DENTAL CEMENTS for Luting and Bonding Stephen C. Bayne Operative Dentistry UNC School of Dentistry Chapel Hill, NC 27599-7450
2004, Bayne and Thompson, UNC School of Dentistry.
RETENTION BY DENTAL CEMENTS Coarse and fine micromechanical retention
DENTIN
DENTAL JOINTS ADHESIVE SYSTEM or LUTING CEMENT
Adherend
ENAMEL, DENTIN > Liner, Base, Cement > Post and Core > Dental Amalgam > Implant >
Adherend
< Composite, Amalgam < Cast Inlay, Onlay, or Crown < All-ceramic Inlay, Onlay, or Crown < Veneers, Maryland Bridges < Orthodontic Brackets
Crown
GOALS: • Retention / resistance form • Sealing (No fluid flow or ML) Microleakage
CEMENT FACTS: • • • • • • • •
???
Tooth Structure
Fluid Flow
No correlation of lab and clinical performance. RMGI for metal substructures and composite for ceramics. Failure occurs by fatigue – crack formation and propagation. Compositions and properties constantly changing. Cements are theoretically strong enough. Initial effectiveness requires “retention and sealing.” Cement more stable at enamel rather than dentin margins. Highest stress in cements occurs at margins.
CEMENT MICROSTRUCTURE Ceramic POWDER Particles (BASIC) Inorganic or organic LIQUID (ACIDIC)
Residual POWDER Particles (FILLER) Acid-Base Salt (REACTION PRODUCT)
Powder reinforces set cement matrix Zinc Phosphate Cement
OVERVIEW OF DENTAL CEMENTS Cement Type:
(Abbr.)
LIQUID
POWDER
Zinc Oxide Eugenol: ZOE Reinforced ZOE ZOE-EBA HV-EBA
(ZOE) (RZOE) (EBA) (HV-EBA)
Eugenol Eugenol Eug, EBA HV, Eug
ZnO ZnO, Polymer, Rosin ZnO, Al2O3, Rosin ZnO, Al2O3, Rosin
Zinc Phosphate Silicate Zinc Silicophosphate
(ZP) (SC) (ZSP)
H3PO4 / H2O H3PO4 / H2O H3PO4 / H2O
ZnO F-Al-Silicate glass ZnO, F-Al-Silicate
Polycarboxylate Glass Ionomer: Conventional Resin-Modified Compomer
(PC)
PAA / H2O
ZnO
(GI) (RMGI) (CM)
PAA / H2O F-Al-Silicate Glass “ + HEMA, … F-Al-Silicate Glass (Monomers) F-Al-Silicate Glass
Composite (with DBS) (CC, CP)
(Monomers)
(Silicate glass fillers)
Dental Cement Timeline 1850
1900
1950
2000
ZOE ZP
SC PCC Compomer GI RMGI CC Contemporary Practice
Generations of Cements
Zinc Phosphate
Polycarboxylate
Resin-Modified Glass Ionomer
Glass Ionomer
Composite Cement
What do you use ???
Clinical Research Associates. Materials use survey. CRA Newsletter. 1990;14(12):1; 1995;19(10):3-4; 2001…
Dental Cement Use • • • • •
1990 1995 2001
EBA (ZOE) --1% --Zinc Phosphate 22% 12% 10% Polycarboxylate 33% 17% 5% GI, RMGI , Compomer 42% 65% 75 % Resin (Composite) 2% 6% 10% MultiLink
3M-ESPE RelyX UNICEM
IVOCLAR / VIVADENT
SETTING REACTIONS Final Set
75
% CONVERSION
% CONVERSION
100
50
25
0.1
1.0
10
Passes Large Indentor
50 Initial Set
Passes Small Indentor
25
100
1000
TIME
TIME
(hrs) Mixing Time
Mixing Interval
Working Time
Working Interval
Setting Time
Setting Interval
Initial Set
Final Set
DENTAL CEMENT PROPERTIES PHYSICAL PROPERTIES: -- Coefficient of Thermal Expansion -- Thermal Conductivity MECHANICAL PROPERTIES: -- Compressive Strength -- Tensile Strength -- Shear Strength -- Bond Strength CHEMICAL PROPERTIES: -- Solubility and Disintegration -- Absorption BIOLOGICAL PROPERTIES: -- Chemical Irritation of Pulp During Setting
CROWN
TOOTH STRUCTURE
DENTAL CEMENT PROPERTIES
ZOE R-ZOE ZOE-EBA HV-EBA ZP PC GI RMGI Composite
Physical Properties
Chemical Properties
Mechanical Properties____
Setting
∆l (µ (µm/cm)
Solubility
CS
(w/o, 37°C, 7d)
(psi, 37°C, 7d)
-31 to -85 ---- to ----12 to -24 ---- to ---+15 to -7 +50 to +420 ??? ??? ???
0.02 to 0.10 ---- to ------- to 0.40 ---- to 0.01 0.05 to 0.10 0.04 to 0.08 ??? ??? ???
2000 to 5500 10000 to 15000 -------- to --------------- to -------19000 to 21000 8000 to 18000 18000 to 24000 24000 to 30000 35000 to 45000
???
Silvey RG, Myers GE. Clinical study of dental cements. VII. A study of bridge retainers luted with three different dental cements. J Dent Res 1978;57:703-707. In a clinical study of three luting cements, 547 bridges and 162 crowns were permanently cemented. Patients were recalled at 6month intervals and the restorations were examined for looseness. A pattern of retainer type, cement type and retainer success was demonstrable.
5-Year Cement Retention: Reinforced ZOE, ZOE-EBA Zinc Phosphate Polycarboxylate
Crowns 98% 100% 96%
Bridges 92% 98% 95%
CEMENT AGING SOLUBILITY and DISINTEGRATION ADA Test
ZINC PHOSPHATE CEMENT
Multifactorial Solubility and Disintegration Events
Water Zn(OH)2 Mg(OH)2 Zn(PO4)2 H2O, Lactic acid Na+, ClFCa+, K+
Cement ZnO (and MgO), Tertiary ZP Crystals
CROWN
CEMENT THICKNESS (100 µm)
100 90 80
CROWN
70 60 50 40
???
30
TOOTH STRUCTURE
Powder CRACK LARGE CEMENT THICKNESS: Particle PORE Erosion • 110 µm is average and 50-350 is typical. • ≤100 µm is generally ideal. New considered Phase RETENTION? Precipitation SEALING?
20 10 0 TOOTH
RELATIVE STRENGTH (%)
100
80
60 y = 100e-0.0598x R2 = 0.9101
40
20
0 0
20
40
60
80
100
POROSITY (%) Ryskewitsch. J Am Ceram Soc 1953;36:65. (Empirical suggestion σ =σoexp(-nP) where n=4-7 and P=volume fraction porosity.)
CEMENT MANIPULATION
“20 different experienced dental assistants mixing the same cement”
Frequency (n)
Success / Failure Factors: MEDIAN (1) (2) (3) (4) (5)
5 4
Operator Design Factors Materials Factors Intraoral Location Factors Patient Factors
3 2 1 40
50
60
70
80
90
Compressive Strength (MPa)
ZOE-EBA Traditional Ceramic Dental Cement
ZnO
Eug + EBA ZnO
CH2-CH=CH2
(Zinc Eugenolate)
HO OCH3 (Eugenol)
CH2-CH=CH2
H3CO HO
Zn+2
HO
ZnO +
OCH3 OCH2-H3 (EBA)
COOH
CH2=CH-CH2
OCH2CH3 C-OH +2 O O- Zn HO-C H3CH2CO
(Zinc Ethoxy Bemzoate)
ZINC PHOSPHATE CEMENT Setting Reaction
ZnO
H3PO4 in H2O
ZnO + 2H3PO4 + H2O Zn(H2PO4)2- nH2O Cautions: Do not use on RDT < 1.0 mm
ZnO
Zn(H2PO4)2-H2O on mixing Zn3(PO4)2- 4H2O (tertiary zinc phosphate)
Mixing Procedure and Precautions Zinc Phosphate Cement Chilled glass slab and dispensing P. Fleck’s Mizzy ZP Cement
Dividing P portions and dispensing L.
Incremental additions and stropping.
CEMENT ACIDITY ON SETTING Zinc Phosphate Cement Mix 0
1 hr 10
100
1 day 1,000
TIME (minutes) pH 7 6 5 4 3 2 1
Mixing, Working, Setting Intervals
1 week 10,000
SILICATE CEMENT Silico-phosphate = Traditional Ceramic Filling Material
SiO2, Al2O3, Na, Ca, F
H3PO4 in H2O
SiO2, Al2O3, Na, Ca, F
Si+4 Al+3 Na+ Ca+2 FPO4-3
Residual Glass Particle SiO2, Al2O3, Na, Ca, F
Alumino-silico-phosphate GLASS Si+4, Al+3, Ca+2, Na+, F- Ions
POLYCARBOXYLATE CEMENT Polymer-Based Dental Cement Zn+2 -OOC -HOOC --- COOZnO
PAA in H2O
-- COOZnO
-- COOH Zn+2 -OOC --
-- COO- Zn+2 -- COO-OOC --OOC --- COOH Residual Glass Particle ZnO
ZINC POLYACRYLATE GEL
Mixing Procedure and Precautions Polycarboxylate Cement A
C
Dispensing P and L.
Folding P into L. D B
E
Stropping.
GLASS IONOMER CEMENT Hybrid = SC(P) and PCC(L), Polymer-Based Dental Cement
SiO2, Al2O3, Na, Ca, F
PAA in H2O
SiO2, Al2O3, Na, Ca, F
Si+4 Al+3 Na+ Ca+2 FPAA
Residual Glass Particle SiO2, Al2O3, Na, Ca, F
POLYACRYLATE GEL (initially Ca polyacrylate gel and later Al polyacrylate gel) Si+4, Al+3, Ca+2, Na+, F- Ions
GLASS IONOMER CEMENT Reactions Ca+2 Al+3 Si+4 F-
H-O-H
¯OOC
COO¯ COO¯
--O --O-Si+4(OH)2
F-AlAl-SiO2, CaF2
H-O-H COO¯ COO¯
H-O-H
¯OOC
Ca+ COO¯ COO¯
COO¯ COO¯
¯OOC COO¯ COO¯ Ca++ ¯OOC
¯OOC Ca+ ¯OOC
COO¯ COO¯ ¯OOC
COO¯ COO¯
¯OOC Al+3 COO¯ COO¯
H-O-H
H-O-H
Hydrophobic POLYMER
GIOMER
COMPOMER
§ VLC Composite and § Pre-reacted GIC powder
§ VLC Composite and § F source
FILLING MATERIALS
Universal CEMENTS FILLING MATERIALS
COMPOSITE CEMENTS FILLING MATERIALS
RM-GIC § GIC and § VLC Hydrophilic monomer and polymer
CEMENTS
MM-GIC
GIC
RR-GIC
§ GIC and § Metallic fillers § Cermet fillers
§ GIC and § Resin-Fillers
A.R.T. and TEMPORARIES
CORES HYDROGEL
Slow long-term F-ion release by diffusion from particle.
Rapid early F-ion release from matrix.
15 F-1, Ca+2, Al+3, Si+4
Cement Matrix
10
5
FluoroFluoroAluminoAluminoSilicate Particle
ST A F
SLOW
F- 1
Dissolution of particle edge for reaction.
MATRIX
FLUORIDE RELEASE (ppm)
20
PARTICLES
0
7
14
TIME (Days)
21
28
15
EFFECTIVE LEVELS 10 RECHARGING: • Fluoride Toothpaste, • Topical Fluoride, • Fluoride Mouthrinse
5
MATRIX
FLUORIDE RELEASE (ppm)
20
PARTICLES
0
7
14
TIME (Days)
21
28
CERAMIC BONDING HF ETCHING • HighHigh-Leucite Porcelains • HighHigh-Alumina Porcelains • Alumina Cores (ProCera) • Zirconia Cores (Cercon, Lava)
ENAMEL CERAMIC INLAY
AcidAcid-etched enamel and dentin Dentin bonding system
DENTIN
RESIN INLAY CEMENT Resin Cement = Composite
HF acidacid-etched surface Silanated / Bonded surface
DENTAL CEMENT EXAMPLES A. Zinc Oxide Eugenol Cements: Cements: ZOE 2200 (LD Caulk) ZOE (J. Bird Moyer Co.) ZOE Temporary (LD Caulk) ZOGENOL (Stratford Cookson) Cookson) Reinforced ZOE Cements (RZOE): ZOE B+T (LD Caulk) IRM (LD Caulk) FYNAL (LD Caulk) ZEBACEM (LD Caulk) OPOTOW ALUMINAALUMINA-EBA (Getz) AURACEM (DMG Hamburg) B. Hexyl Vanillate Cements (HV): (None currently marketed) C. Zinc Phosphate Cements (ZP): MODERN TENACIN (LD Caulk) FLECK'S EXTRAORDINARY (Mizzy (Mizzy)) SMITH'S ZINC CEMENT (Teledyne) AMES ZZ-M (Teledyne) KENT ZINC CEMENT (Stratford Cookson) Cookson) LANGLANG-C+B Only (Lang) S-C (Stratford Cookson) Cookson) DROPSIN (Atwood Industries) ELITE (I.D.T. Corp) D. Silicate Cements (SC):
E. Zinc SilicoSilico-phosphate Cements (ZSP): AMES PLASTIC Porcelain (Teledyne) ASTRALIT (Premier) SYNTREX F (Premier) SILICAP (HD Justi) Justi) F. Polycarboxylate Cements (PC): TYLOK (LD Caulk) DURELON (Premier) CHEMIT (Harry J. Bosworth) CARBOXYLON (3M) POLYPOLY-F (DeTrey (DeTrey)) G. Glass Ionomer (GI): ASPA (LD Caulk) IONOMER (Denmat (Denmat)) FUJI II (GC America) KETACKETAC-CEM (ESPE)) BIOBOND LUTING (Harry J. Bosworth) AQUACEM (DeTrey (DeTrey)) BASELINE (DeTrey (DeTrey)) ResinResin-Modifed Glass Ionomer (RMGI): FUJI I (GC) FUJI PLUS (GC(GC-America) RELYRELY-X LUTING (VITREMER CEMENT) (3M) ADVANCE (LD Caulk) PRINCIPLE (LD Caulk) NEXUS (Kerr) DYRACT CEM (Dentsply) PERMACEM (DMG Hamburg) VITREBOND CEMENT (3M)
Compomer UniCem (3M(3M-ESPE) MaxCem (Kerr) MultiLink (HeraeusHeraeus-Kulzer) Kulzer) H. (Resin) Composite Cements (CC): COMSPAN (LD Caulk) PANAVIA F (Kuraray) PANAVIA 21 (Kuraray) ENFORCE (LD Caulk) RESIN CEMENT (3M) NEXUS (Kerr) MEGABOND (Harry J. Bosworth) DUODUO-CEMENT (Coltene (Coltene)) CALIBRA (LD Caulk) OPAL LUTING (3M) COMPOLUTE (ESPE) CEMENTCEMENT-IT (Jeneric/Pentron (Jeneric/Pentron)) LUTELUTE-IT (Jeneric/Pentron (Jeneric/Pentron)) BUILDBUILD-IT (Jeneric/Pentron (Jeneric/Pentron))
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