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

Adherend

ENAMEL, DENTIN > Liner, Base, Cement > Post and Core > Dental Amalgam > Implant >

< Composite, Amalgam < Cast Inlay, Onlay, or Crown < All-ceramic Inlay, Onlay, or Crown < Veneers, Maryland Bridges < Orthodontic Brackets

GOALS:
Retention / resistance form Sealing (No fluid flow or ML) Microleakage

Crown

???

Tooth Structure

CEMENT FACTS:

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.

Fluid Flow

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: Zinc Oxide Eugenol: ZOE Reinforced ZOE ZOE-EBA HV-EBA Zinc Phosphate Silicate Zinc Silicophosphate Polycarboxylate Glass Ionomer: Conventional Resin-Modified Compomer (Abbr.) (ZOE) (RZOE) (EBA) (HV-EBA) (ZP) (SC) (ZSP) (PC) (GI) (RMGI) (CM) LIQUID Eugenol Eugenol Eug, EBA HV, Eug H3PO4 / H2O H3PO4 / H2O H3PO4 / H2O PAA / H2O POWDER ZnO ZnO, Polymer, Rosin ZnO, Al2O3, Rosin ZnO, Al2O3, Rosin ZnO F-Al-Silicate glass ZnO, F-Al-Silicate ZnO

PAA / H2O F-Al-Silicate Glass + HEMA, F-Al-Silicate Glass (Monomers) F-Al-Silicate Glass (Monomers) (Silicate glass fillers)

Composite (with DBS) (CC, CP)

Dental Cement Timeline

1850 1900 1950 2000

ZOE ZP SC PCC Compomer GI RMGI CC

Contemporary Practice

Generations of Cements

Zinc Phosphate

Polycarboxylate

Glass Ionomer

Resin-Modified 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
100

% CONVERSION

% CONVERSION

75

Final Set

50
Initial Set

Passes Large Indentor

50

25

Passes Small Indentor

25

0.1

1.0

10

100

1000

(hrs)
Mixing Time Working Time

TIME

TIME

Setting Time

Mixing Interval

Working Interval

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

Physical Properties
l (m/cm) (

Chemical Properties Solubility

(w/o, 37C, 7d)

Mechanical Properties____ CS
(psi, 37C, 7d)

Setting

ZOE R-ZOE ZOE-EBA HV-EBA ZP PC GI RMGI Composite

-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
Multifactorial Solubility and Disintegration Events

ZINC PHOSPHATE CEMENT

Water Zn(OH)2 Mg(OH)2 Zn(PO4)2 H2O, Lactic acid Na+, ClFCa+, K+

Cement ZnO (and MgO), Tertiary ZP Crystals

CROWN 100 90 80 70 60 50 40 30 20 10 0 TOOTH

TOOTH STRUCTURE CROWN

CEMENT THICKNESS (100 m)

???

Powder CRACK LARGE CEMENT THICKNESS: PORE Particle Erosion 110 m is average and 50-350 is typical. 100 m is generally considered ideal. New Phase RETENTION? Precipitation SEALING?

100 RELATIVE STRENGTH (%)

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 =oexp(-nP) where n=4-7 and P=volume fraction porosity.)

20 different experienced dental assistants mixing the same cement

Success / Failure Factors: MEDIAN (1) (2) (3) (4) (5) Operator Design Factors Materials Factors Intraoral Location Factors Patient Factors

CEMENT MANIPULATION

Frequency (n)

5 4 3 2 1 40 50 60

70

80

90

Compressive Strength (MPa)

ZOE-EBA
Traditional Ceramic Dental Cement Eug + EBA ZnO ZnO

HO OCH3

(Zinc Eugenolate)

CH2-CH=CH2

CH2-CH=CH2

HO

Zn+2

OCH3 OCH2-H3
(EBA)

COOH

CH2=CH-CH2

HO OCH2CH3 C-OH +2 O O- Zn HO-C H3CH2CO

(Zinc Ethoxy Bemzoate)

ZnO +

(Eugenol)

H3CO

ZINC PHOSPHATE CEMENT

Setting Reaction
H3PO4 in H2O

ZnO

ZnO

ZnO + 2H3PO4 + H2O Zn(H2PO4)2- nH2O

Cautions: Do not use on RDT < 1.0 mm

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.
Flecks Mizzy ZP Cement

Dividing P portions and dispensing L.

Incremental additions and stropping.

CEMENT ACIDITY ON SETTING

Zinc Phosphate Cement
Mix 0 10 1 hr 100 1 day 1,000 1 week 10,000

TIME (minutes) pH 7 6 5 4 3 2 1

Mixing, Working, Setting Intervals

SILICATE CEMENT
Silico-phosphate = Traditional Ceramic Filling Material
SiO2, Al2O3, Na, Ca, F H3PO4 in H2O Si+4 Al+3 Na+ Ca+2 FPO4-3

SiO2, Al2O3, Na, Ca, F

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.
D B

Folding P into L.

Stropping.

GLASS IONOMER CEMENT

Hybrid = SC(P) and PCC(L), Polymer-Based Dental Cement
SiO2, Al2O3, Na, Ca, F PAA in H2O Si+4 Al+3 Na+ Ca+2 FPAA

SiO2, Al2O3, Na, Ca, F

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
H-O-H

Ca+2 Al+3 Si+4 FCOO COO F-Al-SiO2, AlCaF2 Ca+ COO COO --O-Si+4(OH)2 --O H-O-H COO COO

OOC

OOC OOC

H-O-H

COO COO

OOC Ca+ OOC OOC

COO COO Ca++ OOC COO COO COO COO OOC Al+3 COO COO

H-O-H

H-O-H

Hydrophobic POLYMER

GIOMER
VLC Composite and Pre-reacted GIC powder

COMPOMER
Universal CEMENTS FILLING MATERIALS
VLC Composite and F source

COMPOSITE
CEMENTS FILLING MATERIALS

FILLING MATERIALS

RM-GIC
GIC and VLC Hydrophilic monomer and polymer

CEMENTS

MM-GIC
GIC and Metallic fillers Cermet fillers

GIC

RR-GIC
GIC and Resin-Fillers

CORES
HYDROGEL

A.R.T. and TEMPORARIES

20

FLUORIDE RELEASE (ppm)

Rapid early F-ion release from matrix.

Slow long-term F-ion release by diffusion from particle.

15
Cement Matrix

F-1, Ca+2, Al+3, Si+4

T AS F

10

FluoroFluoroAluminoAluminoSilicate Particle MATRIX

SLOW

F- 1

Dissolution of particle edge for reaction.

PARTICLES

14

21

28

TIME (Days)

20

FLUORIDE RELEASE (ppm)

15

EFFECTIVE LEVELS
10
RECHARGING: Fluoride Toothpaste, Topical Fluoride, Fluoride Mouthrinse

MATRIX PARTICLES

14

21

28

TIME (Days)

CERAMIC BONDING
HF ETCHING High-Leucite Porcelains High High-Alumina Porcelains High Alumina Cores (ProCera) Zirconia Cores (Cercon, Lava)

ENAMEL
Acid-etched Acidenamel and dentin Dentin bonding system
RESIN INLAY CEMENT Resin Cement = Composite

CERAMIC INLAY
HF acid-etched acidsurface Silanated / Bonded surface

DENTIN

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 ALUMINA-EBA (Getz) ALUMINAAURACEM (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 Z-M (Teledyne) ZKENT ZINC CEMENT (Stratford Cookson) Cookson) LANG-C+B Only (Lang) LANGS-C (Stratford Cookson) Cookson) DROPSIN (Atwood Industries) ELITE (I.D.T. Corp) D. Silicate Cements (SC): E. Zinc Silico-phosphate Cements (ZSP): SilicoAMES 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) POLY-F (DeTrey) POLY- (DeTrey) G. Glass Ionomer (GI): ASPA (LD Caulk) IONOMER (Denmat) (Denmat) FUJI II (GC America) KETAC-CEM (ESPE)) KETACBIOBOND LUTING (Harry J. Bosworth) AQUACEM (DeTrey) (DeTrey) BASELINE (DeTrey) (DeTrey) Resin-Modifed Glass Ionomer (RMGI): ResinFUJI I (GC) FUJI PLUS (GC-America) (GCRELY-X LUTING (VITREMER CEMENT) (3M) RELYADVANCE (LD Caulk) PRINCIPLE (LD Caulk) NEXUS (Kerr) DYRACT CEM (Dentsply) PERMACEM (DMG Hamburg) VITREBOND CEMENT (3M) Compomer UniCem (3M-ESPE) (3MMaxCem (Kerr) MultiLink (Heraeus-Kulzer) Heraeus-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) DUO-CEMENT (Coltene) DUO(Coltene) CALIBRA (LD Caulk) OPAL LUTING (3M) COMPOLUTE (ESPE) CEMENT-IT (Jeneric/Pentron) CEMENT- (Jeneric/Pentron) LUTE-IT (Jeneric/Pentron) LUTE- (Jeneric/Pentron) BUILD-IT (Jeneric/Pentron) BUILD- (Jeneric/Pentron)

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