and oxide form.
ceramics such as Al2O3 and ZrO2 even up to Dentsply introduced the first glass ceramic
1000 MPa. While some glass ceramics have a dental system Dicor in 1984. It was developed
tooth-like appearance, oxide ceramics can serve jointly with Corning Glass Works. Its basis is a
only as core materials because of their opacity mica – glass ceramic [31]. The tooth crown was
and have to be veneered with more transparent cast of a special glass at 1370 ! C. A centrifugal
ceramics. There are no generally accepted re- casting procedure similar to that used for casting
120 Dental Materials Vol. 11

metal denture restorations was used. In the sub- crowns and even bridges [35]. All these systems
sequent ceramic firing (14 h at 1070 ! C), approx- use industrially produced dense ceramic blocks
imately 55 % of the glass crystallizes. The struc- as starting materials, they are therefore not con-
ture of the resulting translucent glass ceramic is fronted with the problem of shrinkage. The pro-
characterized by platelike, interlaced crystals of a cess can be divided into three steps:
fluoride-containing mica with the formula
K2Mg5Si8O20F4. These crystals, approximately 1. Three-dimensional scanning of the surface
1 mm in size, should lend strength to the material of the prepared cavity or tooth stump by an
and retard crazing. A colored glaze is fired onto optical or mechanical device and transmis-
the structure to provide the desired shade [32]. sion of the data to a computer. Scanning can
The long–term success of this material was not be performed either intra-orally or extra-
sufficient; therefore it has been withdrawn from orally after manufacture of a model from an
the market. impression. Instead of the cavity or the
In 1990, Ivoclar introduced their Empress stump, a preformed model of the desired
system [33]. This is also a glass ceramic system, restoration can be used for the scanning
but with some important differences compared to process.
Dicor. The ingots are not cast but pressed into the 2. Design of the restoration using the three-
form by a special hot-pressing device. For this dimensional computer model derived from
reason, they have to be heated up only to the the scanning device. The operator can either
plastic state, and the reinforcing crystals present complete or change the restoration on the
in the ingots do not dissolve during the hot- screen. The outer form with the occlusal
pressing process. This has the advantage that the surface can be designed with the assistance
time-consuming subsequent ceramic firing is not of different tooth forms stored in the
necessary. The crystal phase in Empress is leu- computer’s database.
cite, but in contrast to metal – ceramics the 3. Fabrication of the restoration from the ceram-
crystallization process is optimized to give a ic block by a computer-controlled precision
flexural strength of about 150 MPa. Similar to milling machine.
Dicor, a colored glaze gives the desired shade.
Similar systems from other manufactures are Many types of ceramic are applicable for this
nowadays common. purpose, but ceramics with a glass-matrix are
Another way to overcome the problems asso- preferred because of their toothlike appearance
ciated with the sintering shrinkage is represented and ease of grinding. The strength of these cera-
by In-Ceram, a product marketed by Vita Zahn- mics is sufficient for inlays and crowns, but for
fabrik since 1989 [34]. The model of the prepared bridges oxide-ceramics have to be chosen. Most
tooth is duplicated with a special gypsum. An CAD/CAM systems can also be used for the
alumina powder slip is applied to this die and milling of metal preforms.
fired. Firing has to be timed in such a way that the The CAD/CAM systems are expensive but
alumina does not shrink and a porous, partially advantageous in that they allow the production
sintered preform is created. This preform is and insertion of restorations at the chairside
infiltrated with a glass melt in a second firing during a single visit.
step. The resulting dense core has a flexural CAD/CAM systems are also used to produce
strength of more than 400 MPa. Therefore, this frameworks for full ceramic bridges even for the
material is useful not only for inlays and crowns, posterior region. Yttrium–stabilized zirconium
but also for bridges. A toothlike appearance can oxide ceramic is mainly used for this purpose.
be achieved by veneering the core with a more Beside the main constituent zirconium oxide the
transparent ceramic. ceramic contains 5 % yttrium oxide and a small
In 1988, the first CAD/CAM system for amount of aluminum oxide. The main impurity is
manufacturing dental restorations was offered hafnium oxide, which is contained in an amount
by Siemens. This CEREC-System was devel- of approximately 2 %. The addition of yttrium
oped by M€ oRMANN and BRANDESTINI. It was suit- stabilizes the tetragonal high–temperature phase
able for the production of inlays only, but today, of zirconium oxide down to room temperature.
systems are available for the production of 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 . Complex formation reaction
stops further growth of the crack. This gives this
type of material its high strength and durability. 4.1. Cements Setting by Neutralization
Originally, frameworks of zirconium oxide Reaction
ceramic were made from dense sintered material.
Because of the rigidity of the material the milling The development of amalgam, gold alloys, and
process took a long time. Nowadays, mainly dental porcelain in the 1800s led to the search
presintered material is used. It has a chalklike for luting and more esthetic restorative materi-
consistency and can be easily milled. To get a als. Cements composed of calcium oxide and
fitting restoration the computer calculates an phosphoric acid, magnesium oxide and solu-
oversized framework to be milled by taking into tions of magnesium chloride (magnesium oxy-
account the firing shrinkage. After dense sinter- chloride cement), or zinc oxide and zinc chlo-
ing of the material the framework is veneered ride solutions were developed. The first dental
with a special veneering ceramic which is adjust- cement with satisfactory properties and rela-
ed to the low expansion coefficient of zirconium tively low pulp irritation was zinc phosphate
oxide. cement. The most important properties of ce-
ments setting by neutralization reaction are
listed in Table 6.
4. Cements
In dentistry the term ‘‘cement’’ is often used with 4.1.1. Zinc Phosphate Cements
two different meanings. Dentists use ‘‘cement’’
for all luting materials for the fixation of crowns, Zinc phosphate cement (phosphate cement) was
bridges, inlays, or onlay, even if the material is introduced in 1879 [93]. The powder contains
resin-based. Chemically speaking, the term ‘‘ce- zinc oxide and small amounts of magnesium
ment’’ describes dental materials that contain oxide. The liquid is an aqueous solution of
reactive fillers as one component of the setting orthophosphoric acid (ca. 50 – 60 %) and alumi-
system. Only these materials are treated in this num phosphate. Both components may contain
chapter. minor amounts of additives to improve various
These cements can be classified according to characteristics. During setting, the oxides are
their type of setting reaction: 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 Vol. 11

consist of unchanged zinc oxide particles embed- 4.1.4. Zinc Polycarboxylate Cements
ded in an amorphous matrix of zinc phosphate
and zinc aluminophosphate [94]. Due to the Zinc polycarboxylate cements were developed
relatively low strength and the opaque appear- by D. C. SMITH in 1964 and became commer-
ance, zinc phosphate cements are used exclusive- cially available in 1968 [93]. The phosphoric
ly as luting materials for restorations. acid of phosphate cements was replaced by an
Trade Names: Fleck’s cement (Mizzy); Har- aqueous solution of polyacrylic acid (20 –
vard Cement (Richter & Hoffmann). 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
4.1.2. Silicate Cements
with water. The major new feature of these
Replacing the zinc oxide of zinc phosphate cements was their chemical adhesion to tooth
cements by ion-leachable glasses gives the sili- tissue [93]. This property can be explained by
the fact that the carboxylic groups of the poly-
cate cements, first developed in 1902 [95].
Glasses are melted from silica, alumina, sodium acid react not only with the zinc ions released
fluoride, cryolite, and calcium sources such as from the powder (setting reaction), but also with
calcium ions of the tooth structure [94]. Zinc
calcium fluoride, calcium oxide, calcium car-
bonate, or calcium phosphate [94]. The liquid is polycarboxylate cements have relatively low
similar to that used with zinc phosphate ce- mechanical strength but are well tolerated by
the pulp. For that reason they are used mainly as
ments. In the setting reaction, the glass is at-
luting materials for metallic restorations and
tacked by acid, and metal ions are released and
precipitated as phosphates. Unconsumed glass base materials.
Trade Names: Durelon (ESPE); Poly F Plus
particles surrounded by silica gel are embedded
(Dentsply).
in the phosphate matrix. Due to the fluoride
content of the glass, silicate cements release
fluoride. Strength and esthetics are better than
4.1.5. Glass Ionomers
those of zinc phosphate cements, but solubility
is higher [94]. Old silicate cements led to some
History. A. D. Wilson investigated the use
extent to pulp necrosis, an effect that was ex-
of ion-leachable glasses with polyacrylic acid.
plained by the relatively high content of arsenic
By increasing the basicity of the glasses, systems
impurities in their glasses. But even cements
with acceptable reactivity were obtained in 1969
with practically arsenic free glasses led to pulp
[97]. That class of materials was named glass
sensitivity [96]. Possibly the slow increase in pH
ionomer (glass þ ionic polymer) or glass poly-
leading to a prolonged contact of the pulp with
alkenoate. The first glass ionomer ASPA I (alu-
an acidic environment can explain these findings
minum silicate polyacrylate) was used clinically
[94], [96]. The major use of silicate cements is in
in 1970 by J. W. MCLEAN. Due to a short working
anterior restorations.
time and a very slow setting, the workability was
Trade Name: Silicap (Vivadent).
restricted [98].

Composition. All glass ionomers contain


4.1.3. Silicophosphate Cements three essential components: an ion-leachable
glass, a polycarboxylic acid, and water.
Silicophosphate cements (stone cements) are a The first glasses were calcium aluminum
combination of zinc phosphate and silicate ce- fluorosilicate glasses (with small amounts of
ments. The powder contains both zinc oxide and sodium and phosphorus), melted from the same
ion-leachable glass. Their properties are in be- raw materials as the glasses for silicate ce-
tween those of zinc phosphate and silicate ce- ments. A typical composition (G 200) is: SiO2
ments [94]. They are used as filling materials, 30.1 %, Al2O3 19.9 %, AlF3 2.6 %, CaF2
like silicate cements. 34.5 %, NaF 3.7 %, AlPO4 10.0 % [2]. After
Trade Name: Drala Steinzement (Detax). introduction of the sandwich technique (1985),
Vol. 11 Dental Materials 123

in which dentin is replaced by glass ionomer, covered by silica gel and water molecules are
and enamel by composite resins, the need for embedded. As a result of ion hydration, the
radio-opaque glass ionomers became evident content of evaporable water decreases with time
[98]. Modern glasses for glass ionomers contain [105], while the cross-linking reaction still
heavy elements such as strontium, barium, or slowly continues. Both effects lead to an in-
lanthanum. For the reactivity of glasses the crease in mechanical strength and Young’s
content of aluminum and the formation of a modulus [106] and reduced wear [107] in the
glass matrix containing Si–O–Al bonds is im- course of time.
portant [99].
For extended use in dentistry an adjusted Further Developments. In a search for im-
working and setting time is needed. Since these proved wear resistance the cermet (ceramic met-
requirements are only partially realizable with al) ionomers were developed in 1985 [108]. In
the glass structure, the setting characteristic has these materials silver is sintered with the glass
to be adjusted by different techniques. Tempera- particles. In other products silver is added as a
ture treatment of the glass powders prolongs the powder component.
working time [98], as does the reduction of By the use of dried polyacid in the powder
reactive ions on the particle surface by a pretreat- setting time was prolonged. An improvement in
ment with dilute acids [100]. Addition of tartaric handling characteristics was obtained by the
acid as chelating agent prolongs the working time introduction of capsules containing predosed
and accelerates the setting reaction [101]. Most components which are mixed mechanically.
modern glass ionomers contain tartaric acid as a Recently, highly viscous glass ionomers were
setting modifier. developed. These materials have high strength,
In the first glass ionomers, an aqueous solu- high wear resistance, and low solubility
tion of polyacrylic acid was used. Many com- [109–113].
mercially available products still contain such
solutions, even though they tend to form gels at Properties. Glass ionomers adhere chemi-
lower temperatures. Copolymers of acrylic and cally to the tooth structure by the same mechan-
itaconic acid [98] or of acrylic and maleic acid isms as zinc polycarboxylate cements. Due to the
[102] are used to overcome this problem and to possibility of reformation of broken bonds during
increase reactivity. In some products the high the remodeling of dentin, the bond has a dynamic
ratio of maleic acid in the copolymer leads to a character. In a humid environment neither
higher degree of cross-linking in the material, shrinkage nor swelling is observed. Fluoride
resulting in high mechanical strength. The use release [114–116] and recharge (e.g., from tooth-
of polyvinylphosphonic acid [103]or copoly- pastes) [117] explain why secondary caries are
mers of acrylic and vinylphosphonic acid only rarely observed near glass ionomer fillings.
[104] has also been reported. The polycar- Fluoride and calcium release promote dentin
boxylic acids used in glass ionomer formula- remineralization [118]. The very good biocom-
tions have a molecular mass in the range of patibility of glass ionomers, demonstrated in
10 000 – 100 000 and are used in concentra- many tests [119], led to their use as bone cements
tions of about 20 – 60 % (depending on the and bone replacement materials in orthopedic
different products). Depending on the indication and ear – nose – throat surgery with good re-
the powder : liquid ratio can vary in a wide sults [120–123].
range of about 1.5 : 1 to 4 : 1. All glass ionomers
contain water, which is the reaction medium Uses. Beside the major use as filling, luting,
and the only liquid component for paste and base or core buildup materials [98], further
formation. indications are endodontic filling [124], fissure
sealant [125], orthodontic luting material [126],
Setting Reaction. After the attack of the filling material for open furcations [127], and
polyacid on the glass, cross-linking of polycar- retrograde root-filling material [128].
boxylate with metal ions released by the glass Trade Names: Ketac-Fil Plus (ESPE), Ke-
takes place. A calcium aluminum polycarbox- tac-Molar (ESPE), Fuji II (GC), Fuji IX (GC)
ylate matrix is formed, in which glass particles (filling materials); Ketac-Cem (ESPE), Fuji I
124 Dental Materials Vol. 11

(GC) (luting materials); Ketac-Silver (ESPE), environment [135], [136]. These materials are
Miracle Mix (GC); HiDense (Shofu) (Cermets); known as polyacid-modified composites [131] or
Ketac-Bond (ESPE) (base material); Ketac- compomers (composite ionomers). These mate-
Endo (ESPE), Endion (Voco) (root-filling rials are composite resins containing ion-leach-
materials). able glass fillers, polymerizable acids, polycar-
boxylic acids, and hydrophilic monomers that are
compatible with the acids and facilitate water
4.1.6. Resin-Modified Glass Ionomers absorption for the glass ionomer reaction [93].
An important property is the ease of handling.
In an attempt to combine the advantages of glass Strength and esthetics are better than those of
ionomers with those of composites, monomers resin-modified glass ionomers and comparable to
and initiators were added to glass ionomers. those of composites. However, they have no self-
Thus, parallel to the glass ionomer reaction a adhesion and only low fluoride release compared
polymerization reaction can be started by photo- to glass ionomers. They shrink comparably to
chemical or redox initiation [129]. Methacry- composites and show the same tendency to swell
lated polycarboxylic acids are also used [130]. as resin-modified glass ionomers [132–134].
Often these materials are called light-curing glass Resin-modified glass ionomers and polyacid-
ionomers; the general term resin-modified glass modified composites are often referred to by the
ionomer cements has been proposed for this class collective term ‘‘glass ionomer composite hy-
of materials [131]. An interpenetrating network brids’’ (or simply hybrids). For both classes the
of ion-cross-linked polycarboxylate and poly most important indications are in fillings, the
(meth)acrylates is formed. To obtain compatibil- luting of metallic restorations, or as a liner or
ity of water-based glass ionomers and resins, all base [94].
materials contain hydroxyethylmethacrylate and Trade Names: Dyract (Dentsply), Compo-
other hydrophylic monomers [93]. Due to the glass (Vivadent),Hytac (ESPE) (filling materi-
hydrophilicity, a relatively high swelling is ob- als); Dyract Cem (Dentsply) (luting material).
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- 4.2. Cements Based on Complex
in-modified glass ionomers have higher strength Formation
and better esthetics than conventional glass io-
nomers but a relatively low wear resistance. These cements harden by the reaction of a metal
Depending on the amount of resins in the struc- oxide, hydroxide or salt with a chelating agent.
ture, these materials can be self-adhesive. Due to Chelates form a matrix in which the inorganic
the ease of handling they are largely used in particles are embedded. These materials gener-
pediatric dentistry. ally have low mechanical strengths and therefore
Trade Names: Photac-Fil Quick (ESPE), Fuji their use is limited to temporary fillings or lut-
II LC (GC), Vitremer (3M) (filling materials); ings, pulp capping materials or root fillings.
Fuji Plus (GC), Vitremer Luting (3M) (luting
materials)
4.2.1. Zinc Oxide – Eugenol Cements

4.1.7. Polyacid-Modified Composites Zinc oxide – eugenol cements (ZOE cements)


contain zinc oxide and eugenol (the principal
Conventional and resin-modified glass ionomers component of oil of cloves) as essential compo-
contain all three essential components of a glass nents. In two-paste systems, zinc oxide is sus-
ionomer, which react spontaneously when they pended in a vegetable or mineral oil, and eugenol
come into contact. In search of light curing ‘‘one- is thickened with resins. Small amounts of water
component-glass ionomers’’, water-free systems or acetic acid are added to initiate and accelerate
were formulated. The glass ionomer reaction the reaction. The strength of these materials is
takes place only on water absorption in the oral low, and their solubility is high compared to other
Vol. 11 Dental Materials 125

cements. Depending on the powder/liquid ratio . ISO 9917-1, Dentistry – Water based ce-
or paste formulation, temporary restorations, ments – Part 1 Powder/liquid acid base
luting cements, or root canal sealers can be cements
prepared. Similar systems are used as impression . ISO 9917–2, Dentistry – Water based ce-
materials [94]. In some formulations part of the ments – Part 2 Light activated cements
eugenol is replaced by o-ethoxybenzoic acid.
These EBA cements are stronger. They are used 5. Synthetic Resins
for the same indications as ZOE cements [94].
Due to the phenolic character of eugenol, the use Synthetic resins are of great significance in den-
of certain resin-based luting materials after tem- tistry. Polymers of the polymethacrylate group
porary cementation with ZOE or EBA cements is have been in use since around 1934, and they are
problematic (inhibition of polymerization by still used today [36].
phenols).
Trade Names: Temp Bond (Kerr), Scutabond
NF (ESPE). 5.1. Denture Base Resins

The first organic base material for dentures was


4.2.2. Calcium Hydroxide Cement hard rubber. Pink India rubber was vulcanized in
a water-filled autoclave at ca. 140 ! C. This den-
First attempts to use calcium hydroxide in den- ture base material was used in combination with
tistry are dated from the late 1700s. Calcium porcelain teeth. The dental prostheses produced
hydroxide has an antimicrobial effect and in- in this way were functional, but not esthetically
duces the formation of secondary dentin. The pleasing. The India rubber procedure is of only
calcium hydroxide has been used in pulp capping historical interest today.
since 1859 [137]. Cements contain salicylate The basic process of denture fabrication has
chelating agents that react with calcium hydrox- remained unchanged. A stone (gypsum) model
ide (e.g., methyl salicylate or butanedioldisali- of the jaw is prepared from an impression of the
cylate) [138], [139]. patient’s oral cavity. The original shape of the
Trade Names: Dycal (Dentsply), Alkaliner denture base is molded in wax on the stone
(ESPE), Life (Kerr). 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
4.2.3. Other Chelating Cements then invested with gypsum in the lower half of a
denture flask. Subsequently, the other half of the
Various chelating agents are used in dentistry, flask, open on the upper side, is attached and the
especially together with zinc oxide. Root canal wax model is embedded completely. The gyp-
filling materials containing a 1,3-diketone and sum on top of the upper half of the mold is
eugenol-free temporary cements containing liq- planed by pressing with a lid. After the plaster
uid carboxylic acids are known. has set, the two halves are separated and the wax
Trade Names: Diaket (ESPE) (root filling is removed by melting. The artificial teeth re-
material);Temp Bond NE (Kerr), Freegenol main fixed in the upper half of the flask. In this
(GC), Procem (ESPE) (temporary cements). way, a precisely fitting cavity is obtained in
which raw, unvulcanized rubber or the resin
mixture to be polymerized is pressed and
4.3. Standards hardened.
Insulation of the stone plays a decisive role in
The international standards for dental cements this process, because the resin must be kept
are: separate from the plaster. Initially, dental tech-
nicians used ductile tinfoil, which could be
. ISO 3107, Dentistry – Zinc oxide/eugenol adapted with perfect precision to the teeth on
and zinc oxide/non eugenol cements the free plaster surface of the model. Tinfoil also
. ISO 6876, Dental root canal sealing materials seals the doughy mass to be polymerized from the
126 Dental Materials Vol. 11

steam that can evolve from hot plaster. More distinguished: heat-, cold-, light-, and micro-
conveniently, a coating consisting of a ca. 3 % wave-cured polymers.
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 5.1.1. Heat-Cured Polymers
alginate film.
The decisive breakthrough in denture base The procedure developed by ROTH is called the
resins was the development of poly(methyl meth- ‘‘Paladon technique’’ in dental laboratory tech-
acrylate) by R€ oHM. ROTH, a dental technician, nology. In heat-cured polymers, 0.1 – 0.5 % di-
mixed ground poly(methyl methacrylate) with benzoyl peroxide [94-36-0] is generally used as
the methyl methacrylate monomer; this gave a the free-radical initiator.
dough that could be used to make a functional and After the resin dough has been added to the
aesthetically satisfactory dental prosthesis, as insulated plaster form and pressed, the form is
described above [37]. The polymer – monomer placed in a hot water bath. Dibenzoyl peroxide
mixture solved two problems of methyl methac- decomposes between 80 and 100 ! C and initiates
rylate polymerization simultaneously: (1) the the radical chain reaction. If heating is too rapid,
pure monomer shrinks by ca. 20 % during poly- polymerization proceeds too vigorously and a
merization and (2) it simultaneously releases a porous product is formed due to boiling of the
large amount of heat (56.6 kJ/mol). monomer (bp 100.2 ! C at 101.3 kPa). Therefore,
Poly(methyl methacrylate) [9011-14-7] has a the initial heating process should be held at 70 –
dominant position in dental resins; it meets best 75 ! C for 30 min; then the water bath is allowed
the following requirements of a denture material: to boil for an additional 30 min.
The resin can be added to the hollow mold by
. Absence of taste or odor, even after long injection or by packing the negative mold and
periods of wear applying pressure with a pneumatic press. In the
. Good tissue compatibility packing and pressing procedure, excess resin is
. Good mechanical properties placed in the denture flask and the two molds are
. Exact reproduction of details of the model joined under pressure; excess material is
. Dimensional stability squeezed out between the casts. The flask is then
. Low water sorption opened, and squeezed out excess material is cut
. Color stability off. The closed flask is then placed in the water
. Good aesthetic appearance bath. Better fit can be obtained by using the
. Simple manipulation (no need for expensive injection technique [38]; in this case, the resin
equipment) is injected under high pressure into the closed
. Good reparability flask. The flask is then placed in the water bath
. Ease of cleaning and held under pressure until polymerization is
complete.
Methacrylates are available as powder and Trade names: Paladon 65 (Heraeus Kulzer,
liquid. The polymer powder, today usually bead Germany); SR 3/60, SR Ivocap (Ivoclar, Liech-
polymer, is mixed with the liquid monomer in a tenstein); Lucitone (Dentsply, USA).
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 5.1.2. Cold-Cured Polymers
molding.
Mineral pigments are the principal coloring In addition to the heat-cured polymers described
agents used; organic dyes are less important. To above, cold-cured polymers (also called autopo-
avoid formation of stress cracks and improve lymers) have increased in significance [36]. In
mechanical properties, the liquid monomer gen- cold-cured polymers, the polymerization is initi-
erally contains up to 10 % of a cross-linking ated by a two-component redox system, one
agent. Ethylene glycol dimethacrylate [97-90- component of which is in the powder and the
5] is preferred. Depending on the polymerization other in the liquid. Such systems are usually
initiator used, four types of materials can be composed of tertiary amines, e.g., N,N-dimeth-
Vol. 11 Dental Materials 127

yl-p-toluidine [99-97-8] (1 – 2 %), and perox- eliminates the need for mixing in the dental
ides, particularly dibenzoyl peroxide (0.5 – laboratory.
2 %) which has been used worldwide since about Instead of methyl methacrylate, diesters of
1940 [39]. The addition of UV stabilizers is methacrylic acid with high molecular mass diols
customary to reduce discoloration. similar to bis-GMA (see Section 5.6) or high
When the components of the redox system are molecular mass urethane dimethacrylates are
combined, numerous radicals form which acti- used as monomer.
vate polymerization. However, the formation of The handling technique has been adjusted
inactive byproducts leads to a yellow-brown because complete investment in plaster is no
discoloration of the resin. Initiator systems that longer possible, since the light must have access
do not produce discoloration were developed in to the resin from all sides. For this reason, for
1956 [40]; they consist of a 5-substituted barbi- example, pontics are provided in prefabricated
turic acid combined with dibenzoyl peroxide or standard sizes. A more detailed description of
heavy-metal salts. The color stability of cold- light curing is given in Section 5.6.2 on resin-
cured polymers having this type of initiator based filling materials.
system is so high that the quality of the polymer Trade name: Triad VLC, Eclipse (Dentsply,
reaches that of heat-cured materials. USA).
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- 5.1.4. Microwave-Cured Polymers
zation takes place in the closed flask at room
temperature in 10 – 30 min. If no injection pres- The reaction of microwave-cured polymers is
sure is used, i.e., in the completion of cast almost the same as for heat-cured materials. The
dentures with resin (partial dentures) and in the main difference is that the flask is not placed in a
fabrication of complete cast dentures, polymeri- water bath and heated to boiling temperature.
zation is carried out in a pressure chamber at Instead, the water contained in the gypsum in the
0.2 – 0.3 MPa and 45 – 55 ! C to avoid porosity flask is boiled by microwave energy. Since metal
of the product. flasks are impermeable to microwaves, flasks for
Cold-cured polymers are preferred today for microwave-cured polymers are made from fiber-
repairing fractured prostheses and for relining reinforced polyester. The initiator system must
poorly fitting ones. The cold-cured resins are also be adjusted to the polymerization process. There-
used almost exclusively for the completion of fore only materials specifically designed for mi-
cast partial dentures. crowave curing can be used for this polymeriza-
For complete dentures, cold-cured polymers tion procedure.
are injected. While heat-cured polymers show Trade name: Acron MC (GC, Japan).
certain strain after cooling, which arises from
differences in expansion coefficients between
plaster and resin, cold-cured resins polymerize 5.1.5. Other Denture Resins
practically free of strain. This results in a better fit
of prostheses fabricated from cold-cured resins. Soft resins are used as liners of dentures. In the
Trade names: Palapress, Paladur (Heraeus past, plasticized acrylic or methacrylic acid es-
Kulzer, Germany); SR 3/60 Quick (Ivoclar, ters or esters of higher alcohols were used;
Liechtenstein), Degupress (Degussa-H€ uls, however, they are not sufficiently durable. If
Germany). made of silicones, the liners have better durabili-
ty but insufficient bonding to the denture base
material.
5.1.3. Light-Cured Polymers Many attempts have been made to replace
methyl methacrylate as the denture base material
The first denture resin that was polymerized by by other plastics [41], [42]. Polyamides and
the action of light from a halogen source was polyurethanes, practically indestructible resins
introduced in 1984 (Triad, Dentsply). The resin in the fabrication of dental prostheses, have failed
material is supplied in a ready-to-use form which because of their insufficient rigidity and their
128 Dental Materials Vol. 11

excessive water sorption. At one time, polycar- Despite its high abrasion resistance, poly
bonates (e.g., Thermpont, Andoran, and Copo- (methyl methacrylate) is not entirely satisfactory
dan) appeared to be alternative resins because of for teeth in the posterior region. The mechanical
their high impact strength. However, their di- properties and the wear resistance of the resin can
mensional stability did not meet clinical require- be increased enormously when it is filled with
ments [41]. The high sensitivity of these materi- 30 – 60 % of very small (mean grain size
als to the steam evolved during injection into the 0.04 mm) particles of hydrophobic (fumed) silica
mold, was responsible for alterations in shape (e.g., Aerosil, Degussa).
and color. Furthermore, polycarbonates are sen- Trade names: SR-Orthosit, SR-Vivodent PE
sitive to alkali which is present in many denture (Ivoclar, Liechtenstein) Vitapan (Vita Zahnfab-
cleansers and leads to the formation of strain, rik, Germany).
tears, and denture fractures. The special injec-
tion techniques required and the associated ex-
pensive devices have also contributed to the 5.3. Crown and Bridge Veneer Resins
elimination of polycarbonates from the denture
[44]
base market.
Resins based on poly(vinyl chloride) [9002-
Resins are also used to veneer the visible parts of
86-2] appear to have a better chance for use as
metal crowns or bridges. Today, polymers of
denture materials. Copolymers of vinyl chlo-
high molecular mass methacrylic acid diesters
ride, vinyl acetate, and methyl methacrylates
are used almost exclusively for this purpose and
(e.g., Luxene and Virlene) are used because of
for jacket crowns. The abrasion resistance of the
their constancy of shape, low water sorption,
methacrylates can be increased by adding inor-
and high fracture resistance. They can only be
ganic fillers such as very fine grained silica, and
handled in licensed laboratories and require
fine grained glass or quartz (particle size
relatively complicated and expensive special
< 1 mm)
apparatus; their market share has, therefore,
remained minor.
5.3.1. Heat-Cured Resins
5.2. Acrylic Teeth [43]
Heat-cured resins provide better results than
Most artificial teeth set up in a denture base resin cold-cured polymers for crowns and bridges.
are acrylic teeth, made from poly(methyl meth- They are available as combinations of powder
acrylate) and methyl methacrylate. The early and liquid or as ready-to-use pastes. The resin
problems of poor shade composition, shade du- pastes are molded directly on the metal frame-
rability, crazing resistance, and particularly, work by the dental technician and are then poly-
abrasion resistance have been solved. Today, merized in a pressure vessel at approximately
resin teeth can replicate natural teeth perfectly. 0.6 MPa and 110 ! C. Steam, water, or glycerol is
The resin tooth is built up from cervical, dentin, used as the heat-transfer medium.
and incisal resins, each of which is colored to Trade names: SR-Chromasit (Ivoclar, Liech-
correspond to the appropriate tooth shade. tenstein); Biodent KþB Paste (Dentsply,
The layers are pressed into metal molds, one Germany); Vita Zeta (Vita Zahnfabrik, Germany).
after the other, and heat-polymerized under pres-
sure. To give greater hardness to the outmost
(incisal) layer for greater abrasion resistance, ca. 5.3.2. Light-Cured Resins
10 % of a cross-linking agent, preferably ethyl-
ene glycol dimethacrylate [97-90-5], is added. A breakthrough, particularly in processing, oc-
The cervical material is not or only weakly cross- curred when light-cured crown and bridge ve-
linked, because it then absorbs the monomer of neer resins were introduced [45]. These materi-
the denture base resin dough more readily, which als consist of ready-to-use single-paste resins,
provides for better bonding of the acrylic tooth to which eliminates the need for mixing. Polymer-
the denture base. ization is induced by irradiation with light
Vol. 11 Dental Materials 129

(wavelength 300 – 500 nm). An aromatic ke- a molecule containing an acidic group (SR-Iso-
tone or camphoroquinone is employed as photo- sit-Spectra-Link) or use tin plating and oxidation
initiator; tertiary amines are frequently used as of the tin layer on the surface (OVS). Another
reaction promoters. Light-initiated polymeriza- method is bonding with 4-methacryl-oxyethyl-
tion can provide resins that are fully equal in trimellitone-hydrid (4-META).
quality to heat-cured ones. Trade names: Silicoater (Heraeus-Kulzer,
Trade names: Signum þ (Heraeus-Kulzer, Germany). Rocatec (Espe, Germany); Sebond-
Germany); Sinfony (Espe, Germany); Cristobal MKV (Sch€utz Dental, Germany); SR-Isosit-
þ (Dentsply, USA). Spectra-Link (Ivoclar, Liechtenstein)

5.4. Resin – Metal Bonding 5.5. Resins for Orthodontics

The question of adhesion between metal and Orthodontic treatment is used to correct the
resin is of great significance for denture resins position of teeth. For removable orthodontic
and for crown and bridge veneer resins. Unfor- devices, cold-cured polymers, such as those
tunately, without special bonding processes, described in Section 5.1.2, are used. For fixed
gaps form between metal and resin in cast orthodontic appliances, resins very similar in
prostheses after short periods of use. Bacteria chemical composition to those used in cold-
and food debris can settle in these gaps, leading cured restorative materials are employed as
to discoloration at the metal – resin interface. adhesives.
The same problem arises in crowns and bridges. Trade names: Orthocryl (Dentaurum,
Formerly, the resin could be held to the metal Germany); Super C Ortho (Amco, USA).
framework only with mechanical devices (metal
beads or wires), which may be visible through
the resin. 5.6. Restorative Resins
In 1984, the Silicoater technique was devel-
oped, which solved the problem of adhesion In the past, only silicate restorations and expen-
between metal and resin for all precious and sive fired porcelain inlays were available to
nonprecious alloys. In this procedure, a silane provide ‘‘invisible’’ tooth restoration. Silicate
is pyrolyzed in a flame and the products are cement fillings have insufficient durability be-
deposited on the metal framework, where an cause their surfaces wash out and they do not
SiOxC layer of 0.1 mm thickness forms. On this esthetically satisfy.
surface, another silane, such as 3-methacrylox- Soon after their discovery, cold-cured poly
ypropyltrimethoxysilane [2530-85-0], can sim- (methyl methacrylate) resins (Section 5.1.2)
ply be painted. If the methacrylate monomer is were also used for restorative fillings. However,
then applied, it reacts with the silane. The metal- the presence of amine – peroxide catalysts in
to-resin bond achieved in this manner is stronger the resins leads to a bright yellow discoloration
than the self-tear resistance of the resin. The bond after service periods of only a few months.
remains stable in the oral milieu [47], [48]. Similarly, the abrasion resistance of the resto-
Another process of silane coupling between ration is not sufficient. In addition, the high
metal and resin is the Rocatec technique. In this concentration of unconverted monomer remain-
process, introduced in 1989, the surface energy ing in the resin can provoke pulp irritation.
of the metal is increased by two-step sandblast- Therefore, these resins have been replaced by
ing with aluminum oxide. The first step uses the new filler resins described in the following
pure aluminum oxide, and the second step with paragraphs.
aluminum oxide coated with a special glass, part BOWEN transferred the structural principle of
of which remains on the metal surface after an epoxy resin to a methacrylate material and
impact. A silane is then applied to the treated thus gave the latter the excellent material prop-
surface. erties of filled epoxies [36]. The key chemical in
Other systems apply hydrophobic fluorinated this method is the so-called Bowen monomer
methacrylates to the surface (Sebond-MKV), use (bis-GMA)
130 Dental Materials 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.
which is made from bisphenol A di(2,3-epoxy- Composite restorative materials are no longer
propyl) ether [1675-54-3] and acrylic acid [79- limited to the anterior region. Nowadays they
10-7]: BOWEN also proposed using a mixture of have the required strength and abrasion resis-
70 % ground quartz glass (average particle size tance for use on occlusal surfaces.
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 5.6.1. Paste – Paste Systems
shrinks less during polymerization because of
the greater molecular mass per double bond. The composites whose chemical composition is
Today monomer mixtures of bis-GMA and described in the previous section have been
triethylene glycol dimethacrylate [109-16-0], as available as two-paste systems: base paste and
well as other dimethacrylates which act as dilu- catalyst paste [36], [50], [51]. Nowadays there
ents and certain urethane dimethacrylates, are are only a few materials of this kind available on
used. In addition, the high content of inorganic the market.
fillers greatly decreases the thermal expansion The tooth-colored base paste contains a ter-
coefficient and thus approaches that of the tiary amine (1 – 2 %), and the catalyst paste
natural tooth. contains dibenzoyl peroxide (1 – 1.5 %). The
The important problem of matrix-to-filler tertiary amine usually is N,N-bis(2-hydro-
bonding is solved by treating the inorganic filler xyethyl)-p-toluidine [3077-12-1]; it does not
material with special silanes [50], [51], e.g.: 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
The silanol groups of the hydrolyzed silane are mixed in a 1 : 1 ratio. Depending on the
react with the hydroxyl groups of the silica particular product, the working time ranges from
filler, and its methacryl groups enable copoly- 1 to 2 min and the setting time from 3 to 5 min.
merization with the matrix resins to occur, Disadvantages of the paste – paste system are
thus providing a chemical bond between matrix the severely limited shelf life of the peroxide
and filler. paste and the still-unsatisfactory color stability.
The structure and particle size of the inorganic Furthermore, air bubbles are generated in the
filler material have also been modified. The pastes during mixing which severely affect the
relatively coarse-grained fillers of the first quality of the restoration.
Vol. 11 Dental Materials 131

5.6.2. Light-Cured Polymers organically-modified-ceramic (ormocer). This is


a cross-linked silicone oligomer bearing meth-
Light-cured polymers do not have the disadvan- acrylate groups. Dimethacrylates are used as
tages of the paste – paste systems described in diluents. Initiators and fillers are like in the
the previous section. The light-cured composites light-cured polymers (Section 5.6.2). Advan-
are almost identical in composition to those tages of this type of material are:
materials described in Section 5.6. However,
they consist of only one component that contains . Lower polymerization shrinkage because of
a photoinitiator system. the size of the oligomer molecule
The advantages of light-cured composites . Lower dissolution rate of residual monomers
over the paste – paste systems are because of the hydrophobic nature of the mol-
ecule, and a higher probability of each mono-
* Immediate readiness for use mer molecule being incorporated in the poly-
* Fewer air bubbles because mixing is not mer network because of the multifunctionality
required . Higher abrasion resistance compared to mate-
* Prolonged working time rials with the same type and size of filler
* Better color stability particles
* Much longer shelf lives (three years)
* No need for cool storage Trade names: Definite (Dentsply De Trey,
* Much higher reaction rate Germany);Admira (Voco, Germany).

The first radiation-cured composites were po-


lymerized with UV radiation (320 – 440 nm) in 5.6.4. Sealant Resins
the presence of an aromatic ketone initiator such
as 1,2-diphenyl-2,2-dimethoxyethanone [24650- Fissures of the posterior teeth are potential sites
42-8]. At an irradiation time of 20 s, a maximum at which carious lesions can arise. However,
depth of cure of only 1.5 mm was attainable. when these fissures are sealed with thin layers
Nowadays, visible light (380 – 500 nm) is used of bis-GMA or related compounds, the occlusal
with camphoroquinone [10373-78-1] as initiator surfaces can largely be protected from caries. The
and certain aliphatic and aromatic amines as sealant resins, like restorative resins, are avail-
polymerization promoters, and only common able as cold-cured and light-cured systems.
halogen lamps (150 – 250 W) or blue LED Trade names: Estiseal F (Heraeus-Kulzer,
lights are required. In addition, the risk of UV Germany); Delton (Dentsply, USA).
radiation to the dentist’s and patient’s eyes dis-
appeared. The most important advantage of po-
lymerization with visible light, however, is the 5.6.5. Resin – Tooth Bonding
much greater cure depth attained. Depending on
the composite and the light source, curing depths Adhesion of the resin to the tooth is very impor-
of 4 – 8 mm can be attained after 20 – 40 s tant because otherwise restorations have short
irradiation time. Fiberoptics conduct the light to lifetimes, and marginal gaps are formed between
the site at which radiation is required. the restorative resin and the tooth [49], [51], [52].
Trade names: Charisma, Soltaire 2 (Heraeus- These gaps can be sites of secondary caries. In
Kulzer, Germany); Artemis, Tetric Ceram (Vi- general, no bonding occurs between tooth and
vadent, Liechtenstein); Prisma TPH, Surefil resin, and the dentist must provide mechanical
(Dentsply, USA); Beautifil (Shofu, Japan); anchorage to ensure retention. However, when
Clearfil posterior (Kuraray, Japan); Prodigy mechanical retention is used, a relatively large
(Kerr, USA); Filtek (3M Espe, USA). amount of sound tooth tissue is lost.
The acid-etch technique has been used to
5.6.3. Ormocer-Based Filling Materials provide bonding of enamel to composite resins.
The dental enamel surface was first roughened
In this type of polymer-based filling material, the with an approximately 35 % solution of phospho-
main component of the monomer matrix is an ric acid so that microretentions result. A thin
132 Dental Materials Vol. 11

layer of resin of the bis-GMA type was then . ISO 1567: Dentistry – Denture Base Polymers
applied to the etched surface; the monomer pe- . ISO 4049: Dentistry – Polymer-based filling,
netrates the pores etched into the enamel and is restorative and luting materials
firmly anchored there. Finally, the restorative . ISO 6874: Dentistry – Polymer--Based Pit and
resin was applied, and a mechanical bond formed Fissure Sealants
between dental enamel and resin. . ISO 6876: Dental Root Canal Sealing
Adhesion to dentin can not so easily be Materials
achieved. It took a while until it was realized . ISO 7491: Dental Materials – Determination of
that chemical bonding is not the way to solve the Color Stability
problem. With modern materials a smear layer . ISO 10139–1: Dentistry – Soft lining materials
that is formed on the dentin surface during cavity for removable dentures — Part 1: Materials for
preparation is dissolved in an acid. Part of the short-term use
inorganic material of the dentin is dissolved, too. . ISO 10139–2: Dentistry – Soft lining materials
Collagen fibers extending into sound dentin re- for removable dentures – Part 2: Materials for
main on the surface. The dissolved material is long-term use
washed away or remains in the adhesive. The . ISO 10477: Dentistry – Polymer-Based Crown
adhesive penetrates the collagen and a part of the and Bridge Materials
dentin tubuli to form a hybrid layer. The meth- . ISO 22112 Dentistry – Artificial teeth for
acrylate groups of the monomers in the adhesive dental prostheses
provide chemical bonding to the filling material.
Since moisture is always present at the dentin,
surface monomers in the adhesive have to be 6. Impression Materials [53–61]
hydrophilic.
Trade names: Scotchbond (3M Espe, USA); According to their handling (chemoplastic or
Clearfil bond (Kuraray, Japan); Dentin Adh€asit thermoplastic) and their properties after setting
(Ivoclar, Liechtenstein); Syntac (Vivadent, (elastic or hard, reversible or irreversible),
Liechtenstein) Prime & Bond NT (Dentsply, impression materials can be grouped as follows:
USA);
Chemoplastic
Elastic, irreversible
5.6.6. Toxicology alginate
elastomers
The toxicology of restorative resins is an impor- Hard, irreversible
tant international issue, especially because of the impression gypsum
relatively high pulp toxicity of methyl methac- ZOE paste
rylate. For this reason, new monomers with high polymer
molecular mass have been developed, e.g., bis-
GMA (LD50 14.15 mL/kg) which is not orally Thermoplastic
toxic and does not irritate skin or mucous Elastic, reversible
membranes. Hydrocolloid
Studies on the biocompatibility of restorative Hard, reversible
resins have increased enormously in the past few impression compound
years. A series of important components of re- wax – resin
storative resins has been examined for tissue gutta-percha
compatibility, and none of the substances exam-
ined caused irritation [46]. The oldest known impression material is plas-
ter of paris (DWINELLE 1840). Dental compound
(STENT 1840) and gutta-percha (1850) were de-
5.7. Standards veloped for use as impression materials in the
mid-1800s. Hydrocolloids (agar) were intro-
The following international standards on poly- duced in 1927 (POLLER), zinc oxide and eugenol
mer based materials apply: pastes in 1935 (KELLY); alginates in 1940
Vol. 11 Dental Materials 133

(WILDING); polysulfides and condensation sili- insoluble in water but has a high ability to swell
cone resins in 1955; polyether resin in 1964 by the absorption of water.
(ESPE); and addition silicone resins in 1976. Dental alginates are powder mixtures with the
The principal requirements for impression following composition: sodium alginate (10 –
materials are: 20 wt %), calcium sulfate (10 wt %), trisodium
phosphate (1 – 4 wt %), diatomite (70 – 80
. Biocompatibility for patient and user wt %), color and flavor (1 – 2 wt %). Mixing
. Physical and chemical properties in accor- with water gives a plastic mass which sets by
dance with the purpose of impression taking chemical reaction to give an elastic hydrogel.
(precision of the dies, recording of the func- Monovalent soluble salts of alginic acid (Na, K,
tion): Flowability during impression taking, NH4 alginate) are precipitated as sparingly solu-
detail reproduction, mechanical strength, di- ble Ca salts. Since 1980 no lead compounds are
mensional stability of the impression, compat- contained in alginate, and low-dust and no-dust
ibility with the die material versions are available. The reaction is prolonged
. Efficient workability to optimal quality (lot to a practical duration by a retarder (trisodium
consistency, storability, ease of dosing phosphate) which initially reacts with the Ca
and mixing), hygienic aspects (disinfectabil- ions. Fast- and normal-setting preparations are
ity), ergonomically favorable methodology, available. The filler (diatomite) influences the
economy plasticity of the mixture as well as the strength
and elasticity of the impression. The plasticity of
The dentist needs a large choice of impression the mixture can be influenced by the powder/
materials, because they fulfill the requirements to liquid ratio, and the working time by the water
different degrees. For each task a certain impres- temperature. Dosing is performed manually, and
sion material is best suited. The choice of an mixing manually or in a mixer. The hydrogel
impression material is mainly governed by the ages (syneresis) and is sensitive to environmental
required precision of the die (documentation, conditions. Storage in air leads to a significant
type of dental restoration), the object to be repli- shrinkage of the impression. Disinfection is pos-
cated (shape and condition), and the method of sible if well-proven recommendations are fol-
impression taking. When equally good results lowed. The die must be manufactured as soon as
can be obtained with different impression mate- possible, preferably 15 min after removal of the
rials, ergonomic and economic aspects are impression from the mouth and not later then
decisive. 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
6.1. Elastic Materials
reproduction requires pressure during impression
taking and is not as good as with reversible
An important advantage of elastic materials is
hydrocolloids or elastomers.
that it is possible to remove them from the object
Handling is simple and cheap. Alginates are
from which the impression is taken without
used in many ways: to obtain dies for documenta-
breakage or extreme deformation, even when
tion, for therapy planning, removable dentures
they fill undercuts.
and removable orthodontic devices. They are not
suited for fixed restorations (crowns and bridges).
A 3 % aqueous solution of alginate is used to
6.1.1. Alginates produce insulating layer on gypsum dies in dental
polymer technology.
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- 6.1.2. Elastomers
nuronic acid and L-guluronic acid 1,4-glycosi-
dicly linked. It is contained in the marine algae in Silicones. Impression silicones can be dif-
the amount of 40 % (dry substance). It is almost ferentiated into condensation cross-linked sili-
134 Dental Materials Vol. 11

cones (C-silicones) and addition cross-linked . Dosed and homogeneously mixed by a ma-
silicones (A-silicones). chine with a dynamic mixer
In the case of C-silicones, organic polysila-
nols and polydimethylsilanediols are condensed Stability of the flowable silicones during ap-
to give macromolecules by cross-linking agents plication results from their thixotropy (reversible
(tri- and tetrafunctional alkoxysilanes) and ac- sol – gel transformation).
celerators (e.g., tin octanoate and dibutyltin di- By addition of small amounts of nonionic
laurate) with cleavage of volatile byproducts tensides, which lower the interfacial tension with
(alcohols). Fillers (10 – 80 wt %) are used to respect to water, the wettability of the hydropho-
adjust the consistency: extra fine, fine, medium, bic A-silicones is enhanced. During impression
heavy, and putty. Dosing and mixing of the taking, A-silicones with added tensides remain
base paste and hardener (as liquid or paste) are mainly hydrophobic, since the tenside micelles
performed manually. The addition of colorants align only during contact with the moist impres-
makes homogeneous mixing easier and sion object. However, contact to the hydrophilic
allows materials of different consistency to be gypsum during die production is enhanced, and
distinguished when combinations of materials this avoids voids (bubbles) on fine edges of the
are used. die. This can be achieved by the treatment of
In the case of A-Silicones, polyvinylsiloxanes nonhydrophilic silicone with a wetting liquid
and siloxanes with terminal SiH groups are (tenside in ca. 40 wt % isopropyl alcohol).
additively coupled by a platinum(0) divinylte- A comparison of C- and A-silicones is given
tramethyldisiloxane complex (Karstedt cata- in Table 7.
lyst). Reactive oligomers are formed as discrete A-silicones can be used for all kinds of im-
intermediates by transfer of H atoms to give pressions in dentistry because of excellent detail
dimethylene bridges without formation of by- reproduction, high elasticity, and superior di-
products (hydrosilylation). The polymerization mensional stability. They are neutral in taste and
reaction can be disturbed by catalyst poisons odor. They are especially suitable where high
(local anesthetics, astringents, traces of sulfur precision is needed (fixed restorations). In cases
from vulcanized latex gloves, accelerators and where other, cheaper impression materials fulfil
cross-linking agents of C-silicones). The consis- the requirements for precision, A-silicones are
tency can be adjusted from low viscosity to not used.
putty by fillers (40 – 70 wt %) and softening For silicones different impression methods
agents or paraffin oil (5 – 10 wt %). The pro- exist. The highest precision is achieved with a
ducts consists of a base paste and a catalyst combination of a high-viscosity material
paste, which are (putty) with a low-viscosity material (double-
mixing impression, corrective impression, sand-
. Dosed and mixed manually wich impression). Pressure during application
. Pressed out of a double cartridge by a static and a dry impression object are important re-
mixer (homogeneous mixing) 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 Dental Materials 135

prepared tooth substances. For functional im- filler (TiO2) and softening agents (neutral oils).
pressions (full dentures) slowly reacting mate- The reaction paste normally consists of 77 wt %
rials are advantageous. PbO2, 3 wt % sulfur, and 20 wt % filler, and
Further uses of A-silicones are: softening agents. Newer products contain organ-
ic peroxides instead of PbO2. Common are one-
. Evaluation of the positional jaw relation of the time impressions with two different consisten-
patient (materials with a high Shore hardness) cies and individual impression trays made of
. Duplication of dies in dental technology with resin material. Handling, indication and proper-
low viscosity materials ties are, at their best, comparable to those of C-
. Rebasing of dentures with a soft A-silicone silicones. The materials are sticky, biocompati-
prosthetic material bility is limited (Pb content), and taste and odor
. Soft A-silicone material in maxillofacial are unpleasant. The market share of this impres-
prosthetics. sion material is very small nowadays.

Polyethers. A poly(ethylene oxide)/poly Agar Hydro Gels. consisting of 8 – 15 wt


(tetramethylene oxide) copolymer with terminal % agar (a heteropolysaccharide from brown
aziridino groups (content in the base paste ca. algae) and 75 wt % water are converted by heat
60 wt %) are linked additively by an organic to a flowable hydro sol and set again by cooling.
sulfonium fluoroborate as starter (content in the Viscosity, plasticity, and elasticity are reversibly
reactor paste ca. 30 wt %). The consistency of the dependent on the temperature. Addition of glyc-
pastes is adjusted by fillers and softening agents erol (7 wt %) and borax (0.2 wt %) enhance
(triglycerides). Mechanical mixing is the method elasticity and strength; fillers (7 wt % kaolin)
of choice. Cooling of the pastes results in sub- affect the consistency. Potassium sulfate
stantial increases in viscosity and makes mixing (0.1 wt %) compensates for the negative influ-
difficult. Before use pastes stored in the refriger- ence of borax on the setting reaction of gypsum.
ator have to be brought to room temperature. Antiseptic additives (thymol) prevent microbial
Detail reproduction, plastic/elastic transition, contamination.
permanent deformation, and dimensional stabil- Hydrocolloid materials are distributed in
ity are the same as those of A-silicones. Resis- tubes (tray material) or in bars (syringe material).
tance to deformation during removal of the im- They have to be conditioned by stepwise heat
pression from the teeth and from the die is higher. treatment (water bath with three tanks): liquefac-
Polyethers are hydrophilic. They can be stored in tion of the gel to a sol in boiling water, tempering
air indefinitely. In aqueous media they exhibit a for storage (62 – 69 ! C); cooling to impression-
small time-dependant swelling. The time avail- taking temperature (45 – 45 ! C). Low-viscosity
able for disinfection is limited. Short-term taste hydrocolloid is placed on the impression object
disturbance may occur with some patients. The from a syringe, and then high-viscosity material
main use is for fixed restorations. Mono-phase is applied on top with an impression tray. Special
impressions and one-time two-phase impressions impression trays are necessary that provide me-
with individual impression trays are preferred. chanical retention for the impression material
The die material is gypsum. Galvanic die fabri- and are equipped with channels for water
cation by silver plating is possible; copper plating cooling.
is not recommended. A special polyether mate- Detail reproduction of the hydrophilic mate-
rial for evaluation of the positional jaw relation is rial is very good, even under low pressure. Per-
available. manent plastic deformation is higher than with
elastomers, and tear resistance is much lower.
Polysulfides. Polysulfide oligomers with The field of use is impressions for fixed restora-
terminal and side-chain SH groups are three- tions (inlays, crowns, bridges). Results equal to
dimensionally linked at the SH groups by lead those of elastomers are reached with correct
dioxide or manganese dioxide. An elastomer is handling. Disinfection is possible only with short
created by polycondensation. The base paste contact time. Hydrocolloid impressions can not
consists of 50 – 90 wt % polysulfide oligomer be stored; immediate casting of a die (gypsum) is
and, depending on the consistency, 10 – 50 wt % necessary.
136 Dental Materials Vol. 11

6.2. Rigid Materials cially those of the oral mucosa change rapidly).
During removal from undercuts, plastic defor-
6.2.1. Plaster of Paris mation of the impression occurs. Impressions can
be disinfected and stored for a long time. The die
A powder of CaSO4 b-hemihydrate (90 wt %), material is gypsum. After setting of the die
fillers (alumina, CaCO3, diatomite; 7 wt %), ac- gypsum, the paste can be softened by immersion
celerators (K2SO4, NaCl; 2 wt %), color, and in water (70 ! C) and pulled off. Zinc oxide pastes
flavor is mixed with water (1.5 to 2 parts of are rarely used nowadays (compression impres-
powder, 1 part of water) and hardens to an sion of the mucosa).
irreversible rigid impression within 3 – 5 min.
Flowability and plasticity can be satisfactorily
adjusted by means of the water content and 6.2.3. Resins
depend on the working temperature. The reaction
is exothermic. Plaster expands slightly (max. Self-hardening methyl methacrylate/poly(meth-
0.15 % linear). Detail reproduction is very good yl methacrylate) systems are no longer used
as long as no small parts of the impression break today for biological and methodological reasons.
off and get lost. In the case of undercuts, the Polymeric materials for temporary rebasing of
hardened material must be broken and put to- dentures can be used as impression materials to
gether again. Plaster impressions can be stored give a working model for a new denture. These
indefinitely. The material for die casting is also materials consist of a polymer bead powder of
gypsum. Before pouring in the die gypsum, the higher acrylates [poly(ethyl methacrylate)],
impression must be disinfected, watered, and which is swelled for a few minutes in a mixture
treated with a release agent. The separation of of phthalate ester and alcohol to give first a
impression and die gypsum is difficult, and the flowable and then a stable gel, without a setting
surface of the die can be damaged during this reaction taking place. The mass reacts on short
procedure. term loading with rebound (elasticity), and on
Plaster of Paris is used for functional and long term loading with flow (plasticity).
anatomic impression taking of the edentulous
jaw and fixation impression of restorations. It is
rarely used for impressions since the introduction 6.2.4. Thermoplastic Impression
of alginate and elastomers. The procedure is Materials
unpleasant for the patient. Another use is fixation
during determination of the positional jaw Thermoplastic impression materials were for-
relation. merly composed of natural materials (copal,
shellac, colophonium, mastics, sandarac resin,
carnauba wax, raw rubber). Today mainly syn-
6.2.2. Zinc Oxide – Eugenol Pastes thetic resins, waxes, and fatty acids (stearic,
palmitic, and oil acids) are used. Added to this
The reactive components ZnO and eugenol are fillers and colors. The masses are reversibly
(80 – 96 wt %) are supplied as two pastes, which plastified in a water bath or by a flame. They can
are adjusted in consistency by oils (olive oil, be disinfected. Gypsum is used as die material.
mineral oil) and fillers (talc, kaolin, rosin, vase- Thermoplastic materials belong to the oldest
line). Zinc acetate and magnesium chloride are impression materials. Today their market share
used as accelerators for the formation of zinc is low.
eugenolate. Addition of a few drops of water Thermoplastic impression compounds consist
during mixing enhances setting. Irritation of of resin, fatty acid, and filler in a ratio of 2/1/3.
tissue by eugenol is possible. Impressions are The usual filler is magnesium silicate (talc). The
taken from the wet mucosa with individual im- necessary plasticity for impression taking is
pression trays (functional impression with thin reached at 50 – 45 ! C. Hardening takes place
layers of paste; unwanted high-detail reproduc- above 37 ! C. At room temperature the materials
tion to avoid micromechanical influences on the remain rigid, even under pressure. Today these
mucosa by the prosthesis since the details espe- materials are used in dentistry only as accessories
Vol. 11 Dental Materials 137

during impression taking (individualization of Dental waxes are generally used after being
impression trays). heated to a softened or liquid state. Below the
Wax/resin materials contain 70 – 80 wt % melting point, a solid – solid change occurs in
synthetic resins, 15 – 25 wt % hard paraffin, par- the crystal lattice; a wax should be molded above
affin oil, and fillers. Some products contain metal this temperature to avoid internal stress which
powders to enhance heat capacity. At mouth can result in distortions of the pattern. The ad-
temperature the materials are flowable under the vantages of waxes include easy workability,
pressure from the soft tissues of the mouth (func- good polishability, broad softening range, low
tional impression), and rigid at room temperature viscosity when melted, hydrophobic behavior,
and pressureless storage. and clean burnout. Among the disadvantages of
Gutta-percha is the trans isomer of natural waxes are high thermal expansion, formation of
rubber. Impression materials contain 60 wt % internal stresses, solid – solid transition, and low
gutta-percha, resins (25 wt %), and fillers hardness at room temperature.
(15 wt %). Gutta-percha is occasionally used for Some dental waxes are used as material for
special impression tasks for removable prosthe- patterns in the lost-wax technique. This tech-
ses and in maxillofacial prosthetics. nique, also called the indirect technique, involves
fabrication of a wax pattern, embedding it in an
investment, burnout of the wax, and casting a
7. Dental Waxes molten alloy in the hollow space. Inlays, crowns,
bridges, and the metal framework of partial
Waxes are used in rather large quantities in dentures are constructed in this manner. Other
various dental laboratory and clinical proce- types of waxes are used for bite registration,
dures. Different types of waxes are required for construction of trial baseplates for complete
various applications. The differences relate dentures, and temporary connection of fragments
chiefly to softening behavior and hardness, and of a broken denture before a repair procedure.
the characteristics desired are usually obtained Many types of dental wax are marketed. Their
by blending natural and synthetic waxes. Waxes names indicate the uses for which they are
are not chemically uniform materials. They are intended:
defined only by their similar properties.
Natural waxes are obtained either from ani- * modeling wax
mals, mostly insects, or from minerals. In the * casting wax, burnout wax, inlay wax
dental literature, the following natural compo- * carding wax, setup wax
nents are often cited: paraffin, ceresin, carnauba * bite registration wax
wax, candelilla wax, and beeswax. * blockout wax
Synthetic waxes, waxlike materials, and ad- * baseplate wax
ditives are often added to the natural waxes. * correction wax
Among these, the most important synthetic * sticky wax, adhesive wax.
waxes are polyethylene wax, polyoxyethylene
glycol wax, and esters of long-chain aliphatic Because of their particular importance, dental
alcohols and organic acids. inlay casting wax and baseplate wax are treated
Various additives, e.g., resins, rosin, dammar, in more detail in the following paragraphs.
myricyl palmitate, or stearates, are added to
special-purpose waxes. Coloring agents, usually Dental Inlay Casting Wax. Inlay wax is
fat-soluble dyes, are dissolved in dental waxes to used to produce cast inlays. It is available in two
differentiate the various types and to approxi- slightly different types: type I for direct modeling
mate the natural color of the gingiva and the in the mouth and type II for indirect modeling on
teeth. the die. Both wax qualities must (1) burn out
Most of the waxes and waxlike substances can without residue, (2) have minimum thermal con-
be melted together to form mixtures that do not traction, (3) be carved without chipping and
separate when cooled. In this way, any special flaking, and (4) be intensely colored. Type I must
dental wax required for specific dental laboratory not solidify at 37 ! C but should flow easily at
and clinical applications can be made. 43 ! C, whereas type II must still not soften at
138 Dental Materials Vol. 11

34 ! C and should flow easily at 40 ! C. Inlay The materials are rarely used because of their
waxes contain a larger fraction of hard waxes, disadvantages. Resins are very rigid and provide
such as carnauba wax, than the related baseplate good reproduction of details. However, they
waxes. require a long setting time, some products are
sticky after mixing is complete, they are not
Dental Baseplate Wax (Modeling Wax). compatible with all impression materials, and
Baseplate wax is preferred in the production of they contract during setting.
dentures to shape the denture base that is later
made from resin. The waxes are mixtures of Metallic Materials. The amalgams used as
paraffin and beeswax with minor additions of die materials are identical with the silver amal-
carnauba wax. The modeling waxes are classified gams described in Chapter 2. They cannot be
into three types which differ slightly in their used with elastic impressions because they must
softening range and hardness. The following be placed by plugging. Hardness and absence of
requirements must be fulfilled: easy removal shrinkage are good; detail reproduction is satis-
with boiling detergent solution, low thermal factory. Their use is restricted to small models or
contraction, easy trimming and carving, and dies.
glossy surface after gentle flaming. Electrolytic plating of the impressions with
copper or silver and, more rarely, with nickel
produces very good models and dies. However,
8. Other Model and Die Materials plaster, alginate, and hydrocolloid impression
materials cannot be electroplated. The impres-
The most important model material is dental sion, made conductive by dusting with metal or
stone (model gypsum); this is treated in detail graphite powder (dental compound), is sus-
in Chapter 9. In this chapter, only model materi- pended in an aqueous electrolyte as the cathode.
als other than gypsum are treated briefly; these The main components of the electrolyte are
materials, however, are much less important than copper sulfate or silver cyanide, respectively.
gypsum. Pure copper or silver is used as the anode.
Appropriate selection of the bath and the electri-
Die Cements. The composition of die ce- cal current leads to development of a thin, but
ments is similar to that of the silicophosphate and smooth and homogeneous, coating of the impres-
stone cements described in Chapter 4. As a result sion. Detail reproduction, precision, and rigidity
of their poor physical properties, these materials of the models are very good. To prevent defor-
are rarely used today. mation during manipulation, dental stone is cast
Only small amounts of powder and liquid into the plated impression. The only disadvan-
(acid) can be mixed to form a thick, homoge- tage is the time required for the plating procedure
neous, plastic mix. For this reason, only small (up to 10 h).
models or single tooth dies can be fabricated. The
advantages of die cements are their high rigidity
and good scratch resistance. Their disadvantages 9. Dental Gypsum Products
are poor flow rate, contraction during setting and
storage, and the fact that they can be used only Gypsum materials have a wide spectrum of use in
with compound impression materials. dentistry. In addition to their use as model ma-
terials, they also serve as impression plasters
Resins. Various resins which cure at room (Section 6.1.1), as a component of alginate im-
temperature are used as binders for chemically pression materials (Section 6.2.2), and as a com-
inert fillers. Methyl methacrylates, polyesters, ponent of investment materials (Chap. 10). His-
epoxies, and ethylenimine resins are available tory, raw materials, phases of the CaSO4– H2O
commercially. Very fine quartz powder and met- system, natural and byproduct gypsum, and pro-
al powders are used as fillers; their chief function duction of calcium sulfate hemihydrate are de-
is to reduce shrinkage during setting. The mate- scribed elsewhere (! Calcium Sulfate) [62].
rials are available as powder and liquid or as two- Dental gypsum products are classified by inter-
paste systems. national standards:
Vol. 11 Dental Materials 139

Type 1: Impression plaster . Type 1 impression plaster (see Section 6.2.1).


Type 2: Dental plaster . Type 2 dental plaster consists of b-CaSO4
Type 3: Dental stone hemihydrate and modifiers.
Type 4: Dental stone, high strength . Type 3 dental stone consists of a-CaSO4 hemi-
hydrate crystals with a small specific surface
Use as Model Material. A dental impres- and modifiers.
sion is a negative reproduction of the teeth and . Type 4 dental stone high strength consists of an
the oral tissues. By pouring a suitable model a-CaSO4 hemihydrate that has been dehy-
material into this negative form, the dental tech- drated in an autoclave with special solutions
nician obtains a positive cast of the form and [65]. This type also contains modifiers, added
relationship of the teeth and oral tissues. Dental by the manufacturer to obtain the properties of
stone and high-strength dental stone are ideally the final product required by national and
suited for high-precision mastercasts. Dental international specifications.
plasters are suitable for study, repair, and refer-
ence casts. Typical ionic additives are potassium sulfate,
potassium citrate and sodium potassium tartrate.
Requirements. The requirements for such Water-soluble melanine resins are used as non-
a material depend on the purpose for which it ionic additives to increase the fluidity of the
is used: type 2 dental plaster should be easy to water – hemihydrate mixture. All these modi-
manipulate and show a smooth surface; type 3 fiers influence the setting expansion, the setting
dental stone and type 4 dental stone, high time, the hardness of the dental stone, and the
strength should be easy to manipulate, be morphology of the dihydrate crystals. Potassium-
compatible with common impression materials, containing additives can produce crystals of syn-
have a very good fluidity in the plastic phase genite (potassium calcium sulfate), which can
thus needing a short time for vibration, and appear as efflorescences on the surface of dental
have a short setting time (max. 30 min). On casts [66–68].
the other hand, the setting time must be long The setting time [69–72] can be shortened by
enough to facilitate pouring of the impression (1) addition of inorganic acids and their salts,
[62–64]. such as calcium sulfate dihydrate, 3 % sodium
In addition to the requirements mentioned sulfate; 2.5 % sodium chloride, or 2 – 3 % po-
above, the final model should show the finest tassium sulfate; (2) intensive and extended spa-
details; have a smooth surface without pores; tulation (excessive spatulation destroys the crys-
have sufficient strength, hardness, and wear re- tal structure and decreases strength); and (3) low
sistance; and have a constant volume (small water-to-powder ratio.
expansion is better than even minimal shrinkage) The setting time can be prolonged by (1)
[63], [64]. addition of organic acids and their salts as well
The requirements for hardness, compressive as the presence of organic colloids such as dried
strength, and the maximum linear setting expan- blood or gelatin; (2) addition of salts of phos-
sion are different for all four types of gypsum. phoric and boric acids; (3) addition of more than
None of the model materials of type 2 – 4 can 3 % of sodium chloride; (4) presence of nitrate or
fulfill perfectly all the requirements mentioned. citrate;and (5) high water-to-powder ratio [62].
Dental stone high strength fulfills them best and The setting reaction does not completely con-
is therefore the most common model material for vert the calcium sulfate hemihydrate to dihy-
casts used for the construction of inlays, crowns, drate. Residual hemihydrate is present in the
bridges and removable partial or full dentures structure of fully set casts [66].
[63], [64].
Physical Properties. The strength of hard-
Chemical Composition. Calcium sulfate ened calcium sulfate dihydrate is directly propor-
hemihydrate occurs in two phases: a and b (for tional to its density; therefore, the strength de-
more details, see ! Calcium Sulfate). The com- pends on the ratio of water to hemihydrate powder
position of dental gypsum products are as and on the porosity of the hardened plaster or
follows: stone. Dental a-CaSO4 hemihydrates (stones)
140 Dental Materials Vol. 11

need small amounts of water for mixing and Volume Change. The absolute volume of a
fluidizing and therefore have a high density and mixture of CaSO4 hemihydrate and water first
great strength; however, they are brittle. The decreases when CaSO4 dihydrate is formed. The
strength of calcium sulfate dihydrate also depends contraction can only be measured for a short time
on the humidity of the atmosphere during storage. after mixing [71], [76–79]. As soon as the rehy-
The hardness of rehydrated type 3 dental drated gypsum hardens, expansion starts. The
stone and type 4 dental stone high strength in- thermal expansion during setting is reversible,
creases with the time of storage. Chemically but the setting expansion is almost irreversible.
produced gypsum reaches its final hardness after This setting expansion is influenced by (1) the
4 d, whereas natural gypsum needs 6 d. Due to water-to-powder ratio: the lower the water con-
sedimentation, the hardness of a cast is greater on tent, the greater is the expansion; (2) the presence
the bottom than on the surface, where more pores of chemicals: for example, potassium sulfate
are located [62], [73–75]. lowers the expansion but also the strength; (3)
The hardness can also be influenced by con- the climate: storage of a model of type 4 dental
tact with some impression materials. Contact stone high strength after the removal of the
with hydrocolloids, condensation-cured sili- impression at 23 ! C and 50 % relative humidity
cones, and polyethers lowers the hardness. This results in a contraction of about 0.05 % of its
tendency can be reduced if the impression with highest setting expansion within 7 d (Figs. 10
the mixed hemihydrate is stored at 95 % R.H. for and 11); and (4) spatulation: high intensity and
30 min or during the entire setting period [62]. 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 stones should be packed and stored in protective,
23 ! C and 50 % rel. humidity) as a function of storage moistureproof, and sealed containers. Each con-
conditions [62], [76] tainer must at least be marked clearly with the
A: Storage in a closed extensometer
B: Storage at 23 ! C and 50 % relative humidity following information: name and/or trademark
C: Immersion in water bath for 5 min and subsequent stor- of the manufacturer, type, lot number, date of
age as in B packaging, and date beyond which the material
For experimental conditions of A, B, C, see Figure 10. should not be used without retesting when stored
under the recommended conditions: ca. 23 ! C
drate mixture increase the expansion of type 3 and not more than 50 % relative humidity.
and type 4 dental stone. Trade names: Type 2: Snow White Plaster
The results of the setting expansion depend on No. 1 (Kerr); Alabaster (Dr. B€ohme); Laboratory
the method and time of measurement (Figs. 10 Plaster (Whip Mix).
and 11). The dental gypsum products are mea- Type 3: Castone, R & R Lab Stone (Dentsply);
sured in an extensometer with a length of 100 mm 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 Vol. 11

(Heraeus-Kulzer); Modelit (Dr. B€ohme); Micro- . Compatibility with the alloys


stone, Quickstone (Whip Mix). . Keeping the high thermal expansion during the
Type 4: Duralit (DeguDent); Duroc (Dents- entire time of casting and reversible thermal
ply); Begodur (Bego); Octa-Stone (Heraeus- expansion on cooling
Kulzer); Gilstone (Giulini); Silky-Rock (Whip . Easy removal from the cast object
Mix); Super-Cal Dental Stone (Coe Lab.); Te- . A possible additional requirement is suitability
westone (Kettenbach); Vel-Mix (Kerr). for the rapid-burnout method.

Chemical Composition. Casting invest-


10. Dental Investments ment materials consist of bonding and refractory
materials. The refractory materials such as silica,
An investment is generally a powder mixture usually quartz or cristobalite or a mixture thereof
which can be mixed with a liquid to give a are responsible for the thermal expansion.
flowable paste that sets in a given time. The a-Cristobalite changes reversibly into b-cristo-
refractory material allows heating above balite, and a-quartz into b-quartz. These two
1100 ! C. These properties make the material crystal structure transformations result in the
suitable as a mold material for alloy casting. reversible thermal expansion of an investment.
In dental technology a model is made from an Standard investments need time for these trans-
impression that reproduces the teeth. The wax formations to take place without formation of
pattern (or resin, adapter cap) is shaped on this cracks; hence, holding times at 270 and 573 ! C
model. The pattern is removed from the model are needed during the heating process.
and provided with sprues on a base former and a
casting ring. The mixed investment material is Gypsum-Bonded Investments. The bond-
then poured into the casting ring. After hardening ing material is a-calcium sulfate hemihydrate
of the investment, the mold is heated to burn out CaSO4 ' 0.5 H2O, which is converted to calcium
the wax model. The casting mold is brought to the sulfate dihydrate CaSO4 ' 2 H2O by mixing with
final temperature required by the particular alloy. water. The excess water is vaporized during
After casting the object is divested and is ready to initial heating to about 100 ! C, and above this
be worked on. temperature water of crystallization is driven out
of the investment. After reaching a temperature
Classification. Investments can be classi- of 150 ! C, gypsum-bonded investments either
fied according to the nature of the bonding mate- show a slight thermal contraction or remain
rial (gypsum- or phosphate-bonded) or the pur- unchanged up to 225 ! C. At higher temperatures,
pose for which they are produced (Co – Cr the presence of silica dominates the thermal
castings, precious metal castings, soldering of expansion. Gypsum-bonded investments should
metallic parts, ceramic pressure technique). not be heated to temperatures exceeding 700 ! C.
Beyond that point, gypsum decomposes in the
Requirements. Investment casting materi- presence of silica to liberate sulfur dioxide, which
als should fulfill the following requirements: causes porosity and corrosion of the casting.

. Expansion control: diluting the liquid compo- 2 CaSO4 ! 2 CaOþ2 SO2 þO2
nent of phosphate-bonded investment materi-
als with distilled water allows the expansion of Expansion control of gypsum bonded invest-
an investment to be controlled in a way that the ments is achieved by varying the mixing ratio
contraction of the particular casting alloy is with water.
compensated
. A suitable setting time Phosphate-Bonded Investments. High-
. Creamy consistency during investment temperature investments require a bonding ma-
. Production of a smooth surface and reproduc- terial other than gypsum. This bonding material
tion of fine details consists of magnesium ammonium phosphate or
. No cracking during heating and on impinge- a soluble acid phosphate such as ammonium
ment of the molten alloy dihydrogenphosphate and a metal oxide such as
Vol. 11 Dental Materials 143

magnesia. These materials are mixed with an investments and should compensate for the
aqueous silica sol. The following simplified shrinkage of the casting alloys; however, the two
chemical reaction occurs during setting at room materials have different thermal contraction
temperature and gives the investment the green curves. The thermal expansion of the investment
strength before heating: materials depends on their composition and, in
the case of phosphate-bonded investments, on the
ðNH4 ÞH2 PO4 þMgOþ5 H2 O ! MgNH4 PO4 '6 H2 O
dilution of the liquid component and the particle
size of the silica. The thermal expansion curves
The next reaction takes place during heating, for quartz and cristobalite are very much differ-
water and ammonia are evolved above 200 and ent. Moreover, both silica modifications show a
300 ! C, respectively. phase transition, each at a different temperature:
quartz at 573 ! C and cristobalite at 200 –
2 ðMgNH4 PO4 '6 H2 OÞ ! Mg2 P2 O7 þ13 H2 Oþ2 NH3
270 ! C. All modifications of silica show a break
in their expansion curves. Therefore, the thermal
The silica-catalyzed decomposition into mag- expansion curves for investment materials are
nesium diphosphate increases the strength and very complicated.
hardness of the phosphate-bonded investment. Setting time of phosphate bonded investment
By heating above 1000 ! C with MgO surplus the materials is dependent on the reaction time of the
following reaction takes place: two bonding materials and consequently on their
mixing ratio and their grain size. Gypsum-bond-
Mg2 P2 O7 þMgO ! Mg3 ðPO4 Þ2
ed investment materials include small amounts of
chemical additives which influence the setting
time.
Physical Properties. The most important
physical property of a dental investment material Hardness. All dental investments need en-
is expansion. The expansion is the sum of setting ough hardness to resist the high temperatures and
and thermal expansions and is responsible for the the casting impact.
outstanding accuracy of dental restorations.
Quality Standards. The classification and
Setting Expansion. The setting of the phos- requirements for investment materials together
phate-bonded investments is accompanied by the with the corresponding test methods are de-
evolution of heat. At the end of the reaction scribed in the standards ISO 9694 (Dental Phos-
process, the temperature reaches a maximum of phate-Bonded Casting Investments, 1996) and
55 – 80 ! C. This temperature increase affects ISO 7490 (Dental Gypsum-Bonded Casting In-
the setting expansion. A standardized method vestments 2000).
for measurement of the setting expansion is
presently under discussion. The setting expan- Application. In general, the instructions of
sion constitutes about 30 – 50 % of the thermal the manufacturer should be strictly followed for
expansion and is caused by the reaction of the optimum results. Gypsum-bonded investment
bonder. The bonder transformation separates the materials should not come into contact with
quartz and cristobalite grains and the result is an phosphate-bonded investment materials. For
increase in volume. This process is intensified by gypsum- and phosphate-bonded investment ma-
mixing the powder with a special liquid and terials, the use of separate mixing bowls and
causes aqueous silica particles to crystallize to spatulas is necessary. Standard investment ma-
long needles. terials need preheating with holding times to
The setting expansion of gypsum-bonded in- withstand the quartz and cristobalite phase tran-
vestments is based on the same principles as for sitions without cracking. Rapid-burnout invest-
gypsum products in Chapter 9. ment materials can be preheated in an oven at the
final temperature. Exact ratios of the bonding and
Thermal Expansion. When dental alloys the silica materials and the use of special liquid
are cast, they contract on cooling. For this reason, components are the reasons for these robust
thermal expansion is very important for dental properties. The advantages are that they do not
144 Dental Materials Vol. 11

require preheating in a controlled oven, have 27 K. Krumbholz, Quintessenz Zahntech. 9 (1983) 1175 –
shorter heating times, and save energy. 1179.
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