Adhesion

General Resins Cements

Microscopic processes for formation of adhesive joint

Clean / stable / rough surface

Good wetting of adhesive

High contact in pores

Strong cured / set adhesive

Adhesive liquid characteristics

Rapid flow Low viscosity High surface wetting Adhesive surface tension < surface energy E Strong liquid / solid physical interaction To fill pores / roughness High surface tension
Wetting Steel PTFE (non stick) E = 230 E = 18mJ / m2 Water = 73 oil = 18 Capillary action

High

low

Physical Interactions
Van de Waals interactions
Attraction between opposite charges on ions and dipoles ion / ion dipole / ion + dipole / dipole + H-bond (particularly strong) + like Materials generally either hydrophilic or hydrophobic - + attracts like

C=O ------H-OR - +

Adhesive Cure
Chemical reaction converts adhesive to strong +-+-+ solid -+-+ Ionic (eg acid + base salt + water) + - + - + Covalent (eg in C-C backbone in polymers) (CH2-CH2)n Bonding interaction with surface Micro mechanical Polymer entanglements Chemical

Dentine and enamel resin adhesion

Composition of enamel and dentine

Enamel wt% Hydroxyapatite Water Noncollagenous proteins Collagen 95 3 1 70 10 2 18 Dentine

Enamel can be wet by hydrophobic or hydrophilic monomers Dentine requires hydrophilic monomers Both surfaces need roughening for good adhesive contact

History of resin bonding

Pre 1970 Acid etch enamel (not dentine) self cured bonding agents 1970s Hydrophobic enamel adhesives Hydrophilic dentine adhesives light cure systems 1980s Acid etch of dentine Acidic hydrophilic monomers for dentine priming Hydrophobic low viscosity resin adhesive

1990s Common dentine and enamel adhesives Light and dual cure systems 5th generation 2 component combine Primer and adhesive or Etchant and primer 6th generation 1 component combine etchant, primer and adhesive

For enamel bonding

Addition of phosphoric acid for 30s
Frosty appearance SEM structure show preferential etching of hydroxyapatite prism
Cores Periphery

Penetration of methacrylate monomers into rough surface provides micromechanical bonding

Enamel etching

SEM of preferential prism core or periphery etching After 30 -120s etch frosty appearance develops

4th generation dentine bonding agent compositions Etchant

37% Phosphoric acid (gel with silica particles or cellulose)

Primer
Hydrophilic monomer + initiators HEMA or MMA Polymerisable carboxylic acid (COOH) 4-META (anhydride) or BPDM, GPDM (acid containing dimethacrylates) Solvent Acetone or ethanol / water

Adhesive
BISGMA (resin) TEGDMA (diluent) + initiators Inorganic fillers (0.5 to 40 wt%) Fluoride

Dentine bonding processes

Phosphoric acid etch for 10s gives
Smear layer removal Hydroxyapatite dissolution

Drying causes
Collagen collapse

Priming gives
Collagen rehydration

Monomer penetration into tubules and collagen provides

Micromechanical adhesion on polymerisation Tubule sealing

Mechanism of dentine bonding

Acid washing / rinsing Removes smear layer Dissolves HA

Drying shrinks remaining Collagen polymer molecules Rehydration / priming Swells collagen

Mechanism of dentine bonding

Monomer polymerisation And collagen entanglement

Monomer penetration

Hybrid layer and resin tags

Cross section SEM

composite

Resin must flow into Collagen hybrid layer Tubules branches especially important for high bond strength

dentine

6th generation dentine adhesives

CH2=CH R COOH CH2=CH R CH2PO(OH)2 5th (eg clearfil (Kuraray) and 6th (eg Prompt L-pop (3M ESPE) generation adhesives often have more acidic phosphoric acid group on polymerisable monomers

4th generation mainly have lower acidity carboxylic acid groups on polymerisable Hydrophilic monomers

6th generation adhesion mechanism

Dissolution of smear layer and HA by methacrylated phosphate

Solvent evaporates Dissolved components bound into polymerised matrix

Bond strength and fatigue

Initial resin bond strengths to enamel and superficial dentine can be 15-35 MPa Combined mechanical and thermal cycling can rapidly decrease bond strength Deep dentine bond strengths generally lower

Cement adhesion

Cements
Hydrophilic and react / associate with dentine / enamel structures
Base Zinc phosphates OP(OH)3 ZnO Zinc polycarboxylate

PAA

Silicates

Al Si Base

GIC

Acid + base

salt + water

GIC types
Type I Luting Uses cementation of crowns orthodontic etc. aesthetic low stress thermal barrier under metal restoration dentine substitute under composite Powder / liquid wt. fraction 1.5

II III

Restorative a)Lining

>3

1.5 >3

b)Base

Cement Strengths
Cementation GIC RMGIC Zn phosphate Zn polycarboxylate Adhesive resin Compressive Tensile 90-220 4 85-120 13 96-130 55-96 50-210 4 4 40 Bases Compressive Tensile 70-210 4-8 150-200 20-40 130-160 80 8 16

Low strength neutral and basic cements

Zinc oxide eugenol (neutral) Sedative effect on pulp polymerisation inhibitor Calcium hydroxide (base) cements Calcium hydroxide with glycol salicylate gives calcium disalicylate (aspirin anologue) Light cure cements contain CaOH and UDMA O OH Acid ZnO + Base

Ion exchange adhesion mechanism in GICs

Sr 2+ H+ Sr 2+

Sr 2+

Sr 2+ H+ Sr 2+

H+ H+ Sr 2+

Sr 2+ Ca 2+ Ca 2+ Ca 2+ dentine enamel

Interfacial layer can be stronger than cement itself

Bond strength of glass ionomer to enamel and dentine after PAA surface treatment
7.5 Conditioning for 10s Cleans surface Only slightly opens tubules Improves strengths 3 fold GIC bond strengths Initially weaker than with resins Increase with time Break less due to low shrinkage

Strength (MPa)

Enamel 5 Dentine 2.5

Control

25% PAA

Texts
R. Van Noort, Introduction to Dental Materials Mosby 1994 (2nd ed. June 2002) R.G. Craig, J.M. Powers, Restorative Dental Materials 11th ed. Mosby 2002 W. J. OBrien, Dental Materials and Their Selection 2nd ed. Quintessence 1997 N. Nakabayashi, D.H. Pashley, Hybridisation of dental hard tissues, Quintessence 1998. G.J. Mount, RW, Bryant, Preservation and restoration of tooth structure Mosby 1998. Biomaterials special issue vol 19 (6), Proceedings of the 1st European Union Conference on Glass Ionomers 1998

References
Resin adhesives
Chapt I.X Principles of Adhesion in ref 1 Chapt 2 Properties of Dentin in ref 4 Chat. 10 Bonding to dental substrates in ref 2

Glass ionomer cements

Chapt. II.III Glass-ionomer Cements in ref 1 Chapt 11 Dental cements in ref 3 Chapt 8 Glass ionomer materials G.J. Mount, R.W. Bryant, in ref 5