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RECENT ADVANCES IN CERAMICS FOR DENTISTRY
Isabelle L. Denry
The Ohio State University, College of Dentistry, Section of Restorative, Prosthodontics, and Endodontics, 305 W. 12th Avenue, Columbus, OH 43210-1241
ABSTRACT: For the last ten years, the application of high-technology processes to dental ceramics allowed for the develop-
ment of new materials such as heat-pressed, injection-molded, and slip-cast ceramics and glass-ceramics. The purpose of the
present paper is to review advances in new materials and processes available for making all-ceramic dental restorations.
Concepts on the structure and strengthening mechanisms of dental ceramics are provided. Major developments in materials
for all-ceramic restorations are addressed. These advances include improved processing techniques and greater mechanical
properties. An overview of the processing techniques available for all-ceramic materials is given, including sintering, casting,
machining, slip-casting, and heat-pressing. The most recent ceramic materials are reviewed with respect to their principal crys-
talline phases, including leucite, alumina, forsterite, zirconia, mica, hydroxyapatite, lithium disilicate, sanidine, and spinel.
Finally, a summary of flexural strength data available for all-ceramic materials is included.
Matches that of glassy phase (GP) Higher than that of GP Higher than that of GP Low fracture probability
Matches that of GP Lower than that of GP Lower than that of GP High fracture probability
Higher than that of GP Higher than that of GP Higher than that of GP Debonding of the crystals
from the matrix
Lower than that of GP Lower or higher than Lower or higher than Radial cracks, very high
that of GP that of GP fracture probability
Several methods are used to improve the strength and piece. The technique involves heating of the glass to a
clinical performance of dental ceramics, including crys- temperature above the glass transition region and below
talline reinforcement, chemical strengthening, and ther- the softening point. It is then cooled to room tempera-
mal tempering. ture in a jet of air or, in some cases, in an oil bath. The
Strengthening by crystalline reinforcement involves residual stresses arise from differences in cooling rates
the introduction of a high proportion of the crystalline for surface and interior regions. The result is similar to
phase into the ceramic to improve its resistance to crack that obtained with chemical strengthening with the for-
propagation. However, the crystalline phase must be mation of a surface compressive layer that results in
carefully selected. Important selection criteria include increased strength. This technique has been successfully
the coefficient of thermal contraction, toughness, and applied to feldspathic dental porcelain and resulted in
the modulus of elasticity. The influence of these crys- mean flexure strength values 2.6 times greater than the
talline-phase characteristics compared with those of the corresponding value for slow-cooled specimens
glassy matrix on the fracture probability of two-phase (Anusavice and Hojjatie, 1991). The stress relaxation
ceramic materials is summarized in Table 1. behavior of dental porcelain when reheated can be char-
Chemical strengthening is another method used to acterized by stress relaxation testing under compression
increase the strength of glasses and ceramics. The prin- at high temperature (DeHoff et al, 1994) or by acoustic
ciple of chemical strengthening relies on the exchange of emission techniques (Asaoka et al, 1992). The principal
small alkali ions for larger ions below the strain point of effect of tempering is the inhibition of crack formation
the ceramic. Since stress relaxation is not possible in rather than the retardation of crack growth (Anusavice et
this temperature range, the exchange leads to the cre- al, 1991; DeHoff and Anusavice, 1992; Hojjatie and
ation of a compressive layer at the surface of the ceram- Anusavice, 1993). However, the combination of thermal
ic (Dunn et al, 1977). Finally, any applied load must first tempering and subsequent ion-exchange does not lead
overcome this built-in compression layer before the sur- to a significant increase in the mean biaxial flexural
face can be placed into tension, resulting in an increase strength values (Anusavice et al, 1992).
in fracture resistance. This technique involves the use of One last method commonly used to strengthen
alkali salts with a melting point lower than the glass tran- ceramics is the glazing procedure. The principle is the
sition temperature of the ceramic material. Ion-exchange formation of a low-expansion surface layer formed at
strengthening has been reported to increase the flexural high temperature. When cooled, the low-expansion glaze
strength of feldspathic dental porcelain up to 80%, places the surface of the ceramic in compression and
depending on the ionic species involved and the compo- reduces the depth and width of surface flaws. However,
sition of the porcelain (Seghi et al, 1990a; Denry et al, glazing does not significantly improve the biaxial flexure
1993). The depth of the ion-exchanged layer has been strength of feldspathic dental porcelain (Fairhurst et al,
shown to be greater than 50 micrometers (Anusavice et 1992; Griggsetal, 1995).
al, 1994a). However, this technique is diffusion-driven,
and its kinetics are limited by factors such as time, tem- REVIEW OF NEW MATERIALS AND PROCESSES
perature, and ionic radius of the exchanged ions. Within the last ten years, an increasing number of ceram-
Thermal tempering is commonly used to strengthen ic materials for all-ceramic restorations has been devel-
glasses and is based on the creation of temperature gra- oped. Each of these materials uses a different approach
dients between the surface and the bulk part of the glass in attempting to improve the mechanical properties
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without being detrimental to the esthetic qualities of the core porcelain is now baked directly onto a refractory die
ceramic. They can be classified first according to the pro- (McLean et al , 1994).
cessing technique and second according to their major
crystalline phase. Magnesia-based core porcelain
Magnesia core ceramic was developed as an experimen-
Sintered porcelains tal material in 1985 (O'Brien, 1985). Its high thermal
expansion coefficient (14.5 x 10'6/C) closely matches
Leucite-reinforced feldspathic porcelain that of body and incisal porcelains designed for bonding
Optec HSP material (leneric/Pentron, Inc.) is a feldspath- to metal (13.5 x 10"6/C). The flexural strength of unglazed
ic porcelain containing up to 45 vol% tetragonal leucite magnesia core ceramic is twice as high (131 MPa) as that
(Schmid et al, 1992; Piche et al, 1994; Denry and of conventional feldspathic porcelain (65 MPa). The core
Rosenstiel, 1995). The greater leucite content of Optec material is made by reacting magnesia with a silica glass
HSP porcelain compared with conventional feldspathic within the 1100-1150C temperature range. This treat-
porcelain for metal-ceramics leads to a higher modulus ment leads to the formation of forsterite (Mg2Si04) in
of rupture and compressive strength (Vaidyanathan et al, various amounts, depending on the holding time. The
1989). The large amount of leucite in the material con- proposed strengthening mechanism is the precipitation
tributes to a high thermal contraction coefficient (Katz, of fine forsterite crystals (O'Brien et al, 1993). The mag-
1989). In addition, the large thermal contraction mis- nesia core material can be significantly strengthened by
match between leucite (22 to 25 x 10"6/C) and the glassy glazing, thereby placing the surface under residual com-
matrix (8 x 10~6/C) results in the development of tangen- pressive stresses that have to be overcome before frac-
tial compressive stresses in the glass around the leucite ture can occur (Wagner et al, 1992).
crystals when cooled. These stresses can act as crack
deflectors and contribute to increase the resistance of Zirconia-based porcelain
the weaker glassy phase to crack propagation. After heat Mirage II (Myron International, Kansas City, KS) is a con-
treatment of Optec HSP for one hour at temperatures ventional feldspathic porcelain in which tetragonal zirco-
ranging from 705 to 980C, a second metastable phase nia fibers have been included. Zirconia undergoes a crys-
identified as sanidine (KAlSi3O8) forms at the expense of tallographic transformation from monoclinic to tetrago-
the glassy matrix (Vaidyanathan et al, 1989). The crystal- nal at 1173C. Partial stabilization can be obtained by
lization of sanidine is associated with a modification of using various oxides such as CaO, MgO, Y2O3, and CeO,
the optical properties of the material from translucent to which allows the high-temperature tetragonal phase to
opaque. However, sanidine does not appear when the be retained at room temperature. The transformation of
porcelain is heated to 980C, since sanidine is partially stabilized tetragonal zirconia into the stable
metastable in the temperature range 500-925C. The pre- monoclinic form can also occur under stress and is asso-
cipitation of sanidine has been reported as well upon ciated with a slight particle volume increase. The result
isothermal heat treatment of conventional feldspathic of this transformation is that compressive stresses are
porcelain for metal-ceramics (Mackert et al, 1986b; established on the crack surface, thereby arresting its
Mackert, 1988; Barreiro et al, 1989). An isothermal time- growth. This mechanism is called transformation tough-
temperature-transformation diagram that makes it pos- ening. The addition of yttria-stabilized zirconia to a con-
sible to predict the amount of leucite and sanidine in ventional feldspathic porcelain has been shown to pro-
samples subjected to different thermal histories has duce substantial improvements in fracture toughness,
been established (Barreiro and Vicente, 1993). strength, and thermal shock resistance (Morena et al
1986a; Kon et al, 1990). However, other properties, such
Alumina-based porcelain as translucency and fusion temperature, can be adverse-
Aluminous core porcelain is a typical example of ly affected. The modulus of rupture of commercially
strengthening by dispersion of a crystalline phase available zirconia-reinforced feldspathic dental porcelain
(McLean and Kedge, 1987). Alumina has a high modulus (Mirage II) is not significantly different from that of con-
of elasticity (350 GPa) and high fracture toughness (3.5 to ventional feldspathic porcelain (Seghi et al, 1990b).
4 MPa.m05). Its dispersion in a glassy matrix of similar
thermal expansion coefficient leads to significant Glass-ceramics
strengthening of the core. The first aluminous core
Mica-based
porcelains contained 40 to 50% alumina by weight
(McLean and Hughes, 1965). The core was baked on a As described earlier, glass-ceramics are obtained by con-
platinum foil and later veneered with matched-expan- trolled devitrification of glasses with a suitable composi-
sion porcelain. Hi-Ceram (Vident, Baldwin Park, CA) is a tion including nucleating agents. Depending on the
more recent development of this technique. Aluminous composition of the glass, various crystalline phases can
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ture ceramic inlays or onlays from resin analogs. The mold made by the lost-wax technique. This temperature
Celay system is a mechanical device based on panto- is held for 20 minutes in a specially designed automatic
graphic tracing of a resin inlay or onlay fabricated direct- press furnace (Dong et al, 1992). The ceramic ingots are
ly onto the prepared tooth or onto the master die available in different shades. They are produced by sin-
(EidenbenzeU/., 1994). tering at 1200C and contain leucite crystals obtained by
As with the Cerec system, the starting material is a surface crystallization (Holand et al. , 1995). The leucite
ceramic blank available in different shades. One ceramic crystals are further dispersed by the hot-pressing step.
material currently available for use with the Celay system The final microstructure of IPS Empress exhibits 40% by
is Vita-Celay (Vident, Baldwin Park, CA). This material volume of tetragonal leucite. The leucite crystals mea-
contains sanidine as the major crystalline phase within a sure 1-5 um and are dispersed in a glassy matrix. Two fin-
glassy matrix. Recently, ln-Ceram pre-sintered slip-cast ishing techniques can be used with IPS Empress: a stain-
alumina blocks (Vident, Baldwin Park, CA) have been ing technique or a layering technique involving the appli-
machined with the Celay copy-milling system used to cation of veneering porcelain. The two techniques lead to
generate copings for crowns and fixed partial dentures comparable mean flexure strength values for the result-
(McLaren and Sorensen, 1995). The alumina copings ing porcelain composite (Luthy et al, 1993). The thermal
were further infiltrated with glass following the conven- expansion coefficient of the IPS Empress material for the
tional ln-Ceram technique, resulting in a final marginal veneering technique (14.9 x 10"6/C) is lower than that of
accuracy within 50 urn. the material for the staining technique (18 x 10~6/C) to
be compatible with the thermal expansion coefficient of
Slip-cast ceramics the veneering porcelain. The flexural strength of IPS
Empress material was significantly improved after addi-
Alumina-based (\n-Ceram) tional firings (Dong et al, 1992). The strength increase is
ln-Ceram (Vident, Baldwin Park, CA) is a slip-cast alumi- attributed to a good dispersion of the fine leucite crys-
nous porcelain. The alumina-based slip is applied to a tals as well as the tangential compressive stresses aris-
gypsum refractory die designed to shrink during firing. ing from the thermal contraction mismatch between the
The alumina content of the slip is more than 90%, with a leucite crystals and the glassy matrix.
particle size between 0.5 and 3.5 micrometers. After
being fired for four hours at 1100C, the porous alumina Spinel-based
coping is shaped and infiltrated with a lanthanum-con- Alceram (Innotek Dental Corp, Lakewood, CO) is a mate-
taining glass during a second firing at 1150C for four rial for injection-molded technology and contains a mag-
hours. After removal of the excess glass, the restoration nesium spinel (MgAl2O4) as the major crystalline phase
is veneered with matched expansion veneer porcelain (McLean and Kedge, 1987). This system was initially
(Probster and Diehl, 1992). This processing technique is introduced as the "shrink-free" Cerestore system, which
unique in dentistry and leads to a high-strength materi- relied on the conversion of alumina and magnesium
al due to the presence of densely packed alumina parti- oxide to a magnesium aluminate spinel. One of the rec-
cles and the reduction of porosity. ognized advantages of this system was the excellent mar-
Two modified porcelain compositions for the In- ginal fit of the restorations (Wohlwend et al, 1989).
ceram technique have been recently introduced. In-
Ceram Spinell contains a magnesium spinel (MgAl2O4) MECHANICAL PROPERTIES
Aluminous core (Pt foil) Vitadur-N core 123 Seghi ef a/., 1990b
Aluminous core Hi-Cera m 139 Seghi ef a/., 1990b
Zirconia-reinforced Mirage II 70 Seghi etai, 1990b
Injection-molded aluminous Alceram 162 Wohlwend et al., 1989
Heat-pressed, leucite-reinforced IPS Empress 97 Seghi and Sorensen, 1995
160-180 Dong et a/., 1992
Leucite-reinforced Optec HSP 104 Seghi et a/., 1990b
Slip-cast alumina In-Ceram 446 Seghi and Sorensen, 1995
Slip-cast alumina In-Ceram Spinell 378 Seghi and Sorensen, 1995
Slip-cast alumina In-Ceram Zirconia 604 Seghi and Sorensen, 1995
Mica glass-ceramic Dicor 125 Seghi et a/., 1990b
Hydroxyapatite glass-ceramic Cerapearl 150 Hobo and Iwata, 1985
Lithia-based glass-ceramic Experimental 188 Anusavice et a/., 1994b
Machinable glass-ceramic Dicor MGCm 229 Seghi and Sorensen, 1995
Machinable ceramic Vita Mark II 122 Seghi and Sorensen, 1995
Magnesia core (glazed) Experimental 269 Wagner et a/., 1992
lain. Other researchers use devices that try to simulate tistry. In vivo failure stress of clinically failed all-ceramic
dental morphology (Probster, 1992). However, the exper- crowns can be determined by fractography (Kelly et al,
imental variables can become extremely complex and 1989). A protocol for retrieval and fractographic analysis
difficult to reproduce in this latter type of testing. Finite of failed ceramic restorations has been proposed
Element (FE) Analysis constitutes another approach to (Thompson et al, 1994) from which critical flaw sizes and
the simulation of clinical conditions. Failure predictions failure stresses can be calculated.
of ceramic inlays by the FE technique successfully It is well-established that glasses and ceramic mate-
matched fractographic analyses of clinically failed rials are susceptible to stress corrosion and slow crack
restorations (Peters et al, 1993). growth (Michalske and Freiman, 1982). The fatigue param-
Fractography is well-established as a means of fail- eters of an all-ceramic material (IPS Empress) compared
ure analysis in the field of glasses and ceramics. It has with those of feldspathic porcelain have recently been
been recognized as a powerful analytical tool in den- investigated (Myers et al, 1994). The results showed that
TABLE 3
Product Information
Material Product Manufacturer Reinforcing Component
Aluminous core (Pt foil) Vitadur-N core Vident, Baldwin Park, CA Alumina
Aluminous core Hi-Ceram Vident, Baldwin Park, CA Alumina
Zirconia-reinforced Mirage II Myron International, Kansas City, KS Zirconia fibers
Injection-molded aluminous Alceram Innotek Dental Corp, Lakewood, CO Alumina
Heat-pressed, leucite-reinforced IPS Empress Ivoclar North America, Inc., Amherst, NY Leucite
Leucite-reinforced Optec HSP Jeneric/Pentron, Inc., Wallingford, CT Leucite
Slip-cast alumina In-Ceram Vident, Baldwin Park, CA Alumina
Slip-cast alumina In-Ceram Spinell Vident, Baldwin Park, CA Spinel
Slip-cast alumina In-Ceram Zirconia Vident, Baldwin Park, CA Zirconia, alumina
Mica glass-ceramic Dicor Dentsply International, Inc., York, PA Tetrasilicic fluormica
Hydroxyapatite glass-ceramic Cerapearl Kyocera, San Diego, CA Hydroxyapatite
Lithia-based glass-ceramic Experimental N/A Lithium disilicate
Machinable glass-ceramic Dicor MGC Dentsply International, Inc., York, PA Tetrasilicic fluormica
Machinable ceramic Vita Mark II Vident, Baldwin Park, CA Sanidine
Magnesia core (glazed) Experimental N/A Forsterite
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