DENT2113, unit 2.

3
Acid-base and MTA
cements

Brendan M. Leung, Ph.D.

Department of Applied Oral Sciences

School of Biomedical Engineering

bleung@dal.ca
Topics to be covered in this module

1. Understanding the basics of acid-base cements

¨ Classification
¨ Applications
¨ General chemistry
¨ Material properties

2. Zn-base and MTA cement – structure, function and

biocompatibility
¨ Zinc Phosphate
¨ Zinc Polyacrylate (Polycarboxylate)
¨ Zinc Oxide Eugenol (ZOE)
¨ Modified ZOE (EBA-ZOE)
¨ Metal trioxide aggregate (MTA)
Continuing our discussion on acid-base cements

Materials Formulation and Reacting Components Reaction Type

Zinc phosphate Powder: zinc oxide and magnesium oxide Acid-base reaction
Liquid: phosphoric acid, water

Zinc oxide–eugenol Powder: zinc oxide Acid-base reaction

Liquid: eugenol

Zinc oxide–eugenol (EBA Powder: zinc oxide Acid-base reaction

modified) Liquid: eugenol and ethoxybenzoic acid

Zinc polycarboxylate Powder: zinc oxide and magnesium oxide Acid-base reaction
Liquid: polyacrylic acid, water

Glass ionomer Powder: fluoroaluminosilicate glass Acid-base reaction

Liquid: polyacrylic acid, polyprotic carboxylic
acid, water

Resin-modified glass ionomer Powder: fluoroaluminosilicate glass, Light- or chemically activated

chemically and/or light-activated initiator(s) polymerization and acid-base
Liquid: polyacrylic acid, water-soluble reaction
methacrylate monomer, water, activator

Covered in
previous units
Overview of Acid-Base Cements
Dental cement and luting agents
n Bonding of biomaterials to tooth
structure.

n Mechanical vs Chemical bonding

¨ Mechanical = friction and entanglement
¨ Chemical = bonding to dentin

n In both cases, quality and quantity of

contact surfaces dictate strength of
bond
Dental cement for cavity liner and pulp capping
n Less thermal conductive = less irritation
¨ This is especially true for metallic restorations
n Also protect again chemical irritation
¨ Restoration containing phosphoric acids, for example

Thermal Conductivity
Material (W/m·K)
Zinc phosphate cement (dry) 1.26
Zinc phosphate cement (wet) 1.63
Zinc oxide−eugenol 1.67
Corkboard 0.04
Gypsum plaster board 0.17
Portland cement 0.29
Glass 1.01
Zirconia ceramic 1.7
Ice 2.18
Stainless steel 15.9
Alumina 30
Pure gold 297
General components in dental cement
n powder-liquid system
n Powder: Mineral oxides or glass
n Liquid: Acids (Polycarboxylic acid, tartaric acid)

Also supplied in single-

unit capsules mixed
using an amalgamator
Acid – Base Reaction

Chemical reaction between a compound

with replaceable hydrogen ions (acid) and
a substance with replaceable hydroxide
ions (base) that yields a salt and water; for
aqueous cements, the liquid is an acid and
the powder is a base.
“Salt bridge”

Powder (Metal Oxide or Silicate) = Base

Liquid = Acid

Yields a cement matrix (salt) + water

Acid + Base = Salt + Water

pH of acid base cements over time
GLASS IONOMER
Time (minutes) Zinc Phosphate Polycarboxylate Polyacid Liquid Water-Settable
2 2.1 3.4 2.3 1.8
5 2.6 3.9 3.0 2.0
10 3.1 4.4 3.8 3.4
15 3.3 4.8 3.9 3.9
20 3.6 4.9 4.0 4.2
30 3.7 5.0 4.2 4.5
60 4.3 5.1 4.6 4.8
1440 5.5 5.9 5.7 6.0

n Every acid-base cement starts acidic when first made,

and becomes more basic over time
Zinc phosphate cement
Typical composition of Zinc Phosphate Cement

Adapted from Paffenbarger GC, Sweeny WT, Issacs A: J Am Dent Assoc 20:1960, 1933.(Powers 595)
Powers, John M. Restorative Dental Materials, 11th Edition. C.V. Mosby, 082001. VitalBook file.
Zinc phosphate cement
n Oldest of the luting cement
¨ First appeared in the literature in 1897. Modern day formulation as early as 1902.

n Strong and fast setting materials – 50% strength at 10min, full strength in 24hr

n No adhesive properties to teeth or prosthesis – bonding is simply mechanical

n Reaction of zinc oxide and phosphoric acid is very violent – exothermic!

¨ Methods were invented to slowing down the reaction, so that hydration and gelation can happen
before crystallization of salt cage
¨ Use of cool, dry mixing slab as well as slowly introducing powder into liquid

n Powder contain more than 75% zinc oxide and up to 13% magnesium oxide

n The liquid contains phosphoric acid (38% to 59%), water (30% to 55%),
aluminum phosphate (2% to 3%), and in some cases zinc phosphate (up to
10%)
¨ Aluminum phosphate is essential. Cement won’t form without it.
Zinc phosphate cement – setting reaction

n Phosphoric acid dissolve zinc oxide and reacts with

aluminum phosphate to form a zinc aluminophosphate gel
on the remaining undissolved zinc oxide.
¨ The set cement contains unreacted zinc oxide particles encased in an
amorphous matrix of zinc aluminophosphate

n Zn2+ ions move through the gel into the liquid phase to react
with phosphoric acid to form salt bridge - this takes some
time and will slow the reaction down

n The water formed will go back to hydrate more zinc

aluminophosphate gel
¨ It is an autocatalytic reaction and there is net loss of water in set Zn
phosphate cement
Hydration of chia seeds
 Zinc Phosphate Cement – recap
n Powder: ZnO (+ MgO and other oxides)
n Liquid: Phosphoric acid, water, aluminum
phosphate
n High modulus and compressive strength, but
pulpal irritation (acidic)
n Thermal insulating base under metallic dental
restorations (thermal conductivity similar to
enamel)
n Applications:
¨ Long-span bridges
¨ Metal and PFM crowns
¨ Orthodontic bands
¨ Cavity liners
Mixing of zinc phosphate cement
n Careful mixing in small portion
to prevent overheating.

n Cool mixing slab before use

n Use the entire slab area to

maximize heat dissipation.
Zinc Polycarboxylate cement
 Zinc polycarboxylate cement
n First cement to demonstrate chemical bonding to tooth
¨ Like zinc phosphate, it is opaque and thus generally only used for
temporary restoration
n Permanent cement for crowns, bridges, inlays and onlays
n Powder: ZnO (+ MgO and other oxides)
n Liquid: Poly acrylic/carboxylic acid
Acetic acid

Acrylic acid

Polyacrylic acid
MW = 15-50k
Setting reaction of zinc polyacrylic cement

1. Acid attack on Zn oxide (or glass) causing ion release.

2. Migration of ions into aqueous phase.

3. Ionization of polyacid and unwinding of polymer chain.

4. Charged chain interacts with oxide, leading to ion

binding and amorphous gelation.

5. Hardening caused by continuation of ion binding.

6. Resulting cement consist of undissolved metal oxide

particles surrounded by a matrix of zinc polyacrylate.
Mechanism of adhesion between
polycarboxylate cement and dentin/enamel
n The carboxylic residues on the poly-acid chain can form ionic bonds
with the calcium ions on the surface of dentin and enamel.
¨ The bond to enamel is greater than that to dentin, because the enamel has a
higher concentration of calcium ions
n The polyacrylate displaces calcium and phosphate ions and enters
the hydroxyapatite structure.
n Note that this type of bonding also happens with glass ionomer
cements.
Biocompatibility of Zn polycarboxylate cement
n Quick setting, gets viscous and hard to handle quickly.
¨ Much faster than Zn phosphate
¨ Undergo shear thinning due to chain alignment during mixing

n More elastic than Zn phosphate.

n Well tolerated, low cytotoxicity, less acidic than Zn phosphate.
¨ Polyacrylic acid is a weak acid, also high molecular weight so they do not enter
dentinal tubules.
Let’s take a 10min break
Zinc oxide eugenol (ZOE) cements and
derivatives (EBA-ZOE and EBA-HV)
 Zinc Oxide Eugenol (ZOE) Cement
n Powder: ZnO (with a few other Zn salts and
rosin)

n Liquid: Eugenol (a weak acid) plus other oils

to adjust paste consistency
¨ Main component in essential oil of cloves

n Water needed to form Zn hydroxide to yield

Zn and hydroxyl ions

n Neutral pH (less irritation, inflammation) but

one of the weakest cements
¨ Medicament quality. Can have a blunting /
dulling effect on pulpal tissue *Simplified mechanism

n Applications
¨ Endodontic sealers and root-end filling
¨ Cavity base
¨ Temporary crowns, bridges
¨ Provisional tooth restoration
Zinc eugenolate dimer and cement matrix

Zinc eugenolate
 Setting reaction of ZOE
n Mixing reactive zinc oxide with eugenol. Water is essential.
n Acid-base reaction involving zinc and eugenolate ions:
n Hydration and generation of Zn2+ within surface water layer of ZnO particles (HE =
eugenol)
ZnO+H2O ßà ZnOH+ + OH-
(occurs on the surface of ZnO)

ZnOH+ ßàZn2+ + OH-

HE ßà H+ + E-
Overall: Zn2+ + 2E- + H+ + OH- ßà ZnE2 + H2O

n Note that Zn(OH)2 is not one of the intermediate species. Zn(OH)2 does not react
with eugenol because they do not dissolve, hence Zn2+ will not be released.
n The presence of an accelerator, like acetic acid, directly attack zinc oxide thus
eliminates the need of water to generate zinc ion

ZnO+2H+ ßà Zn2++ H2O

HE ßà H+ + E-
Acetic acid Zn2+ + 2E- ßà ZnE2
Key ZOE properties
n Sets in 4-10 minutes, mediated by ZnO surface hydration.

n Low mechanical strength, but can be strengthened in several ways using

additive.
¨ PMMA resin in powder phase
¨ Fine ZnO power also improves mechanical strength
¨ Polymerizations of resin monomer in liquid phase (IPN)

n High setting shrinkage and thermal expansion –compensated by creeps and

flow under stress.

n Will dissolve in oral cavity over time – release eugenol and ZnO, both with
therapeutic properties.

n Note that eugenol inhibits polymerization of methacrylate-based resins –

nonphenolic (no aromatic rings) components should be used instead.
¨ Eugenol acts as free radical scavenger
 EBA modified ZnO-eugenol cement
n Problem with ZOE: Slow setting and low strength
¨ Increase the rate of Zn2+ ion generation with stronger acid (EBA) that can participate in cement
matrix formation (acetic acid can’t do that!)

n 2-ethoxybenzoic acid (62.5%) mixed with eugenol (37.5%), roughly 2:1

¨ EBA speed up formation of Zn2+ from ZnO (~4 min)

¨ Allows a very high powder-to-liquid ratio (6:1 or more)

¨ Increase compressive strength by forming mixed Zn-EBA-eugenolate chelates, although exact

structure remains unknown
¨ Note that EBA alone cannot form a stable cement with ZnO (why?)

n Tabular alumina (30%) and hydrogenated rosin (6%) mixed in with ZnO (64%)
¨ Form much stronger cement (91MPa)

2-ethoxybenzoic acid (EBA) Eugenol

Bye ZOE! - EBA-HV, a non-eugenol cement
n n-hexyl vanillate (HV) dissolves in EBA, which forms
quick setting (5-10 min) and stronger (1.5-3x) than ZOE.
¨ HV replaces eugenol
¨ Sets stronger than ZOE
¨ HV does not inhibit acrylate polymerization

Eugenol 2-ethoxybenzoic n-hexyl vanillate

acid (EBA)
EBA-HV polymer cement
n Poly(methyl methacrylate) can now be incorporated into
the EBA-HV-ZnO cement structure to form an IPN.

n Resulting cement is extremely strong (>150MPa)

Endodontic cement sealer - MTA
n Necessary to ensure hermetic seal of
root canal

n Functionally serves as base, liner,

filling material, or adhesive to bind
devices and prostheses to tooth
structures or to each other.

n Types of sealant
¨ Zinc oxide-eugenol (ZOE)
¨ ortho-ethoxybenzoic (EBA)-ZOE
¨ Mineral trioxide aggregate (MTA)
¨ Polyketone product
¨ Epoxy resin
¨ Calcium phosphate cement
¨ Calcium hydroxide material
¨ Silicone sealer
Mineral trioxide aggregates (MTA)
n Mixture of tricalcium silicate, tricalcium aluminate,
tricalcium oxide and silicate oxide
¨ With bismuth oxide to make MTA radiopaque
n Very similar composition as Portland cement
Mineral trioxide aggregates (MTA)
n Mixed with water to form a colloidal gel
¨ Silicate hydrate gel
¨ Create and release calcium hydroxide as by-product
(antimicrobial)
¨ Can be mixed with polypropylene glycol to improve handling

n Sets in 3 to 4 hrs, followed by maturation period over 28

days
¨ Setting not affected by water (hydraulic cement)
¨ Compressive strength increases to 50 MPa when matured
Handling properties of MTA
n MTA will set over a large powder:liquid ratio; between 4:1
and 2:1

n Mixed material can achieve a putty-like consistency and

be rolled into a ‘log’ by hand.
 also interesting finding that hydrated MTA immersed i
It was reported that physical and chemical properties of phosphate buffered saline (PBS) produced more miner
MTA are adversely affected in a low-pH environment.35 It precipitation than those immersed in distilled water.
was also reported that the quality of crystals which is a These tag-like structures are believed to be the result o
Hydration and maturation of MTA
reaction product of hydrated MTA was poor in acidic pH
compared to alkaline pH.35 Another study recommended
ionic dissolution of MTA which resulted in growth an
nucleation of the apatite layer.44,45 Dreger et al. reporte
that the acid-etching of ProRoot MTA should be delayed that the calcium ions released from the cements diffuse
n Consist of series of complex hydration process
until 96 hours after MTA placement to avoid the harmful through the dentinal tubules and reacted with phosphat
effect of acid etching on MTA surface. 36 Regarding the ions in the tissue fluids, and yield calcium phosphate.
Mustenvironment,
¨alkaline have water theretois proceed
a report that calcium And eventually, this calcium phosphate incorporate
hydroxide induced alkalinity increased porosity and un- other ions and matured into carbonated apatite (CDHA).
n Initial hydration of tricalcium silicate to form calcium hydroxide
hydrated microstructure of MTA.34 Generally, there is no This phenomenon suggested the possibility that th
(épH) and calcium silicate hydrate gel (fills void).
consensus on whether the calcium hydroxide affects the
sealability of MTA.37,38 In this sense, further studies on the
precipitated minerals formed the mineralized layer betwee
MTA and dentin which yielded chemical bonding betwee
n Calcium hydroxide reacts with phosphate ion in body fluid to
effect of calcium hydroxide on hydration reaction of MTA is
necessary.
MTA and dentin.33 Han and Okiji demonstrated that dent
which was in contact with MTA uptook Ca and Si from th
form amorphous calcium phosphate, later turning into calcium silicate based materials.46 They reported that th
Interface between MTA and dentin Ca and Si uptake of dentin caused chemical and structur
hydroxyapatite. modification of it, which might result in higher aci
Although the superior sealing ability of MTA was well resistance and physical strength (Figure 1).
¨ Forms tag-like structures
¨ Seals the dentin-MTA interface
(a) (b)

http://dx.doi.org/10.5395/rde.2012.37.4.188
Biocompatibility of MTA
n Less cytotoxic than amalgam, ZOE, GIC and epoxy sealer
¨ Good for pulp capping

n Considered antimicrobial due to calcium hydroxide release,

but not as good as ZOE

n MTA is osteoinductive and osteoconductive

¨ Increases the expression of alkaline phosphatase, osteonectin,
osteopontin, and osteocalcin (osteogenic phenotype) in different cell
lines

n Minimal leakage around margin and apex

¨ ISO 6876 for root canal sealers (<3% solubility and < 0.01%
expansion after 30 days)

n Wash-out resistant version exist (MTA Plus)