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Presented at the 17th International Conference on Biomechanics and Biomedical Engineering, Dubai, United Arab Emirates, December 2015.
a
Doctoral student, University of New South Wales Sydney, Sydney, New South Wales, Australia.
b
Deputy Head and Senior Lecturer, School of Materials Science and Engineering, University of New South Wales Sydney, Sydney, New South Wales, Australia.
c
Lecturer, School of Materials Science & Engineering, University of New South Wales Sydney, Sydney, New South Wales, Australia.
d
Professor, School of Materials Science & Engineering, University of New South Wales Sydney, Sydney, New South Wales, Australia.
Table 2. Zirconia materials developed for fabrication of monolithic restorations in esthetic zone
Material Code Microstructure Advantages Disadvantages
Tetragonal TZP 3 mol% Y2O3 doped ZrO2 (Y-TZP)9 Desirable characteristics, well Shade matching, elastic modulus mismatch
zirconia characterized, and hence most widely (enhanced wear of teeth), long-term clinical
polycrystal used for dental applications6 stability (phase transformation)7,28,29
Zirconia- ZTLS ZrO2 toughened (20 wt% Y-TZP) glassy Excellent mechanical and optical High ZrO2 contents can result in
toughened Li2O$SiO27,32,33 properties for dental applications;34 agglomeration, which may affect
lithium silicate increases refractive index32,35 deleteriously matrix grain growth and
transformation-toughening36
ZrO2 toughened (Y-TZP) crystalline Li2O$2SiO2 Improves translucency due to increasing High ZrO2 contents can result in
glass-ceramic4,23 refractive index and reduced light agglomeration, which may affect
scattering due to decreasing grain size35 deleteriously matrix grain growth and
transformation-toughening36
Interpenetrating- IPCZ Vita In-Ceram: Glass (20-25 vol%) infiltrated into Fully dense net-shape ceramic7 Lengthy process, complex technique, labor-
phase composite porous ZTA (69 vol% Al2O3 + 21 vol% intensive
zirconia Ce-TZP)7,8
3M Paradigm MZ100*: Porous mixture of 85 wt% CEREC: Acquisition of CAD-CAM facility Optical properties insufficiently
nanocrystalline zirconia-silica (sol-gel allows fabrication in clinical setting7 characterized7
processed) + solid bisGMA (bisphenol A
diglycidyl ether dimethacrylate), infiltrated with
liquid TEGDMA (tri[ethylene glycol]
dimethacrylate) monomer37
Lava Ultimate: 80 wt% zirconia-silica CEREC, E4D and Straumann CARES: Significantly lower flexural modulus and
(combination of discrete zirconia and silica plus Acquisition of CAD-CAM facility allows flexural strength than zirconia restoration;
zirconia-silica nano-cluster) + nanomer filler38 fabrication in clinical setting and use of mechanical properties influenced negatively
Lava Milling center by storage in water38
*3M. 3M Paradigm MZ100 Block Technical product profile.http://multimedia.3m.com/mws/media/471861O/lavatm-zirconia-scientific-facts.pdf, 2007.
most ceramics difficult. Thus, processing methods for the 1.8-3.1 Partial Partial Colored and opaque
(690-400 nm)
fabrication of ultrafine nanopowders and densification >3.1 eV (400 nm) None Complete Colorless and transparent
methods other than pressureless sintering have been a
Adapted from Callister.43 bLight absorption involves excitation of electrons from valence band
developed (Table 6). to conduction band.
Optical properties of ZrO2 The optical properties can be modified through pro-
cessing by intentionally adding dopants (as distinct from
the stabilizers). Transition and rare earth metals are used
Intrinsic Extrinsic as they impart color tints to typically colorless oxides.87
Research on controlling the color of zirconia to match
• Chemical composition
• Microstructural defects • ZrO2 surface structure natural tooth color has focused mainly on the effects of
Porosity • ZrO2 thickness Fe2O3 doping or co-doping of 3Y-TZP nanopowders on
• Underlying tooth structure
Secondary phases
• Light source
the microstructure and mechanical properties.88-92
Exaggerated grain growth
• Phase distribution
This review evaluates the characterization and
modification of the optical properties of zirconia dental
ceramics for esthetic dental restorations.
Effect on
MATERIAL AND METHODS
This systematic review was developed according to the
• Transmission preferred reporting items for systematic reviews and
• Absorption
• Refraction meta-analyses (PRISMA) statement.93 The review ques-
• Reflection tion was formulated using the participant, intervention,
• Scattering comparison, and outcome (PICO) approach,94 where
participant = restoration of esthetic zone; intervention =
monolithic zirconia; comparison = zirconia layered or
Translucence and color other types of zirconia ceramics; and outcome = clinical
performance and satisfactory esthetic appearance.
Figure 2. Effect of intrinsic and extrinsic factors on optical properties The following databases were searched electronically:
of ZrO2. Technology research via ProQuest, EMBASE, SciFinder,
MRS online proceedings library, Medline, Compendex,
and Journal of the American Ceramic Society. The
Different techniques of synthesizing nanoscale zirco-
following search terms were used alone or in combina-
nia have been reported, including coprecipitation,76 sol-
tion: “dental material,” “monolithic zirconia,” “sinter-
gel,77 hydrothermal treatment,78 combustion synthesis,79
ing,” “optical properties,” “light scattering,” “light
and mechanochemical processing.80 These techniques
transmission,” “zirconia,” and “zirconia nano-materials.”
must be undertaken carefully to minimize agglomera-
In addition, a manual search of the years 2005 to 2017
tion.81 They also offer the potential to achieve narrow
was done using the following journals: Journal of Dental
particle size distributions, which can reduce exaggerated
Materials, Journal of the American Ceramic Society, Dental
grain growth and the extent of densification.82,83 Ultra-
Materials Journal, and Journal of Prosthetic Dentistry. Bib-
fine nanopowders of zirconia and processing methods
liographies of selected papers were subjected to more
have been developed to improve densification, resulting
detailed searches for potentially relevant articles. The
in enhanced optical properties (Table 7). However, the
following inclusion criteria were used: publications in
stability of the zirconia polymorphs is influenced by the
English and publications of nonclinical studies of mate-
size and shape of the grains. The surface energy and
rials and microstructures of monolithic zirconia. Figure 5
associated surface area of zirconia are critical. Below a
summarizes the literature search strategy according to
critical size, tetragonal zirconia grains are stable at room
the PRISMA guidelines.
temperature; if larger, they transform to the monoclinic
polymorph. Grains of irregular shape are more likely to
RESULTS
undergo this transformation owing to increased matrix
stresses at the asperities.12 The electronic search identified 96 titles and abstracts, of
Low-temperature sintering of TZP produces micro- which 63 were chosen for evaluation. Another 6 articles
structures in which the pores are closed and intergran- were excluded, of which 2 reported thermal barrier
ular,84 thus enabling sinter hot isostatic pressing (sinter data,95,96 1 described the thermodynamics,97 2 were
HIPping). It is difficult for manufacturers to separate peripherally relevant overviews,98,99 and 1 was a clinical
hafnia (HfO2) from ZrO2 owing to the stability of their study of zirconia dental implants.100 Hence, 57 studies
complete solid solution,85 so commercial zirconias were included in the review. Of these, 8 discussed the
contain 5 wt% HfO2.86 Also, other oxides are generally interaction of light with zirconia (Table 4); 13 studies
present at levels of 1.0 wt%, where Na2O, SiO2, and reported the effects of extrinsic factors on the optical
Al2O3 are the main contaminants.62 properties of zirconia (Table 5); 18 considered the effects
18
16
14
12
10
8
450 500 550 600 650
Wavelength (nm)
Figure 4. Spectral values for scattering coefficient of zirconia (450 to
650 nm).57
Figure 3. Interaction of light with materials and their microstructures.
DISCUSSION
of pores and/or agglomerates as well as the densification
method on the optical properties (Table 6); 2 reported Minimal scattering of light at the wavelength w520 nm
grain size effects on the optical properties (Table 7); 7 by zirconia has been reported (Fig. 4).57 Since lower
covered the synthesis of zirconia; and 10 reported the scattering corresponds to greater translucency (the ratio
effects of impurities on the optical properties. between the intensity of light passing through a material
and that of the incident light), data for the scattering primary determinant of the translucency. Finally, the
coefficient are relevant, as seen in Figure 4. The general extent to which light can penetrate a solid (penetration
ranges of values of the relevant variables for dental zir- depth) also affects its translucency and opacity; this is the
conia are ma=0.01 to 0.10, g= −0.19 to −0.15, and ms=9 to reciprocal of coefficient of transmission.58
17. The large value of the latter causes it to dominate the Monolithic zirconia is used in dental restorations to
optics [mt0 =ma+(1−g)ms]. Since the band gap is high replace enamel. Zirconia’s lack of fluorescence
(transparent and colorless material), this emphasizes the diminishes its natural appearance, which is accentuated
fact that the microstructure is critical to the transmission. by its propensity to change from white to gray under
Also, since 3Y-TZP has a very high band gap of w5.2 to low-light conditions.45 In contrast, enamel remains
6.0 eV (w239 to 207 nm)101 and a very low distribution essentially unchanged under these conditions. If the
density of pores,7 the grain boundaries assume the role of fluorescence of zirconia is increased by chemical or other
means, the extent must be limited since dentin is 3 times requirement, equiaxed grains with critical grain size of 0.6
more fluorescent than enamel owing to dentin’s mm stabilize 3Y-TZP. In the presence of moisture, this
ultraviolet-photosensitive organic component.3 Further, critical grain size is decreased to 0.3 mm, avoiding the
in common with dentin, zirconia backscatters incident tetragonal-to-monoclinic phase transformation. In addi-
light, also enhancing its similarity to dentin. tion to the deleterious effect on the mechanical proper-
Features, such as interfaces between different phases ties, optical anisotropy is introduced by the birefringence
(including pores), birefringence, pores and grains of di- of the monoclinic phase due to its alteration of the
ameters similar to those of the wavelengths of visible refractive index at the grain boundaries.12
light, and rough surface finishes, can lower the trans- Most dental polycrystalline zirconia is processed by
lucency of zirconia. TZP is a highly dense, single-phase, sinter HIPping, thereby achieving grain sizes <50 nm,
fine-grained, polycrystalline material. Since the lattice nearly theoretical densities, and nearly pore-free micro-
parameters of tetragonal zirconia are nearly identical to structures.101 However, processing can be affected by the
those of the cubic form,15 birefringence is minimal. Since unintentional presence of contaminants, such as HfO2,
TZP dental restorations generally are glazed or polished, Na2O, and/or SiO2. The last 2 contribute to glass for-
surface roughness is minimal. Hence, light scattering in mation, which can suppress grain growth but lower
TZP (Fig. 6) is not dissimilar to that in a homogeneous strength and toughness.2 Al2O3 is of particular impor-
and isotropic material, so light scattering can be mini- tance as a contaminant because it enhances the densifi-
mized through microstructural control, thereby allowing cation rate of zirconia but reduces the transmission of
optimization of the translucency. visible light because of the segregation of Al2O3 on the
Densification of powders generally is done at high ZrO2 grain boundaries.67
temperatures, with and without applied pressure. While More recent work has examined the effect of inten-
pressureless sintering techniques require the use of a tional dopants on the optical properties of zirconia.
furnace only, it is difficult to achieve relative densities Mechanochemical processing of Pr2O3-doped 3Y-TZP
approaching the theoretical maximum. Consequently, enhanced translucency and color saturation. In another
techniques involving concurrent pressure and heat study, the addition of 0.2 mol% La2O3 and 0.1 wt%
application have been developed (Table 6). These have Al2O3 to 3Y-TZP significantly improved translucency.91
the main advantages that pore elimination is facilitated The La2O3 also suppressed grain growth, thus yielding
and they are rapid, which allows the maintenance of fine a finer microstructure, thereby improving the mechanical
grain sizes. More details can be found in published re- properties.
views.44,51-55 The main factors controlling the optical properties of
The particle sizes of TZP powders are important nanocrystalline 8Y-CSZ (8 mol% Y2O3-doped cubic
because they must facilitate densification while ZrO2) also have been investigated.78 The absorption co-
enhancing translucency. Since the visible light wave- efficient decreased and light transmission increased
lengths are in the range w400 to 700 nm, this particle after annealing in air at 750 C, even though the true
size range must be avoided owing to the potential for porosity and grain size would not be expected to have
enhanced light scattering. Due to the surface energy changed at this low temperature. It is probable that the
oxygen vacancies, which are intrinsic features of oxides this involves shade communication using a light-
(ZrO2-x),59 were filled during annealing. Conversely, emitting diode light of 5500 K (D50) illumination.
reduction at the same temperature, which would have In the dental laboratory, this involves the use of
increased the oxygen vacancy concentration, increased both high- and low-light intensities during
the absorption coefficient and decreased the trans- fabrication.
mission. Thus, the oxygen vacancy concentration also
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barrier coatings resistant to degradation by molten CMAS: part II, in- University of New South Wales Sydney
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96. Krause AR, Senturk BS, Garces HF, Dwivedi G, Ortiz AL, Sampath S, et al. AUSTRALIA
2ZrO2.Y2O3 thermal barrier coatings resistant to degradation by molten Email: r.shahmiri@unsw.edu.au
CMAS: part I, optical basicity considerations and processing. J Am Ceram
Soc 2014;97:3943-9. Copyright © 2017 by the Editorial Council for The Journal of Prosthetic Dentistry.