Ceramics Overview Classification by Microstructure and Processing Methods.
Ceramics Overview Classification by Microstructure and Processing Methods.
Ceramics Overview: ^^
Classification by Microstructure
and Processing Methods
Russell Giordano, DMD, CAGS, DMSc;^ and Edward A. McLaren, DDS, M D C
Abstract: The plethora of ceramic systems available today system established on how the ceramics are processed will
for all types of indirect restorations can be confusing—and provide the main guidelines for their use.
overwhelming—for the clinician. Having a better under- The term ceramic is derived from the Creek word "kera-
standing of them is key. The authors use classification mos," which means "potter" or "pottery." This is related to
systems based on the microstructural components of ce- a Sanskrit term meaning "burned earth," because the basic
ramics and the processing techniques to help illustrate the components were clays from the earth that were heated to
various properties and uses. form pottery. Ceramics are nonmetallic inorganic materials
and refer to numerous materials, including metal oxides,
M
any different ceramic systems have been intro- borides, carbides, and nitrides, as well as complex mixtures
duced in recent years for all types of indirect of these materials.' Their structure is crystalline, displaying a
restorations from conservative no-preparation regular periodic arrangement of the component atoms, and
veneers to multiple-unit posterior fixed partial dentures may exhibit ionic or covalent bonding. Although ceramics
(FPDs) and everything in between. Knowing the various can be very strong, they are also extremely brittle and will
nuances of materials and processing systems is overwhelming catastrophically fail after minor flexure. Thus, these materials
and can be confusing. Using a classification of the micro- are strong in compression but weak in tension.
structural components of ceramics, this article covers the Contrast that to metals, which are nonbrittle (display
types of ceramics available. A second simpler classification elastic behavior) and ductile (display plastic behavior). This
Learning Objectives
After reading this article, the reader should be able to:
'Associate Professor, Director of Biomaterials, Boston University Goldman School of Dental Medicine, Boston, Massachusetts
^ Professor, Founder, and Director, UCLA Post Graduate Esthetics; Director, UCLA Center for Esthetic Dentistry, Los Angeles, California
MICROSTRUCTURAL CLASSIFICATION
At a microstructural level, ceramics can be defined by their
composition of glass-to-crystalline ratio. There can be infi-
nite variability of the microstructures of materials; however,
they can be divided into four basic compositional categories
with a few subgroups:
synthetic even though there have been claims to the con- and onlays with all studies showing a less than 1% per year
trary. These materials were first used in dentistry to make failure rate, which compares favorably with metal-ceramic
porcelain dentures. survival data.' ' A pre-manufactured block has no residual
Mechanical properties are low, with fiexural strength porosity in the finished core that could act as a weak point
usually from 60 MPa to 70 MPa. Thus, they tend to be em- and lead to catastrophic failure.
ployed as veneer materials for metal or ceramic substructures,
as well as for veneers, using either a refractory die technique Subcategory 2.1
or platinum foil. The microstructure of a glass is shown in Low-to-Moderate Leucite-Containing Feldspathic Glass
Figure 1. This is an electron micrograph of an acid-etched Even though other categories have a feldspathic-like glass,
glass surface. The holes indicate a second glass, which was these materials have been aàled feldspathic porcelains by de-
removed by the acid. The veneer restoration uses a glassy fault. Leucite may alter the coefficient of thermal expansion
porcelain (Figure 2A and Figure 2B). (CTE), as well as inhibit crack prop^ation, thereby improving
the material's strength. The amount of leucite may be adjusted
COMPOSITION CATEGORY 2: in the glass based on the type of core and required CTE.
Glass-Based Systems with These materials are the typical powder/liquid materials used
Crystalline Second Phase, Porcelain to veneer core systems and are also ideal for porcelain veneers.
This category has a large range of glass-crystalline ratios The original materials had a fairly random size and dis-
and crystal types, so much so that the authors subdivided tribution of leucite crystals with the average particle size of
this category into three groups. The glass composition is approximately several htindred microns. This random distri-
similar to the pure glass Category 1. The difference is vary- bution and large particle size contributed to the material's low
ing amounts of crystal types have either been added to or fracture resistance and abrasive properties relative to enamel."
grown in the glassy matrix. The primary crystal types today Newer generations of tnaterials have been developed with
are either leucite, lithium disilicate, or fluorapatite. Leucite much finer leucite crystals (10 |im to 20 pm) and very even
is created in dental porcelain by increasing the K^O (potas- particle distribution throughout the glass. These materials
sium oxide) content of the aluminosilicate glass. Lithium are less abrasive and have much higher fiexural strengths.'
disilicate crystals are made by adding Li^O (lithium oxide) In Figure 3, an electron micrograph of a rypical feldspathic
to the aluminosilicate glass. It also acts a flux, lowering the porcelain reveals a glass matrix surrounding leucite crystals.
melting temperature of the material. These materials are most commonly used as veneer porcelains
These materials have also been developed into fine-grain for metal-ceramic restorations (Figure 4).
machinable blocks—Vitablocs Mark II (Vident, vident.com)
for use with the CEREC* computer-aided design/computer- Subcategory 2.2
aided manufacturing (CAD/CAM) system (Sirona, www. High-Leucite (Approximately 50%)-
sirona.com). Sirona CEREC Blocs are fabricated by Vita Containing Glass, Glass-Ceramics
using the Vitablocs Mark II powders; however, Sirona has a The microstructure of these materials consists of a glass ma-
different shade system. This material is the most successfully trix surrounding a second phase of individual crystals. The
documented machinable glass for the fabrication of inlays material starts as a homogeneous glass. A secondary beat
Figure 3 Scanning electron micrograph of the microstruc- Figure 4 Metal ceramic restoration. Ceramics performed by
ture of a feldspathic veneer porcelain. Acid etching removes Yi-Wing Chang.
the glass and reveals the leucite crystals.
stronger materials. Glass-ceramics are in widespread use for of a pressable ceramic. Leucite crystals reinforce the glass.
veneer and crown restorations. core to create the final morphology and shade of the restora-
tion. The shape and volume of crystals increase the fiexural
Subcategory 2.3 strength to approximately 360 MPa, or about three times
Lithium-Disilicate Glass-Ceramics that of Empress." ''' This material can be translucent even
This is a true glass-ceramic introduced initially by Ivoclar with the high crystalline content; this is due to the rela-
as Empress II (and now in the form of IPS e.max* pressable tively low refractive index of the lithium-disilicate crystals.
and machinable ceramics). Increasing the crystal content to The material is translucent enough that it can be used for
COMPOSITION CATEGORY 3:
Interpenetrating Phase Ceramics
In-Ceram* (Vident, www.vident.com) consists of a family of
all-ceramic restorative materials based on the same principle
introduced in 1988. The family includes a range of strengths,
translucencies, and fabrication methodology designed to cover
the wide scope of all-ceramic restorations, including veneers,
inlays, onlays, and anterior/posterior crowns and bridges.
A « y Spei Maqn 1 6iim
I r, 0 kv :t 8 "looox 1 smooth etch 10 í In-Ceram Spinell (alumina and magnesia matrix) is the most
Figure 7 Scanning electron micrograph of the microstruc- translucent, with moderately high strength and is used for
ture of a lithium-disilicate glass-ceramic. Acid etching anterior crowns. In-Ceram Alumina (alumina matrix) has high
reveals the fine crystal structure. strength and moderate translucency and is used for anterior
and posterior crowns. In-Ceram Zirconia (alumina and zirco-
nia matrix) has very high strength and lower translucency and
is used primarily for three-unit posterior bridges. In addition,
these materials are supplied in a block form for producing
milled restorations using a variety of machining systems.
In-Ceram is in a class called interpenetrating phase com-
posites.^-^ They consist of at least two phases, which are in-
tertwined and extend continuously from the internal to
external surfaces (Figure 9). This class has better mechanical
and physical properties relative to the individual compo-
nents; a tortuous route through alternating layers of both
components is required in order for these materials to break.
Interpenetrating phase materials are generally fabricated
by first creating a porous matrix; in the case of In-Ceram, it
would be a ceramic "sponge." The pores are then filled by
a second-phase material, lanthanum aluminosilicate glass,
using capillary action to draw a liquid or molten glass into
all the pores to produce the dense interpenetrating material.
Figure 8A and Figure 8B IPS e.max restorations replacing The system was developed as an alternative to conven-
existing amalgams. tional metal-ceramics and has met with great clinical suc-
cess. The system uses a sintered crystalline matrix of a
full-contour restorations or for the highest esthetics and can high-modulus material (85% of the volume) in which there
be veneered with special porcelain. Veneer porcelain consist- is a junction of the particles in the crystalline phase. This is
ing of fiuorapatite crystals in an aluminosilicate glass may different than glasses or glass-ceramic materials in that these
be layered on the core to create the final morphology and ceramics consist of a glass matrix with or without a crystalline
shade of the restoration. Fluorapatite is a fiuoride-containing filler in which there is no junction of particles (crystals). Slip
calcium phosphate, Ca^(PO^)jF. The fiuorapatite crystals casting^'' may be used to fabricate the ceramic matrix, or it
contribute to the veneering porcelain's optical properties and can be milled from a presintered block." Flexural strengths
CTE, so it matches the lithium-disilicate pressable or ma- range from 350 MPa for spinell, 450 MPa for alumina, and
chinable material. Both the veneering and lithium-disilicate up to 650 MPa for zirconia. Several clinical studies support
materials are etchable due to the glassy phase. Initial clinical the use of In-Ceram Alumina for single units placed anywhere
data for single restorations are excellent with this material, in the mouth. In-Ceram Alumina had the same survival rates
especially if it is bonded.^" A material with similar proper- as porcelain-fiised-to-metal restorations up to the first molar,
ties and structure called 3G OPC is available as a pressable with a slightly higher failure rate for the second molar.^"^
glass-ceramic irom Pentron. In-Ceram Zirconia should only be used on molars due to its
COMPOSITION CATEGORY 4:
Polycrystalline Solids
Solid-sintered monophase ceramics are formed by directly
c V Spot Magn Det WD Exp
sintering crystals together without any intervening matrix 6 0 k V 3 0 lOOOx SE 32 0 2269
to form a dense, air-free, glass-free polycrystalline structure. Figure 9 Scanning electron micrograph of the mitiostruc-
Several processing techniques allow the fabrication of ei- ture of In-Ceram Alumina.
ther a solid-sintered aluminous oxide (alumina, Al O ) or
zirconium oxide (ZrO^) framework. The first fully dense
polycrystalline material for dental applications was Procera*
AllCeram alumina (Nobel Biocare, www.nobelbiocare.com),
with a strength of approximately 600 MPa.'^'' The alumina
powder is pressed and milled on a die and sintered at about
1600°C, leading to a dense coping but with approximately
20% shrinkage (Figure 11 through Figure 12B).
The use of what is commonly referred to in dentistry as
zirconia has increased rapidly in the past few years. This is
not pure zirconia; it is partially stabilized by the addition of
small amounts of other metal oxides. Partially stabilized zir-
conia allows production of reliable multiple-unit all-ceramic
restorations for high-stress areas, such as the posterior region
of the mouth. Zirconia may exist in several crystal types
(phases) depending on the addition of minor components,
such as calcia (CaO), magnesia (MgO), yttria (Y^O ), and
ceria (CeO^). Specific phases are said to be stabilized at
room temperature by the minor components. Typically for
dental applications, about 3 weight% of yttria is added to
pure zirconia (Figure 13 through Figure 14B).
Zirconia has unique physical characteristics that make it
twice as strong and tough as alumina-based ceramics. Values
for fiexural strength range from approximately 900 MPa to
1100 MPa.'"''' There is no direct correlation between fiexural
strength (modulus of rupture) and clinical performance.
Another important physical property is fracture toughness,
which has been reported between 8 MPa m"'' and 10 MPa
m"' for zirconia.'" This is significantly higher than any previ-
ous dental ceramic. Fracture toughness is a measure of a mate- 10A through Figure IOC In Ceram Spinell crown.
rial s ability to resist crack growth. Zirconia has the apparent
physical properties to be used for multiple-unit anterior and to equalize the heat dissipation from zirconia and porcelain
posterior FPDs. Clinical reports on zirconia have not dem- increased the fracture resistance of the porcelain by 20%.
onstrated a problem with the zirconia framework.'^"''' The Zirconia may be in the form of porous or dense blocks that
problems have been associated with chipping and cracking are milled to create the frameworks or recently, full-contour
of porcelain. Using a slow-cooling protocol at the glaze bake single-unit restorations. Most are fabricated from a porous
block, milled oversized by about 25%, and sintered to full powdered form that is then fabricated using a wet-brush
density in a 4- to 6-hour cycle. An alternate approach involves technique, or they can also be preprocessed into a block that
milling a ftilly dense block. However, due to the nature of can be pressed or machined. As a general rule, powder/liquid
zirconia, this approach requires approximately 2 hours of systems have much lower strength than pre-manufactured
milling time per unit whereas milling of the porous block blocks due to a much larger amount of bubbles and flaws
necessitates only 30 to 45 minutes for a three-unit bridge. in the finished restoration.
Within Classifications 2 and 3, compositions can vary
greatly. Several commercial materials are in these groups. CLASSIFICATION BASED
Glass-based systems (Category 1 and Category 2) are etch- ON PROCESSING TECHNIQUE
able and thus easily bondable. Crystalline-based systems A more user-friendly and simplistic way to classify the ce-
(Category 3 and Category 4) are not etchable and much ramics used in dentistry is by how they are processed. All
more difficult to bond. Categories 1 to 3 can exist in a materials can be processed by varied techniques; however, in
^cc V Spot Magn Det WD Exp I ,cc V Spot Magn Dot WD Exp
15 0 k V 4 0 lOOOOx SE 5 7 2308 Procera crown i25 0 k V 2 0 20000X SE 12 5 11
Figure 11 Scanning electron micrograph of the microstruc- Figure 13 Scanning electron micrograph of the microstruc-
ture of an alumina ceramic. ture of a zirconia ceramic.
12A and Figure 12B Alumina anterior crowns. Figure 14A and Figure 14B Zirconia crown on tooth No. 9.
general for dentistry, ceramics can be classified as: 1) powder/ in the fabrication involves application of aluminotis porcelain
liquid glass-based systems; 2) machinable or pressable blocks on the core to produce the final form of the restoration. Other
of glass-based systems; and 3) CAD/CAM or slurry die- powder dispersions, such as those created with zirconia, may
processed, mostly crystalline (alumina or zirconia) systems. be poured into a gypsum mold that withdraws the water and
It is an important classification method, as there appears to leads to a homogeneous block of zirconia being formed.
be a greater correlation to clinical success (and thus failure)
due to processing techniques. Even though a material may 2. PRESSABLE
have the same chemistry and microstructure, the processing Pressed ceramic restorations are fabricated using a method
methodology used to produce a restoration may improve or similar to injection molding. Monochromatic porcelain or
decrease the final properties and clinical success. Specifically, glass-ceramic ingots are heated to allow the material to flow un-
machined blocks of materials have performed better than der pressure into a mold formed using a conventional lost-wax
powder/liquid versions of the same material. technique. The restoration may be cast to its final contours and
subsequently stained and glazed to provide an esthetic match.
1. POWDER/LIQUID Alternatively, a coping may be molded on which porcelain
is added to achieve the restorations final shape and shade.
IA. Conventional Empress restorations and other materials with a similar leucite/
These are typically veneer materials, which may be all glass glass structure are fabricated in this manner. The glass-ceramic
or a mixture of glass and crystal components. These include IPS e.max is also created this way. Pressables may be used for
veneers for all-ceramic and metal frameworks and may also inlays, onlays, veneers, and single-unit crowns.
be used alone as anterior veneer restorations. Typically, these
materials are hand-mixed with de-ionized water or a special
modeling liquid supplied by the manufacturer. They are built
up by hand and vibrated (condensed) to remove water and
air. These are fired in a vacuum to help remove remaining air
and improve the density and esthetics of the veneer. Because
these restorations are handmade, voids are often present in
the fired material. This is inherent to the process and may
be better or worse depending on environmental conditions,
the technician's skill, and the firing cycle. Frequently, one
sees bubbles remaining in the hand-layered veneer material.
3. CAD/CAM
Full-Contour
Full-contour restorations such as inlays, onlays, crowns, and
veneers may be fabricated from various blocks of materials.
In general, these blocks are fabricated from starting powders
that are mixed with a binder and then pressed into a mold or
extruded like a sausage into a block form. The binder helps
hold the powder together so that the shape is maintained
afi:er pressing or extrusion. Then, the blocks are transferred
to a furnace to remove the binder and sinter to full density.
As mentioned previously, restorations milled from blocks
tend to have improved density and mechanical properties
as compared with powder/liquid or pressed restorations due
to the standardized manufacturing process (Figure 1 6 ) . " ' '
Glass/Crystal
Vitablocs are fabricated using fine-grain powders, producing
17A and Figure 17B Milled crown. a nearly pore-free ceramic with fine crystals. This was the first
material specifically produced for the CEREC system and
has an excellent history of clinical success for inlays, onlays,
and anterior and posterior crowns.^'' Sirona CEREC Blocs
are fabricated from the same powders. The restoration may
be characterized with external stains, or porcelain may also
be added to produce a layered effect (Í7A and Figure 17B).
H«at These blocks are available as monochromatic, polychro-
matic with stacked shades as in a layer cake, and in a form
pressure replicating the hand-fabricated crowns in which an enamel
ÖÜÜ bar
porcelain is layered on top of dentin porcelain.
Glass/Leucite
Glass/leucite materials include Empress CAD and Authentic*
up to ?000 *C (Jensen Dental, www.jensendental.com). Empress CAD is
based on the pressable Empress and has the same microstruc-
ture—a feldspathic glass with approximately 45% leucite crystal
component. These blocks also have a fine leucite crystal struc-
ture (approximately 5 fim to 10 (im) and may also be further
characterized using external stains or porcelain. Empress CAD is
available in monochromatic and polychromatic stacked shades.
Strength properties are similar to Vitablocs. A common theme
to all of these blocks is a fine particle-size microstructure that
High pressure vessel helps resist machining damage, improve mechanical properties,
Figure 18 Diagram of d liot isobtdtie and decrease polishing time of the finished restoration.
disadvantages; however, the desired result is the same—that is, systems were given to aid the reader in understanding the types of
to produce a homogeneotis block that shritiks uniformly. As is ceramics available for dental use. Processing technique has a large
the case with the alumina block, the milled zirconia framework impact on strength and thus clinical performance and should
shrinks about 25% after a 4- to 6-hour cycle at approximately be one of the primary considerations in choosing a material.
1300°Cto 1500°C. The particle size is about 0.1 iimto0.5pm. There are many clinical aspects that are important for
success with all-ceramic materials but are not as critical with
Partially Stabilized Zirconia: "HIP" blocks metal-based restorations and not possible to cover here (eg,
Fully dense zirconia is produced by hot isostatic pressing. The preparation design, management of stresses, cementation tech-
zirconia powder may be prepressed in a block, or the powder niques). A basic clinical use guide is shown in Table 1. The
itself is packed into a fiexible mold. Either the blocks or mold reader is advised that significant knowledge and training in
is then vacuum-sealed in an airtight rubber or plastic bag and these areas are requisites for success with all-ceramic materials.
placed into a fluid-filled chamber. Pressure is then applied to
the fiuid and transmitted evenly around the zirconia. Heat DISCLOSURE
is applied to the chamber, which sinters the zirconia to full Dr. Ciordano has received material and/or financial support
density (Figure 18). Zirconia blocks produced in this manner from 3M ESPE, DENTSPLY, Ivoclar Vivadent, Sirona,
may achieve fiexural strength values of approximately 1200 and Vita.
MPa to 1400 MPa. However, it requires extended milling to
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