Zirconia overview

Mohamed M. Abdul-Monem
Mohamed M. Abdul-MonemLecturer of Dental Biomaterials ,Faculty of Dentistry, Alexandria University,Egypt. em Faculty of Dentistry, Alexandria University, Egypt.
Zirconia in Dentistry :
Overview
Mohamed Mahmoud Abdul-Monem
Assistant lecturer
Dental Biomaterials Department
Contents
• Introduction
• What is Zirconia ?
• History of Zirconia as a biomaterial
• Zirconia phase transformation
• Zirconia (Ceramic steel)
• Properties of Zirconia
• Uses of Zirconia
• Uses of Zirconia in dentistry
• Bonding to Zirconia
• References
Introduction
• Ceramics are very important in the science of
dental biomaterials.
• Among all dental ceramics, Zirconia is the dental
biomaterial of choice in contemporary
restorative dentistry.
What is Zirconia ?
• Zirconium oxide (ZrO2), or zirconia, is a metal
oxide that was identified as a reaction product of
heating the gem( zircon) by the German chemist
Martin Heinrich Klaproth in 1789 .
• The name of the metal, zirconium, comes from
the Arabic Zargon (golden in colour) which in
turn comes from the two Persian
words Zar (Gold) and Gun (Colour).
• Zirconia occurs as a natural mineral called
baddeleyite.
• Baddeleyite was first found in Sri Lanka in 1892.
It was named for Joseph Baddeley.
• This mineral contains 80–90% zirconium
oxide(zirconia). The major impurities are usually
TiO2, SiO2 and Fe2O3.
Baddeleyite
• It shouldn’t be confused with Zirconium (Zr ) which is
found in the form of (zircon) or zirconium
silicate(ZrSiO4 ) .
• It is lusturous gray-white transition metal .
History of zirconia as a biomaterial
• Zirconia has been used as a biomaterial since the
1970s.
• It has been widely used as a hip replacement
material.
• Its use in dentistry began in 2004.
Zirconia hip implants
Zirconia phase transformation
• Zirconium oxide exists in three different crystal
structures: monoclinic at room temperature,
tetragonal at ~1200°C and cubic at 2370°C.
• Zirconium oxide is transformed from one
crystalline state to another during firing.
• At the firing temperature, zirconia is tetragonal and
at room temperature, it is monoclinic, with a unit
cell of monoclinic occupying about 4.4% more
volume than when tetragonal.
Zirconia phase transformation
Zirconia overview
• The volume expansion caused by the cubic to
tetragonal to monoclinic transformation induces
large stresses, and these stresses cause ZrO2 to
crack upon cooling from high temperatures.
• When the zirconia is blended with some other
oxides, the tetragonal and/or cubic phases are
stabilized.
• Effective stabilizers include magnesium oxide
(MgO), yttrium oxide (Y2O3, yttria), calcium oxide
(CaO), and cerium(III) oxide (Ce2O3).
Zirconia overview
• Zirconia is often more useful in its phase 'stabilized'
state. Upon heating, zirconia undergoes disruptive
phase changes.
• By adding small percentages of yttria, these phase
changes are eliminated, and the resulting material
has superior thermal, mechanical, and electrical
properties.
• In some cases, the tetragonal phase can be
metastable.
• If sufficient quantities of the metastable
tetragonal phase is present, then an applied
stress, magnified by the stress concentration at a
crack tip, can cause the tetragonal phase to
convert to monoclinic, with the associated
volume expansion(4.4%).
• This phase transformation can then put the
crack into compression, retarding its growth,
and enhancing the fracture toughness.
• This mechanism is known as transformation
toughening, and significantly extends the
reliability and lifetime of products made with
stabilized zirconia.
Zirconia transformation toughening
Zirconia overview
Zirconia = Ceramic steel
• It may be noted that zirconia has many features
in common with systems based on iron
(stainless steel )as :
1. Three allotropes
2. Martesnitic transformation
3. Metastable phases
Thus it is known as ceramic steel (Garvie et al ,
1975).
Properties of Zirconia
Physical properties :
• Low thermal conductivity (20% that of alumina)
• Opaque
Chemical properties:
• Chemically inert and corrosion resistant
Biological properties:
• Biocompatible
Mechanical properties:
• Flexural strength 900 Mpa
• Compresive strength 2000MPa
• Fracture toughness 8-10 MPa · m1/2
• High fracture resistance
• Wear of opposing dentition (Monolithic Zirconia)
• Difficulty in adjusting occlusion
Hydrothermal degradation of zirconia
• Hydrothermal degradation of zirconia occurs
between 200-400 ˚C .
• Longer exposure times at oral temperature may
also degrade zirconia leading to increased
surface roughness , fragmanted grains and
microcracks .
Uses of Zirconia
• Protective coating on particles of TiO2 pigments.
• Refractory material .
• In Oxygen sensors.
• Electroceramics.
• Thermal barrier coating (low thermal
conductivity) in jet and diesel engines.
• Ceramic knives.
• Diamond simulant (cubic zirconia).
Zirconia overview
Uses of Zirconia in dentistry
• Crowns and bridges
• Inlays and Onlays
• Veneers
• Endodontic post and cores
• Fillers in dental composite
• Implants
• Implant abutments
• Orthodontic brackets
• Pedodontic crowns
Zirconia as fillers in dental composite
• Surface-modified
zirconia/silica with a median
particle size of approximately
3 microns or less
Zirconia inlays ,onlays and crowns
Zirconia bridges
Multilayered monolithic zirconia
Zirconia CAD/CAM Blocks
Soft machining Hard machining
• Mostly, they are
fabricated from a porous
block, milled oversized by
about 25%, and sintered
to full density in a 4 - 6
hours cycle.
• Alternatively, fully dense
blocks are milled.
• However, this approach
requires approximately 2
hours of milling time per
unit whereas milling of
the porous block
necessitates only 30 to 45
minutes for a three-unit
bridge.
Zirconia sintering Temperature
• Currently available zirconia for soft machining
of dental restorations utilize final sintering
temperatures varying between 1350 and 1550 ◦C
depending on the manufacturer.
• The microstructure of 3Y-TZP ceramics for
dental applications consists of small equiaxed
grains (0.2–0.5 µm) in diameter, depending on
the sintering temperature
Steps of fabrication of zirconia
restorations
Digital impression
Virtual model on software
Milling of zirconia blocks
Zirconia cores
Zirconia toughened alumina ZTA
• 70-90% alumina
• 10-20% zironia
• Toughened by a stress-induced
transformation mechanism of
zirconia leading to
compressive stresses within
alumina.
• The strength of alumina is
doubled and toughness is
increase 2-4 times .
Zirconia overview
Zirconia veneers
Zirconia endodontic post and cores
Zirconia implants and abutments
Surface treatment of zirconia implants
• Changing the surface chemistry using bioactive
coating with different materials (calcium
phosphates, bisphosphonate, collagen, etc.)
• Optimizing surface architecture and
microroughness using different techniques.
Scanning electron microscopy (SEM) observation of fibroblasts cultured on
zirconia: cells grow on the whole zirconia surface, covering it with a cellular
layer.
Zirconia individualized CAD/CAM implants
• Austrian Surgeons have
designed a system to produce
via CAD/CAM individualized
Zirconium Dental Implants for
use in case of immediate
implant placement.
• In short, after a tooth is
extracted it is scanned and a
zirconium copy is milled.
• The milled copy has macro-
retentive features which help
secure the new implant in the
extraction socket. They report
a 90% success rate.
Zirconia orthodontic brackets
Pedodontic zirconia crowns
Bonding to Zirconia
• One problem of zirconia application is its adhesion
to different substrates.
• Surface treatment of zirconia produces an activated
surface in different applications.
• Since zirconia is resistant to aggressive chemical
treatment.
• Very aggressive mechanical abrasion methods
must be used to provide sufficient surface
roughness.
Conventional surface treatment
techniques are:
(1)acid etching with hot acids
• This procedure based on corrosion–controlled
process and metallic nature of pure zirconium.
• It selectively etches the zirconia and creates
micro-retentions on the surface by modifying
the grain boundaries through removal of the
less arranged atoms .
• Hot acid etching with combinations of highly
corrosive acids (HNO3, H2SO4, and HF)
improves both initial bond strengths and
durability .
• Sulfuric acid in solution with hydrogen
peroxide (H2O2) (Piranha solution) appeared
to have a positive effect on the bonding of
zirconia with resin cements .
(2)Abrasion with diamond (or other)
rotary instruments (can cause microcracks)
(3)Coatings of low melting temperature
porcelain micro pearls.
(4)Selective infiltration etching (SIE)
• SIE uses a heat-induced maturation process to
pre-stress surface grain boundaries in ZrO2 to
allow infiltration of boundaries(1) with molten
glass.
• The glass is then etched out (2)using HF,
creating a network of inter-granular porosity
that allows nano-mechanical interlocking of
resin cement .
SIE of Zirconia
(5)Fusion sputtering :
• Fusion sputtering is a new technique used to create
rough zirconia surface by spraying an air-water jet
carrying microscopic zirconia particles onto
unsintered zirconia frameworks.
• Upon impact with the surface, the particles achieve
good contact and adherence.
• After sintering, these particles become
structurally fused with the underlying framework
and create undercuts suitable for establishing
mechanical retention with resin adhesives.
(6) Air abrasion with alumina (Mechnical)
low pressure particle abrasion (LPPA)
(7)Application of different laser types
(8) Plasma oxyfluoride
This process presents a method to chemically
modify zirconia by creating thin oxyfluoride
conversion layer on its surface that is receptive
to organosilane attachment .
(9) Tribiochemical silica coating
(1o) Plasma spray (siloxane coating)
Conclusion in bonding to zirconia
• The use of phosphate monomer luting cements
on freshly air-abraded zirconia is the simplest
and most effective way for zirconia
cementation procedure.
• These resin cements have shown good
mechanical retention.
MDP resin cements
• MDP-containing resin cement
continues to be a popular
choice for luting ZrO2
prosthetics in clinical
applications due to its low
failure rate and loss of
retention.
• The hydroxyl groups of the
passive zirconia surface bond
to the phosphate ester group of
the MDP.
• 10-Methacryloyloxydecyl
dihydrogen phosphate
Zirconia overview
References
1. A D Bonna et.alZirconia as a dental
biomaterial.Materials.2015;8:4978-91
2. Z Khamverdi et al.Zirconia :An up- to-date literature
review.DJH.2012;4:1-15
3. MN Aboushelib et al.Bonding to Zirconia(A systematic
review).Open Access Journal of Dental Sciences.2016
4. K Nakamura et al.Zirconia as a Dental Implant
AbutmentMaterial: A Systematic Review.Int. J
Prosth.2010
5. R Pandero et al .Zirconia in fixed prosthesis. A
literature review . Journal Clin Exp Dent.2014;6:66-73
6. Philips’ science of dental materials.12th edition.
Zirconia overview
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Zirconia overview

  • 1. Zirconia in Dentistry : Overview Mohamed Mahmoud Abdul-Monem Assistant lecturer Dental Biomaterials Department
  • 2. Contents • Introduction • What is Zirconia ? • History of Zirconia as a biomaterial • Zirconia phase transformation • Zirconia (Ceramic steel) • Properties of Zirconia • Uses of Zirconia • Uses of Zirconia in dentistry • Bonding to Zirconia • References
  • 3. Introduction • Ceramics are very important in the science of dental biomaterials. • Among all dental ceramics, Zirconia is the dental biomaterial of choice in contemporary restorative dentistry.
  • 4. What is Zirconia ? • Zirconium oxide (ZrO2), or zirconia, is a metal oxide that was identified as a reaction product of heating the gem( zircon) by the German chemist Martin Heinrich Klaproth in 1789 . • The name of the metal, zirconium, comes from the Arabic Zargon (golden in colour) which in turn comes from the two Persian words Zar (Gold) and Gun (Colour).
  • 5. • Zirconia occurs as a natural mineral called baddeleyite. • Baddeleyite was first found in Sri Lanka in 1892. It was named for Joseph Baddeley. • This mineral contains 80–90% zirconium oxide(zirconia). The major impurities are usually TiO2, SiO2 and Fe2O3.
  • 7. • It shouldn’t be confused with Zirconium (Zr ) which is found in the form of (zircon) or zirconium silicate(ZrSiO4 ) . • It is lusturous gray-white transition metal .
  • 8. History of zirconia as a biomaterial • Zirconia has been used as a biomaterial since the 1970s. • It has been widely used as a hip replacement material. • Its use in dentistry began in 2004.
  • 10. Zirconia phase transformation • Zirconium oxide exists in three different crystal structures: monoclinic at room temperature, tetragonal at ~1200°C and cubic at 2370°C. • Zirconium oxide is transformed from one crystalline state to another during firing. • At the firing temperature, zirconia is tetragonal and at room temperature, it is monoclinic, with a unit cell of monoclinic occupying about 4.4% more volume than when tetragonal.
  • 13. • The volume expansion caused by the cubic to tetragonal to monoclinic transformation induces large stresses, and these stresses cause ZrO2 to crack upon cooling from high temperatures. • When the zirconia is blended with some other oxides, the tetragonal and/or cubic phases are stabilized. • Effective stabilizers include magnesium oxide (MgO), yttrium oxide (Y2O3, yttria), calcium oxide (CaO), and cerium(III) oxide (Ce2O3).
  • 15. • Zirconia is often more useful in its phase 'stabilized' state. Upon heating, zirconia undergoes disruptive phase changes. • By adding small percentages of yttria, these phase changes are eliminated, and the resulting material has superior thermal, mechanical, and electrical properties.
  • 16. • In some cases, the tetragonal phase can be metastable. • If sufficient quantities of the metastable tetragonal phase is present, then an applied stress, magnified by the stress concentration at a crack tip, can cause the tetragonal phase to convert to monoclinic, with the associated volume expansion(4.4%).
  • 17. • This phase transformation can then put the crack into compression, retarding its growth, and enhancing the fracture toughness. • This mechanism is known as transformation toughening, and significantly extends the reliability and lifetime of products made with stabilized zirconia.
  • 20. Zirconia = Ceramic steel • It may be noted that zirconia has many features in common with systems based on iron (stainless steel )as : 1. Three allotropes 2. Martesnitic transformation 3. Metastable phases Thus it is known as ceramic steel (Garvie et al , 1975).
  • 21. Properties of Zirconia Physical properties : • Low thermal conductivity (20% that of alumina) • Opaque Chemical properties: • Chemically inert and corrosion resistant Biological properties: • Biocompatible
  • 22. Mechanical properties: • Flexural strength 900 Mpa • Compresive strength 2000MPa • Fracture toughness 8-10 MPa · m1/2 • High fracture resistance • Wear of opposing dentition (Monolithic Zirconia) • Difficulty in adjusting occlusion
  • 23. Hydrothermal degradation of zirconia • Hydrothermal degradation of zirconia occurs between 200-400 ˚C . • Longer exposure times at oral temperature may also degrade zirconia leading to increased surface roughness , fragmanted grains and microcracks .
  • 24. Uses of Zirconia • Protective coating on particles of TiO2 pigments. • Refractory material . • In Oxygen sensors. • Electroceramics. • Thermal barrier coating (low thermal conductivity) in jet and diesel engines. • Ceramic knives. • Diamond simulant (cubic zirconia).
  • 26. Uses of Zirconia in dentistry • Crowns and bridges • Inlays and Onlays • Veneers • Endodontic post and cores • Fillers in dental composite • Implants • Implant abutments • Orthodontic brackets • Pedodontic crowns
  • 27. Zirconia as fillers in dental composite • Surface-modified zirconia/silica with a median particle size of approximately 3 microns or less
  • 31. Zirconia CAD/CAM Blocks Soft machining Hard machining • Mostly, they are fabricated from a porous block, milled oversized by about 25%, and sintered to full density in a 4 - 6 hours cycle. • Alternatively, fully dense blocks are milled. • However, this approach requires approximately 2 hours of milling time per unit whereas milling of the porous block necessitates only 30 to 45 minutes for a three-unit bridge.
  • 32. Zirconia sintering Temperature • Currently available zirconia for soft machining of dental restorations utilize final sintering temperatures varying between 1350 and 1550 ◦C depending on the manufacturer. • The microstructure of 3Y-TZP ceramics for dental applications consists of small equiaxed grains (0.2–0.5 µm) in diameter, depending on the sintering temperature
  • 33. Steps of fabrication of zirconia restorations
  • 35. Virtual model on software
  • 38. Zirconia toughened alumina ZTA • 70-90% alumina • 10-20% zironia • Toughened by a stress-induced transformation mechanism of zirconia leading to compressive stresses within alumina. • The strength of alumina is doubled and toughness is increase 2-4 times .
  • 43. Surface treatment of zirconia implants • Changing the surface chemistry using bioactive coating with different materials (calcium phosphates, bisphosphonate, collagen, etc.) • Optimizing surface architecture and microroughness using different techniques.
  • 44. Scanning electron microscopy (SEM) observation of fibroblasts cultured on zirconia: cells grow on the whole zirconia surface, covering it with a cellular layer.
  • 45. Zirconia individualized CAD/CAM implants • Austrian Surgeons have designed a system to produce via CAD/CAM individualized Zirconium Dental Implants for use in case of immediate implant placement. • In short, after a tooth is extracted it is scanned and a zirconium copy is milled. • The milled copy has macro- retentive features which help secure the new implant in the extraction socket. They report a 90% success rate.
  • 48. Bonding to Zirconia • One problem of zirconia application is its adhesion to different substrates. • Surface treatment of zirconia produces an activated surface in different applications. • Since zirconia is resistant to aggressive chemical treatment. • Very aggressive mechanical abrasion methods must be used to provide sufficient surface roughness.
  • 49. Conventional surface treatment techniques are: (1)acid etching with hot acids • This procedure based on corrosion–controlled process and metallic nature of pure zirconium. • It selectively etches the zirconia and creates micro-retentions on the surface by modifying the grain boundaries through removal of the less arranged atoms .
  • 50. • Hot acid etching with combinations of highly corrosive acids (HNO3, H2SO4, and HF) improves both initial bond strengths and durability . • Sulfuric acid in solution with hydrogen peroxide (H2O2) (Piranha solution) appeared to have a positive effect on the bonding of zirconia with resin cements .
  • 51. (2)Abrasion with diamond (or other) rotary instruments (can cause microcracks) (3)Coatings of low melting temperature porcelain micro pearls.
  • 52. (4)Selective infiltration etching (SIE) • SIE uses a heat-induced maturation process to pre-stress surface grain boundaries in ZrO2 to allow infiltration of boundaries(1) with molten glass. • The glass is then etched out (2)using HF, creating a network of inter-granular porosity that allows nano-mechanical interlocking of resin cement .
  • 54. (5)Fusion sputtering : • Fusion sputtering is a new technique used to create rough zirconia surface by spraying an air-water jet carrying microscopic zirconia particles onto unsintered zirconia frameworks. • Upon impact with the surface, the particles achieve good contact and adherence. • After sintering, these particles become structurally fused with the underlying framework and create undercuts suitable for establishing mechanical retention with resin adhesives.
  • 55. (6) Air abrasion with alumina (Mechnical) low pressure particle abrasion (LPPA) (7)Application of different laser types (8) Plasma oxyfluoride This process presents a method to chemically modify zirconia by creating thin oxyfluoride conversion layer on its surface that is receptive to organosilane attachment .
  • 56. (9) Tribiochemical silica coating (1o) Plasma spray (siloxane coating)
  • 57. Conclusion in bonding to zirconia • The use of phosphate monomer luting cements on freshly air-abraded zirconia is the simplest and most effective way for zirconia cementation procedure. • These resin cements have shown good mechanical retention.
  • 58. MDP resin cements • MDP-containing resin cement continues to be a popular choice for luting ZrO2 prosthetics in clinical applications due to its low failure rate and loss of retention. • The hydroxyl groups of the passive zirconia surface bond to the phosphate ester group of the MDP. • 10-Methacryloyloxydecyl dihydrogen phosphate
  • 60. References 1. A D Bonna et.alZirconia as a dental biomaterial.Materials.2015;8:4978-91 2. Z Khamverdi et al.Zirconia :An up- to-date literature review.DJH.2012;4:1-15 3. MN Aboushelib et al.Bonding to Zirconia(A systematic review).Open Access Journal of Dental Sciences.2016 4. K Nakamura et al.Zirconia as a Dental Implant AbutmentMaterial: A Systematic Review.Int. J Prosth.2010 5. R Pandero et al .Zirconia in fixed prosthesis. A literature review . Journal Clin Exp Dent.2014;6:66-73 6. Philips’ science of dental materials.12th edition.