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DENTAL MATERIALS IV

DENTAL CEMENTS

 Traditionally dental cements were inorganic zinc oxide–based materials but nowadays
polyacid-based materials predominate.
 They are used as direct filling materials and luting agents for indirect dental restorations.

CLASSIFICATION OF DENTAL CEMENTS


Many criteria may be used to classify dental cements. The most widely used method is to
classify them according to composition.

I. Classification of dental cements according to composition:

A. Cements based on phosphoric acid


a) Zinc phosphate cements
b) Silicate cements
c) Silicophosphate cements
d) Copper phosphate cements
B. Cements based on organometallic chelate compounds
a) Zinc oxide-eugenol cements (ZOE)
b) Ortho-ethoxybenzoic acid cements (EBA)
c) Calcium hydroxide cements
C. Cements based on polyacids
a) Polycarboxylate cements
b) Glass ionomer cements (GIC)
c) Resin-modified glass ionomer cements (RMGIC)
d) Resin cements

II. Classification of dental cements according to their application:

1. Filling materials
1) Permanent (e.g., GIC)
2) Temporary (e.g., ZOE)
2. Base/liner cements (calcium hydroxide cement)
3. Luting cements
1) Permanent (e.g., zinc phosphate cement, GIC, RMGIC)
2) Temporary (e.g., ZOE, EBA, NE cements)

Luting cements
 In dentistry cements are luting agents that are used to ‘cement’ a restoration to prepared teeth,
usually by mechanical retention.
 Two categories exist: permanent luting agents and those for temporary (provisional) luting
and/or a protective action.
 Traditionally dental luting cements were inorganic zinc oxide–based materials.

III. Based on their chemistry, cements are broadly classified as:

 Inorganic (e.g., zinc phosphate cement);


 Organic salt (e.g., zinc polycarboxylate and glass ionomer cement);
 Resins and resin-reinforced adhesives.

 Inorganic and organic salt cements rely on mechanical interlocking into surface
discontinuities and roughness although, with organic salt cements, there is some chemical
bonding between the organic acid and calcium in hard tissue.
 Resin cements rely more upon chemical interactions for their retentive action (adhesive
dentistry).
 Thus, until the advent of resin-based cements, retention by dental cements was primarily
mechanical in nature.

Selection criteria for dental cements:


 Biological compatibility
 Low thermal conductivity
 Low thermal expansion
 Low solubility
 Easy manipulation
 Long shelf life
 Low film thickness
 Low viscosity
 Long working time, snap set
 High strength
 Good adhesion
 Opacity
Cement consistency
 For good retention, the cement must flow over both tooth and restoration, providing a thin,
strong film between the two surfaces.
 Good flow is necessary to prevent voids and esure intimate surface contact, behaviour
determined by the cement characteristics and the powder/liquid (P/L) ratio, which determines
film thickness.
 Thicker mixes are used for provisional restorations.

Thermal properties
 Cast restorations have higher thermal conductivities than enamel and dentin, and dental
cements must have low conductivity to provide a thermal barrier between restoration and
tooth.

Mechanical properties
 Cements must possess sufficient strength to support the restoration and withstand transmitted
masticatory forces.

PROVISIONAL LUTING AGENTS


Provisional or temporary cements are used for:
 luting of provisional indirect restorations, including crowns, fixed partial dentures, inlays and
onlays;
 temporary cementation of definitive (final) restorations;
 temporary filling of the access opening between root canal treatments (endodontic sealants);
 interim restorations on implants.

Desirable properties of provisional cements


 Biocompatibility with hard and soft tissues.
 Easy dispensing, mixing and application.
 Adequate working and setting times.
 Good retention.
 Easy removal of excess cement from the external and internal restoration surfaces.
 Easy removal of the restoration without damage to hard and soft tissues.
 Minimal or no reaction with the restorative material.
 No interference with adhesion of a final cement.
 Good shelf life.

Zinc oxide-eugenol (ZOE) cements


 ZOE cements are available as handmix (powder–liquid as well as paste–paste) and
automix systems; the latter are more convenient and provide greater accuracy in
proportioning.

Composition of zinc oxide-eugenol (ZOE) cements

COMPONENT FUNCTION
Powder
Zinc oxide Primary reactive ingredient
Zinc acetate (1-5%) Accelerator
Liquid
Eugenol Primary reactive ingredient
Olive oil (5-15%) To control viscosity

 Provisional luting agents commonly are based on zinc oxide‒eugenol (ZOE) and set by
initial hydrolysis of ZnO to Zn(OH)2 the latter reacting with eugenol to form zinc
eugenolate gel at the ZnO particle surface.
 With time, the gel crystallizes, increasing the strength of the set mass, crystallite
formation being accelerated by zinc acetate.
 Zinc eugenolate decomposes in water to form Zn(OH)2 with liberation of eugenol.
 Eugenol release by hydrolysis of ZOE can leave residues that interfere with the setting
reaction (polymerization) of subsequently applied resin-based permanent luting agents.
 Despite an anesthetic effect, eugenol is severely inflammatory.
 ZOE sets in 4‒10 min with a film thickness of 25µm but the set material has low
compressive strength (27.6 MPa).
 The P/L ratio determines the consistency and mechanical properties of ZOE cements
 ZOE is hydrolytically unstable which, with its low strength, predicates its use as a
provisional luting agent.
EBA cement
 This cement is a modified ZOE cement.
 Modification with ortho-ethoxybenzoic acid (EBA) with a 1.66 : 1 EBA-to-eugenol ratio
markedly increases cement strength.

NE cements
 Eugenol-free or non‒eugenol‒based provisional cements with carboxylic acids replacing
eugenol are increasingly available.
 NE provisional cements are supplied as paste-paste systems or in automix syringes.
 NE provisional cements are stronger, more retentive, and have longer working and setting
times than ZOE but may have slightly inferior flow properties and somewhat greater film
thicknesses.
 These cements are less susceptible to hydrolytic breakdown and, consequently, are
considered to be more suitable for long-term provisional cements than ZOE.

PERMANENT LUTING AGENTS


Traditionally, permanent dental luting cements were acid–base setting inorganic zinc oxide–based
materials, but the modern trend is greater use of glass ionomers and resin-based materials.
Types of permanent luting dental cement:
 Zinc phosphate cements (ZNP)
 Zinc polycarboxylate cements (ZNC)
 Glass ionomer cements (GIC)
 Calcium aluminate/glass ionomer cements
 Hybrid (resin-reinforced) ionomer cements (RMGIC)
 Resin cements

Zinc phosphate cement (ZNP)


 Zinc phosphate is a powder/liquid system and was once the most widely used permanent
cement.
 During setting H3PO4 and ZnO react to form a hydrated amorphous zinc phosphate
[Zn3(PO4)2] matrix surrounding unreacted ZnO particles.
Composition of zinc phosphate cement

POWDER LIQUID
Zinc oxide (90.3%) Phosphoric acid (38.2%)
Magnesium oxide (8.2%) Phosphoric acid buffered with Al and Zn
(16.2%)
Silica (1.4%)
Bismuth oxide (0.1%)
Barium oxide, barium sulfate and calcium
oxide (≤0.1%)

 Setting occurs within 5–7 min, the low initial pH (about 2.1) increasing to pH 4 within 60
min.
 Strength increases with time, achieving about 90% (100 MPa) of final strength in 24 h, while
solubility decreases.
 After mixing and cement placement within the crown, the restoration should be seated
immediately to ensure low film thickness.

Zinc polyacrylate (polycarboxylate) cement (ZNC)


 Zinc polycarboxylate cement sets by ZnO reacting with an aqueous polyacrylic acid solution
to form an amorphous gel matrix of zinc polyacrylate surrounding unreacted ZnO.
 The polyacrylic acid may chemically bond to calcium in enamel, enhancing retention.
 Physical properties are comparable to ZNP.
 Despite the low initial pH, dentinal tubule penetration of unreacted acid is limited by its large
molecular size.
 Presently, this cement is used primarily for long-term provisional cementation.

Glass ionomer cements (GIC)


 There are several categories of glass ionomer cements all comprising a calcium
fluoroaluminosilicate glass powder and a liquid based on polyacrylic, icatonic and tartaric
(polyalkenoic) acid.
 GIC is a two-component system available in mechanically mixable and autodispensing
systems.
Categories of glass ionomers

CATEGORY APPLICATION
Type I Luting agents
Type II Filling material
Type III Base/liner
Type IV Core build-up

Setting reaction of glass ionomer cement


 During setting, the polyacid attacks the glass, releasing Ca2+, Al3+ and F‒ ions which react
with the polyanions forming a salt gel matrix stabilized by bound Al3+ ions.
 Fully set cement is a composite of glass particles surrounded by silica gel in a matrix of
polyanions cross-linked by ionic bridges.
 The gel matrix also contains small particles of silica gel encapsulating fluoride crystallites.
 GICs may be antimicrobial and, through fluoride release, provide protection against
secondary caries.
 Bonding to tooth is improved by dentin smear layer removal with acid followed by dilute
ferric chloride solution to deposit Fe3+ ions, which promote ionic interactions with GIC.

Zinc polycarboxylate and GIC characteristics compared with those of zinc phosphate
(ZNP) cement

Characteristic Zinc polycarboxylate Glass ionomer cement


Film thickness Same or slightly greater Same or slightly less
Compressive strength Lower Greater
Tensile strength Greater Lower (brittle)
Solubility Lower Greater
Working time Comparable Slightly shorter
Setting time Comparable Longer (initial isolation)
Bonding (ZNP only bonds Mechanical and chemical Mechanical and chemical
mechanically)
Biological reactions Less Less

Resin-modified and resin cements


 Modern dental practice is moving toward resin-modified and resin-based luting agents.
 Most of these materials satisfy demanding clinical requirements and exhibit excellent
adhesion, high strength, biocompatibility and low solubility.
Requirements of resin-modified and resin cements
 Consistency and handling
 Working and setting time
 Film thickness
 Radiopacity
 Strength and wear resistance
 Retention (bond strength)
 Shade availability
 Fluoride release

Resin-modified glass ionomers (RMGIs)


 The resin-modified glass ionomers are hybrid ionomer cements.
 RMGIs are versatile materials with a variety of applications.

Types of RMGI and their applications

RMGI APPLICATIONS
Type I Luting agents of cast metal and porcelain
restorations, posts, and orthodontic appliances
Type II Filling material as provisional restorations
Type III Base/liner for amalgam restorations
Type IV Core build-up

 RMGIs are available in self-, light-, or dual-cured forms and are supplied as powder–liquid
systems, as paste–paste systems, and in automix cartridges and syringes as well as pre-dosed
capsules.

Composition of RMGI cements


 The powder component is principally an ion-leachable glass whereas the liquid contains four
or more components: methacrylate resin, polyacid, HEMA (hydroxyethylmethacrylate) and
water (with differences existing between individual commercial products).
Components of liquid portion of RMGI cements

COMPONENT FUNCTION
Methacrylate resin Permits setting by polymerization.
Polyacid Reacts with the glass causing setting by an
acid–base reaction.
HEMA (hydroxyethylmethacrylate) Facilitates coexistence of resin and acid in
aqueous solution and participation in
polymerization.
Water Essential for ionization of acid required for
acid–base reaction.

Setting reaction
 RMGIs may have three setting mechanisms: acid–base reaction, ligh-tactivated
polymerization, and chemically activated polymerization.
 Initial setting is polymerization of methacrylate groups in the liquid component whereas the
slower acid–base reaction provides final strength.
 Some products use conditioning or bonding agents such as polyacrylic acid and aluminum
chloride or citric acid containing ferric chloride.
 Water must be present, either by incorporation or inward diffusion following the initial set,
for the acid–base reaction to occur.

Properties
 Compared with GICs, RMGIs have improved translucency, the same fluoride release, and
greater strength.
 Bonding to dentin is comparable to that of GICs but RMGIs bond better to resin-based
restorations.
 Initial pH is low (3.5) but increases over time.
 Some RMGIs (and GICs), particularly the light-curing types, sorb water and will expand after
placement.
 This hygroscopic expansion can cause fracture of sintered alumina copings of all-ceramic
crowns and zirconia crowns.
Resin cements
 Resin cements are essentially low-viscosity composite filling materials having a resin matrix
containing silane-treated inorganic fillers (silica, glass, or ceramic particles and/or colloidal
silica).
 The polymer systems of resin cements include acrylic resin (PMMA) or methacrylate
copolymers, bis-GMA resins, and urethane dimethacrylate resins with diluents such as
triethylene glycol dimethacrylate (TEGMA).
 The fillers, approximately 75% by weight, 47% by volume, have a particle size of
approximately 1 micron and provide wear resistance, increased strength, and reduced
expansion and contraction.
 Polymerization is by conventional chemical-cure or light activation.
 Dual-cure systems, which utilize both curing mechanisms, are usually radiopaque whereas
light-cured systems are not radiopaque but are available in different shades.
 Most resin cements require a bonding agent to promote adhesion to tooth structure.
 Some cements are available with high- and low-viscosity catalyst pastes.

Average properties of GICs, RMGIs and resin cements

GIC RMGI Resin cement


Setting time (min) 7 4 4.5
Film thickness (µm) 25 15 10‒25
Solubility (%) 0.7 0.2 0.13
Compressive strength (MPa) 150 110 400
Tensile strength (MPa) 5 20 45
Elastic modulus (GPa) 5 5 3.5

Properties
 Resin cements have greater strength and lower solubilities than inorganic cements, GICs and
hybrid ionomers.
 They form thinner films but set faster.
 They adhere to hard tissue but bond strengths to tooth and metals are lower than for adhesive
resin cements.
 The disadvantages of resin cements are technique sensitivity, radiolucency with some
materials, difficulty in removing excess material, and higher cost.
Types of resin cements and their applications

Cement type Clinical application


Light-cure Metal-free restorations (≤1.5mm thickness)
Nonmetal fixed orthodontic appliances
Nonmetal periodontal splints
Dual-cure Metal-free inlays
Metal-free onlays
Ceramic crowns
Nonmetallic bridges
Self-cure Metal-based inlays and onlays
Ceramometal crowns and bridges
Metallic crowns and bridges
Metal-based resin-bonded bridges
Bonded amalgams
Endodontic posts

Adhesive resin cements


 Adhesive resin cements are self-cure systems that incorporate bonding agents to promote
adhesion.
 The dentin-bonding agent (DBA) provides coupling between the resin matrix and the tooth.
 The 4-META system is a liquid adhesive containing methyl methacrylate monomer and
acrylic resin filler and is catalyzed by tributyl borane.
 Incorporation of polymer beads increases the viscosity to cement consistency.
 The cements containing an organophosphate (MDP) are based on bis-GMA (Bowen’s resin)
and silanated quartz filler, provide bonding through reaction of the phosphate end of the chain
with calcium of tooth or the metal oxide on metallic restorations.