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DENTAL CEMENTS

INTRODUCTION:
A variety of cements has been used in dentistry through years. In general cements
are employed as
1. luting agents to bond preformed restorations and orthodontic attachments in or on
the tooth.
2. Cavity liners and bases to protect the pulp and as a foundation and anchor for
restorations.
3. Restorative materials.
These different applications require different physical properties and appropriate
clinical manipulative characteristics and so in response to changing situation, new
international standards are being developed (international standards organisation) as
well as various national standards (American National Standards Institute/American
Dental Association) based on performance criteria rather than specific composition.
For acceptable performance in luting and restorative applications, the cement
must have adequate resistance to dissolution is the oral environment. It must also
develop an adequately strong bond through mechanical/chemical interlocking and
adhesion. High strength in tension, shear and compression are required, as in good
fracture toughness to resist stresses at the restoration/ tooth interface. Good
manipulation properties, such as adequate working and setting time are essential for
successful use. The material must be biologically acceptable.
Introduction of new types of cements was prompted by the emphasis on
improved bio compatibility to the tooth that began to develop 20 years ago.
New information on pulpal histopathology resulting from particular clinical
techniques and materials as well as the demonstration of marginal leakage involving
penetration of bacteria in to the dentin interface and a reduction in retention of
restoration led to the realization that new materials were needed that possessed good
wetting and bonding to enamel and dentin and that had low toxicity. These concepts
were the basis of development of cements based on polyacrylic acid: first the
polycarboxylate and later the glass-ionomer cements. The advent of resin based
cements came in 1950s. in the last decade, polymerizable BIS-GMA and other
dimethylacrylate monomer cements became available. The cements based on the
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reaction between calcium hydroxide and a liquid salicylate originated about 25 years
ago.

CLASSIFICATION OF DENTAL CEMENTS:

Based on matrix forming species:

Matrix bond Class of cement Type

Phosphate Zinc phosphate Zinc phosphate
Zinc phosphate fluoride
Zinc phosphate copper oxide/salts
Zinc phosphate silver salts
Zinc silicophosphate Zinc silico phosphate
Zinc silicophosphate mercury salts
Phenolate Zincoxide eugenol Zincoxide eugenol
Zincoxide eugenol polymer
Zincoxide eugenol EBA alumina
Calcium hydroxide Calcium hydroxide salicylate
salicylate
Polycarboxylate Zinc polycarboxylate Zinc polycarboxylate
Zinc polycarboxylate fluoride
Glass ionomer Calcium alumino polyalkenoate
Calcium aluminium
Polyalkenote polymethylacrylate
Polymethylacrylate Acrylic Poly (methyl methacrylate)
diethylacrylate Dimethylacrylate unfilled
Dimethylacrylate filled

SELECTION OF DENTAL CEMENTS:

Application Cement type

Fixed partial denture, inlays crown GIC

posts, multi retainers, vital teeth with Zinc phosphate
average retention. Zinc polycarboxylate

Multi retainer splints on vital; teeth with Zinc oxide eugenol polymer
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above average retention, minimal

dentin thickness, hypersensitivity
patients.

Temporary cementation Zincoxide eugenol polymer

Zinc polycarboxylate

Base or liner in cavity with remaining GIC

dentin more than about 0.5 mm Zinc polycarboxylate
Zinc phosphate

Cavity with remaining dentin or Calcium hydroxide

exposure Zincoxide eugenol

CLASSIFICATION OF DENTAL CEMENTS BASED ON USES

Cement Principal use Secondary use

Zinc phosphate Luting agent for restorations Intermediate restoration, thermal
and orthodontic appliances insulating base
Zinc phosphate with Intermediate restoration
silver/copper salts
Zincoxide eugenol Temporary and permanent Root canal restorative,
luting agent, temporary and Periodontic dressing
intermediate restoration,
thermal insulating bases,
pulp capping agent.
Polycarboxylate Luting agent, thermal Luting agent for orthodontic,
insulating bases intermediate restoration.
Silicates Anterior restorations
Silico phosphate Luting agent Luting for orthodontic,
intermediate restoration.
GIC Luting agent, coating for Pit and fissure, anterior
eroded areas restorative, thermal insulting
bases.

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Resin Luting agent Temporary restorative

Calcium hydroxide Pulp capping agent, thermal
insulating bases
According to E.C.Combe,
1. Acid –base reaction cement
2. Polymerizing materials.
a. Cyano acrylates
b. Dimethacrylate polymers
c. Polymer – ceramic composites
3. Other materials
a. Calcium hydroxide
b. Guttapercha
c. Varnishes
Zincxide eugenol

Eugenol
Zinc phosphate Zinc

Zinc oxide polycarboxylate

Phosphori Polyacryli
c acid c acid
Fluorine containing alumino
Silicate Glass
silicate glass
ionomer

Luting cement requirements:

1. They should be non toxic and non irritant to the tissues.
2. Insoluble in saliva and liquids taken into the mouth.
3. Film thickness should be 18 m – 25 m Rheological properties are important. It
should have sufficiently low viscosity to give a low film thickness and should have
adequate working time at mouth temperature to permit placement of the
restoration.
4. Capable of bonding to enamel, dentin and to dental ceramic and cast alloy.
5. Suitable mechanical properties, particularly where bonding is achieved by
micromechanical retention.

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6. Optical properties for the cementation of a translucent restoration such as an all

ceramic crown, the optical properties of cement should be similar to those of
tooth substance.
ZINC PHOSPHATE CEMENT:
Zinc phosphate cement is the oldest of the luting cement and is thus one that has
longest “track record”
Composition Use of each ingredients
Powder:
Zinc oxide : 90.2% Principal ingredient.
Magnesium oxide : 8.2 % Aids in sintering.
Other oxides like : 0.2 % Improves smoothness of mix.
(Bismuth, Trioxide,
calcium oxide, barium oxide)
silica : 1.4 % Filler, aids in sintering.
Liquid:
Phosphoric acid : 38.2 % Reacts with zinc oxide.
Water : 36.0 % Controls rate of reaction.
Aluminium phosphate : 16.2% Buffers to reduce rate of reaction.
or some times zinc
phosphate
Aluminium : 2.5 % Reaction between powder and liquid,
Zinc : 7.1 % allowing adequate working time.

The ingredient of the powder are heated together at temperatures ranging from
10000C - 13000C for a prolonged period of time of approximately 4-8 hrs. This
calcination results in a fused or sintered mass. The mass is then ground and pulverized
to a fine powder.
The zinc phosphate cement powders may be obtained in a variety of colours.
The lighter shades of yellow and gray are most popular.
Chemistry of Setting :-
When a zinc oxide powder is mixed with phosphoric and, a solid substance is
rapidly formed with considerable evolution of heat. The exact nature of the reaction
product is not certain. In the past it has been supposed that the teritiary zinc phosphate
[Zn3 (Po4)2 4H2O] (hopeite) is the final product. However this has been revised by recent
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studies. Zinc oxide powders that have not been deactivated do react to form hopeite,
but the crystalline mass that is formed is not cohesive. Properly deactivated zinc oxide
powder, such as that in dental cement powder, reacts with the liquid initially to form an
amorphous cement matrix of zinc orthophosphate, apparently without the intermediate
formation of and phosphates. After a few minutes, crystallizes of hopeite develop, but
only on the surface of the cement. Thus the set cement consists of matrix of amorphous
zinc phosphate which binds un-reacted zinc oxide particles together with crystallites of
hopeite developing at the surface of cement mass. The final is a "CORED" structure.
Zinc oxide + phosphoric acid → Amorphous zinc phosphate
In the dental cement, the reaction by the addition of Aluminium and zinc to the
liquid. The Aluminium appears to be the most important additive, as it forms
aluminophosphoric acid complexes with phosphoric acid. These complexes apparently
moderate the reaction and help prevent the cement base from forming undesirable
crystallites.
Manipulation:
The proper amount of powder should be incorporated in the liquid slowly on a
cool slab ( app. 210C) to attain the desired consistency.
Mixing Slab:
Since the combination of modified zinc oxide and phosphoric acid results in the
liberation of heat, in the immediate environment of the reaction, this heat must be
dissipated readily or the reaction will proceed too fast toward completion. If this rapid
reaction occurs, ample working time is not available for proper manipulation of cement
before hardening or setting occurs.
A properly cooled glass slab thick enough that is not readily influenced by the
environment will dissipate the heat of reaction. The mixing slab temperature should be
low enough to be effective in cooling the cement mass but must not be below the dew
point unless the frozen slab technique is used. A temperature of 18 0 to 240 C is
indicated when room humidity permits. The moisture condensation upon a slab cooled
down below the dew point contaminates the mix, diluting the liquid and shortening the
setting time. The ability of the mixing slab to be cooled and yet to be free of moisture
greatly influences proper control of the rate of the reaction of the zinc phosphate
cement.
Powder/ liquid ratio:
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Both the experienced and inexperienced operator can produce better mixes
consistently by having a measured amount of powder and liquid available or at least a
close approximation of the proper amount of powder and liquid dispensed on the mixing
slab.
Although the ultimate quantity of powder that can be incorporated is determined
by a number of factors. A slight excess of powder should be placed on one side of
mixing slab is the event it is needed to avoid redispencing from the stock bottle during
the mixing procedure.
The minimum size of any cement mix should be that which can be conveniently
handled and judged for proper consistency rather that the amount of cement actually
needed. The amount of liquid with which the powder is combined to form a sufficient
quantity of inlay cement of luting consistency.
Care of the liquid:
The zinc phosphate cement liquid consists of the partially neutralized diluted
phosphoric acid. When this liquid is exposed to a humid atmosphere, it will absorb
water, where as exposure to dry air will tend to result in a loss of water.
It has been established that during the use of dispensing bottle, the cap is of for a
sufficient period time to effect significantly the water content of the liquid if exposure has
been made to an unfavorable atmospheric humidity. Therefore it is good practice to
keep the bottle highly closed. As a safeguard, the significance stipulates that the
manufacture should supply an excess of 20% of liquid.
The setting time of the mixed cement is quite noticeably affected by water addition or
subtraction form cement liquid. The addition of water results in shortening and setting
time and subtraction of water results in lengthened setting time.
Mixing procedure:
By the initial incorporation of small portions of powder into liquid, minimal heat is
liberated and dissipated. The dissipation of heat is most effectively accomplished when
the cement is mixed over a large area of cooled slab. A relatively long narrow bladed
stainless steel spatula may be used conveniently to spread the cement across this large
area, thereby controlling the setting time and temperature of the mass. During
neutralization of liquid by the powder, temperature of the mixing site is inversely
proportional to the time consumed in accomplishing the mix. Thus if a large volume of
powder is carried to the liquid all at once rather than spatulated over a large area of the
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slab, for a sufficient time, temperature at the site of the reaction becomes higher. This
temperature rise speeds the reaction and hardens the control over the consistency
being developed. In this case, consistency of the mass is achieved by the rapid
approach of the initial setting rather than by the establishment of the higher P-L ratio.
Larger amounts of powder may be incorporated during the middle of the mixing
period to further saturate the liquid with the newly forming complex zinc phosphates.
The quantity of the unreacted acid is less at this time because of prior neutralization
gained with the addition of small initial powder. The amount of heat liberated is also less
and easily dissipated.
Finally smaller amounts of powder again are incorporated, so that one does not
go beyond the desired ultimate consistency. Thus the mixing procedures begins and
ends with small increment, first to achieve slow neutralization of the liquid.
The time consumed during the mixing of the cement should allow adequate
dissipation of heat so as to maintain control over setting reaction and to produce a
smooth homogeneous consistency. Mixing time is 60-90 Secs (depending on the
product)

Frozen slab method:

The mixes used in the normal mixing procedure have adequate working and
setting time for cementation of inlays and crowns. However in the cementation of
orthodontic bands, the short working time of normal mixes allows the cementation of
only a few bands with one mix and setting time is too long for convenience. The frozen
slab method has been developed to overcome their difficulties. In this method a glass
slab is cooled in a refrigerator at 6 0 C or freezer at -10 0 C a mix of cement is made on
the cold slab by addition of powder until correct consistency is reacted. The amount of
powder incorporated with the frozen slab method is 50% to 75% more than with normal
procedures.
No difference exists in solubility as well as tensile and compressive strengths of
cements prepared with normal procedure and frozen slab method.

Advantages of frozen slab method:

1. Substantial rise in working time of the mix on the slab and a shorter setting
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time of mix after placement.

2. Setting time is decreased by 20 - 40% compared with normal mixes.
3. Recently method has been employed for cementation of bridges and multiple
pins.
Characteristic properties:
ANSI/ADA specification No. 8

Setting time at Max. Film thickness Max. Tensile Modulus of

370C comp Str solubility strength elasticity
(24 Hrs) and disint. MN/m2 [GN/m2
(24 Hrs.) [lb/inch2] [106lb/inch2]
Minimum 5 min 68.7 Mpa Type I- 25m 0.2% by wt 3.1 – 4.5 9.3 – 13.4
Maximum 9 min [9956 Psi] Type II – 40 m [450–650]

Consistency:
Two arbitrary consistency, termed inlay seating or luting cement base or filling
are in general use.
A third consistency of zinc phosphate cement, which lies midway between the
inlay seating and the cement base, is used for retention of orthodontic bands and has
been termed "band seating consistency"
The consistency of the cement is related to P-L ratio. The more powder
incorporated into the liquid, the thicker is the mix. The mix of the cement prepared on
cool slab is suitable for cementation of cast restorations and mixture made on warm
slab is much viscous used for precession fitting castings.
Owing to the difference is brands of cement; P-L ratio to produce desired
consistency varies. The manufacture should specify the P-L ratio to provide the desired
consistency.
The inlay and crown seating consistency is desired to retain the restoration. The
retaining action is its hardened state is one of the mechanical interlocking between the
surface irregularities of tooth and restoration for inlay and crown seating, it should string
up from the slab on the spatula, 2 - 3 cm.
Film thickness:

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For an inlay or crown to be seated properly, the film of the cement should be
sufficiently thin, so that it does not interfere with fit of the restoration.
In order to facilitate complete seating of cemented restorations of certain design
(eg. Full cast crown with long parallel walls), it is often desired to provide escape route
for excess cement. One technique is referred to as "VENTING" the casting. It is
accomplished by drilling a hole in the occlusal surface of cast gold crown. The hole is
subsequently filled with condensation of gold foil.
The minimum thickness is related to particle size of powder employed. The size
of these parties is termed as the “ effective grain size". The finer the size, lower is the
film thickness.
For Type I – 25 m
For Type II – 40 m (medium particle size)
The other factor affecting film thickness is the amount of force and manner in
which force is applied to a casting during cementation.
Viscosity:
The consistency of cements can be measured by viscosity. The initial viscosity of
zinc phosphate cement of inlay consistency at 18 0, 200 and 250 show as increase is
viscosity at high temperatures with 2 minute interval.
Setting time:
According to ANSI/ADA sp.No.8, setting time of zinc phosphate is between 5-9
minutes.

Factors governing setting time:

a. Effect of P/L ratio:
When a greater surface area of powder is allowed to react with the liquid, the
reaction will terminate more readily when all other factors are constant. This
effect can be obtained by smaller particle size, more rapid rate of incorporation of
the powder and higher P/L ratio.
b. Larger the particle size of the powder, less rapid is the reaction because of
decreased surface area (contact) of powder with liquid.
c. The composition and sintering temperature of the powder. Higher the
temperature, more slowly cement sets.

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d. The composition of the liquid, - salts of Aluminium and water definitely influence
setting time.

Factors under influence of dental assistant:

a. Lower the temperature during the mixing, longer is the setting time.
b. More slowly powder is added, longer is the setting time. A slow addition of
powder, prolong the mixing time and therefore delays the setting time.
c. Longer the mixing time within practical limits, longer is the setting time.
d. More liquid employed, slower is the setting time.

Water content of the mix (liquid):

The addition of water to liquid, shortens the setting time and vice-versa.
Measurement of setting time:
The setting time is usually measured with 1 pound Gillmore needle at a
temperature of 370 C and a relatively humidity of 100%. It is defined as the time
elapsing from the start of mixing until the point of the needle no longer penetrates the
surface of the cement, when the needle gently lowered onto it.
Strength:
Strength is determined by compressive strength. Strength of the cement depends
on P-L ratio. Th compressive strength increases rapidly as the amount of powder is
increased. The set cement attains 75% of its maximal strength during first hour. When
zinc phosphate is in contact with water for long periods of time, there is gradual
decrease in strength, probably because of slow dissolution of material. The strength of
cement is probably sufficient when it is placed under inlay or crown. 103.5 Mpa (15000
Psi)
Solubility and disintegration:
This property is one of the most important considerations in the use and selection
of any dental material. In the cemented cast restorations, solubility of the cement is of
almost significance. A thin line of cement is always exposed to oral environment, even
though cement line is not visible, which has been estimated to be "50 m"
Other errors in cavity preparation, cement solubility is the probably main factor
contributing to caries around inlay and crown.

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The solubility is measured by immersion of cement disk in distilled water for 24

hours. The Sp. is then removed the water evaporated and the weight of the non-volatile
solubility products determined. In this test, max allowable solubility is 0.2%. If the
cement is immersed in dilute organic acids like lactic, acetic and citric acids, solubility is
much higher. Solubility in organic acids is also higher as compared to distilled water.
Like wise solubility increases with pH of the medium is lowered. The increase in
solubility with reduced pH is probably due to the greater solubility of the ZnO component
of the cement and also, but to a lesser extent, the increased solubility of the phosphate
material.
The durability of the cement also depends on type and pH of acids, it is exposed.
Biological property:
PH of zinc phosphate:
3 Min 1 Hr 24 Hr 48 Hr 7 Days 28 Days
3.5 5.9 6.6 6.8 6.9 6.9

An increase in P-L ratio, from the standard consistency to provide thicker mixes
of the cement appear to have little influence on either rate of change or its 48 hrs pH
value. Thinner Zinc phosphate mixers formed from lower P-L ratio, exhibits a slower
rate of increase and appears to reach a pH that is nearly as high as that of standard and
thick mixes.
Investigations have revealed that, initial acidity of zinc phosphate cement at the
time of insertion exhibit pulpal response, especially where only thin layer of dentin
remains.
Thermal and electrical conductivity:
Recent studies have indicated that this cement used as a base material is an
effective thermal insulator. Moisture preset under clinical conditions greatly reduces
insulating properties. 3.11 [Cal Sec-1 Cm-2 (0C/Cm)-1] x 104
Retention:
Zinc phosphate cement exhibits mechanical interlocking with rough tooth surface. This
is mainly a true mechanical. The thickness of the film is also as important factor.
Thinner the film better is the action. The mechanical retention is also dependent upon
the dimensional change occurring is the cement during setting, as a result of water gain

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or loss, or as a result of the differences in the co-efficient of thermal expansion of tooth

of the structural luted and of cement itself.
Applications:
Type of Cement Principal uses Secondary uses

Zinc Phosphate Luting agents for restoration. Intermediate restoration.

Cementing orthodontic bands. Thermal insulating bases.
Root canal restorations.

Classification of Zinc phosphate cement:

Type I Type II

Fine grain cement with Medium grain size.

Small particle size.

Used for cementation. Used for thermal insulation and

cementation of orthodontic bands.

Film thickness should be 25 m or less. Film thickness should not be more than
40 m.

ZINC SILICO PHOSPHATE CEMENT:

Zinc silico phosphate cements are a combination of silicate and zinc phosphate.
It is also called as zinc silicate or silicate zinc cement.
Composition:
Powder liquid
Silicate glass Phosphoric acid
Zinc oxide water
Magnesium oxide Zinc and Aluminium salt
Setting reaction:
Zinc oxide / alumino silicate glass + phosphoric acid  zinc alumino silicate
phosphate gel
The set cement consists of unreacted glass and ZnO particles bounded together
by alumino silicate phosphate gel matrix.
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Types and characteristics:

ANSI/ADA SP. NO. 21
Type I Type II Type III
Setting time at 370C
Minimum 5 min 3 min 5 min
Maximum 9 min 6 min 9 min

Compressive strength (24 Hrs) 135 165 135

( MN/m2[lb/inch2] ) (19,600) (23,900) (19,600)

Maximum film thickness (m) 25 - 25

Maximum solubility and disintegration 0.9 0.6 0.9

(24 Hrs) (% by wt)

Opacity
Minimum 0.35 - 0.35
Maximum 0.90 - 0.90

Maximum arsenic content 0.0002 0.002 0.0002

The film thickness of inlay and crown seating consistency of silico phosphate
cement is greater than that of zinc phosphate cement. The acidity of the cement is
similar to that of zinc phosphate cement, although it exhibit slightly lower initial pH and a
slightly slower rise in pH, its value are essential same after 48 Hrs.
Clinical solubility of silico phosphate cement is less in the mouth than the zinc
phosphate cement. Fluoride content of the cement, adds to its anticariogenic properties.
The comparison of orthodontic band seating consistency of silico phosphate and
zinc phosphate cement reveals substantial differences in strength values. Silico
phosphate cement exhibits lower values. The presence of glass enhances grater
translucency than zinc phosphate cement, making these materials useful for
cementation porcelain restorations.
Biological effects:
Because of the acidity of the mix and the prolonged low pH 4 – 5 after setting,
pulp protection is necessary for vital teeth.
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Advantage:
The silicophosphate cements have better strength, toughness, abrasion
resistance, lower solubility.
Considerable fluoride release adds to anticariogenic effects.
Disadvantages:
Initial pH and total acidity greater than zinc phosphate cement.
Manipulation:
The powder and liquid are dispensed on a cool glass slab. The powder is
incorporated into liquid in 2 or 3 large increments. Mixing time is 1 min. mix it in a
circular motion to obtain a required consistency.

COPPER CEMENT:
Silver salts or copper oxides are added to powders of zinc phosphate cements,
to increase antibacterial activity.
The cement may be white, black or red depending on type of oxide added.
Copper cement is classified according to the percentage of the copper oxide.
The chemistry of copper cement is similar to that of zinc phosphate cement.
pH of set cement:
Copper cement:
3 Min 1 Hr 24 Hr 48 Hr 7 Days 24 Days
0.8 3.0 4.7 5.1 5.2 5.3

Uses:
They have been primarily used as temporary restorative materials, particularly in
pediatric dentistry.
They are now rarely used because of poor biological properties.
Manipulation:
The chemistry of copper cements is very similar to that of zinc phosphate
cements and they should be manipulated in the same manner.
ZINC OXIDE EUGENOL CEMENT:
Cements of this have been used in dentistry since 1890's

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Composition Use of each ingredient

Powder
Principal ingredient

ZnO (69%) Reduces brittle of set cement plasticizer

White rosin (29.3 %) To improve strength of set cement

Zinc stearate (1.0 %)

Zinc acetate (0.7 %)
Liquid Plasticizer and reduces burning sensation

Eugenol (85.0%) caused by eugenol

Olive oil (15%) To accelerate set of ZnOE preparation

H2O
Acetic acid

Chemistry of settings :-
The most important zinc oxide powders are those formed by decomposing zinc
hydroxide & zinc carbonate by heating at 300 0.
The setting reaction is basically an acid –base reaction to form chelate the first
reaction consists of hydrolysis of zinc oxide to its hydroxide, thus indicating, water is
essential for the reaction.
ZnO + H2O  Zn(OH)2
Zn(OH)2 + 2HE  ZnE2 + 2H2O
Base Acid salt
[eugenol] [zinc eugenolate]
The reaction takes place either in solution or at the surface of ZnO particles. The
chelate is thought to form as an amorphous gel that tends to crystallize. The water that
is formed probably aids in binding the individual chelate units, together probably is a
chain or octohedral structure.
Classification R.C Craig
Type I : Class 1 – powder & liquid
Class 2 – paste & paste
Class 3 – paste & paste ( non-setting]
Type II : Class 1 – powder & liquid
Type III : Class 1 – powder & liquid
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Type IV: Class 1 – powder & liquid

Class 2 – paste & paste.

Manipulation :-
A P-L ratio of 4 : 1 is used, powder is after incorporated into a dispensed liquid in
general, more powder added, the stronger will be the cement & more viscous the mixed
cement. The setting reaction is not usually exothermic, a cooled mixing slab is not
required. There is no need to incorporate powder into liquid in small increments, usually
bulk of powder is added to liquid. Prolonged & vigorous spatulation is required,
especially for a thick mix. Mixing time is usually between 30-60 seconds.
Characteristic properties :-
 Setting time: 4-10 minutes.
 Higher the P-L ratio, faster is the set.
 Cooling the mixing slab slows the setting reaction unless the temperature is
below the dew point.
 Compressive strength : 27.6 Mpa
(24Hrs) [4000 psi]
 Smaller the particle size, stronger is the cement.
 Addition of alumina or of fused silica to the powder also improves strength.
 Addition of EBA also improves strength.
 film thickness : 25mm
 solubility & disintegration : 0.04% (wt %)

Type I : pH of the ZnOE cement is 7 & exceedingly biocompatible with the pulp.
It seals cavity well against ingress of oral fluids, at least for a short time, hence
irritation form micro leakage is minimized.
The strength of temporary cement must be low in order to permit removal of
restoration without trauma to teeth, in case of permanent restoration, without damage to
casting. [31 Mpa or 4500 Psi, should be the range] maximum.

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Type II: The upgrading of strength properties has been accomplished via the addition
of alumina or inorganic filler to the powder & EBA to liquid.
 The end results are so called "IMPROVED' ZnO cements for permanent
restoration (type II)
 Compressive strength should be at least (31Mpa or 4500 Psi)
 As the compressive strength is low, same amount of tensile force is required to
remove inlays cemented with ZnOE cement.
 Solubility & disintegration of Type II cement is 0.06%
Biological properties:
The presence of eugenol appears to exhibit anodyne & of uptudent effect on pulp
in deep cavities.
If it comes in direct contact with connective is it causes moderate irritation.
Mechanism by which strength of cement is increased :
EBA acts as chelating agent to form zinc polycarboxylate other additives may
segregate in the matrix that surrounds the ZnO core, in essence to form composite
structure.
Applications :
Type I: Designed for temporary cementation.
Type II: Permanent cementation of appliances fabricated outside the
month.
Type III: Temporary filling material & thermal insulating base
Type IV: Cavity liner.
Other uses:
1. Periodontal dressing.
2. Palliative dressing in sensitive teeth prior to insertion of permanent restorations.
3. Endodontic sealer.
Biological properties :-
The convention of sealers client mild to moderate reactions as indicated by
invitro studies, such as behavior of hela cells, human skin fibroblasts, bovine pulp
tissue, fillings is monkey, dogs, rats etc.
Advantages :
 Obtundent effect on pulp tissue
 Resistance to marginal penetration.
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Disadvantages :
 Low strength & abrasion resistance as a cavity timer & base material.
 Pot mitrate – ZnOE Temporary cement for provisional crowns to diminish post –
operative tooth pain-
Temporary interim cement of 4% KNO 3 - ZNOE significantly reduced the
incidence of pain initiated by post tooth preparation & impression. This hunting agent
facilitated removal of provisional crown, while promoting patient co- operation, it also
enables comfortable filling, seating & cementing casting.
RECENT DEVELOPMENTS:
REINFORCED ZINC OXIDE EUGENOL CEMENTS :
Composition :
Powder: ZnO – principle ingredients.
Natural & synthetic Resins. [colophony (pineresin) (polymethyl
methacrylate) (poly sterene)

Liquid: Eugenol which may also contain dissolved resins.

Acetic acid - accelerator.
Thymol or 8-hydroxyquinolone  anti-microbial agents

Setting reaction:
Setting reaction is similar to zincoxide– eugenol cements Acidic resins such as
colophony (abetic acid) may react with ZnO strengthening the matrix.
Manipulation :
More powder is required for a cementing mix mixing pad or slab should be
thoroughly dry. The powder is mixed into a liquid in small portions with vigorous
spatulation. Adequate time should be allowed for setting without disturbance of cement.
Both powder & liquid containers should be kept closed & stored under dry conditions.
Properties :
 These cements may have long working time, because moisture is needed for
setting.
 Film thickness is achieved in the range of 35-75mm
 Compressive strength ranges from 35 to 55 Mpa or (5000 to 8000 Psi)
 Tensile strength is 5 to 8 Mpa (700 to 1000 Psi).
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 Modulus of elasticity 2 to 39 Gpa (300,000 –400,000 Psi)

 Cement exhibits lower solubility due to presence if resin.
 These polymer- reinforced ZnO –eugenol cements have similar biologic prop of
basic cements.
 Setting time 6-10 min, film thickness – 32 m.
Advantages :
 Good initial sealing properties
 Adequate strength for final cementation.
Disadvantages :
Lower strength, higher disintegration & softening, discolouration of resin
restorative material.
Setting time : 6 - 10 min
Mod. of Elast : 300.000 – 400.000 Psi.
Comp strength : 5000 – 8000 Psi
EBA CEMENTS:
In order to further improve the strength of basic zinc oxide–eugenol system, O–
EBA has been added to liquid. The end result is called improved zincoxide eugenol
cement. Recently, cements for luting & intermediate restorations based on vanillic acid
(4-hydroxy–3 methoxybenzoic acid ) have been studied.
Composition:
Powder
ZnO (20 – 30%)
Aluminium oxide
Polymethyl methacrylate
Liquid
EBA (50 – 66 %)
Eugenol (34%)
Setting reaction :
The setting reaction appears to involve chelate salt formation between EBA,
eugenol & ZnO.

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Manipulation:
The cement mixes readily to a very fluid consistency even at higher P/L ratio. In
order to obtain optimal properties , P/L ratio should be 3.5 g/ml for vigorous spatulation
is required for about 2-3 min. to in corporate all powder in to liquid.
Properties :
 Setting time ranges between 2 - 7 minutes under oral conditions.
 Compressive strength (24 hrs ) 55.2 Mpa (8000 psi).
 Film thickness  25mm.
 Solubility & disintegration (by wt %)  0.05%
 Tensile strength (24hrs)  4.1 Mpa.(600 psi)
 modulus of elasticity  700.000 psi
Biologic effects:
Similar to that of Zincoxide eugenol cement
Advantages:
Easy mixing, long working time, good flow characteristics & low irritation to the
pulp.
Disadvantages:
 Hydrolytic breakdown in oral fluids
 Liability to plastic deformation.
 Poorer retention.

POLYMER BASED CEMENTS:

The majority of materials in this group are poly (methacrylates) of two types:
1. Materials based on methyl-methacrylate [MMA]
2. Materials based on automatic dimethacrylates of BISGMA types [DMA]
Acrylic resin cements: methylmethacrylate
Composition:
Powder Liquid
Methyl methacrylate Methyl methacrylate Benzoyl
peroxide –Initiator Tertiary amines – Activator
Setting:

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The monomer dissolves and soften the polymer particles and concurrently
polymerizes through the action of free radicals from peroxide amine interaction. The set
mass consists of new polymer matrix uniting the undissolved but swollen original
polymer granules.
Manipulation:
The liquid is added to the powder with minimum spatulation to avoid air
incorporation. Excess material is removed at the final set hard stage and not when the
material is rubbery, otherwise marginal deficiency occurs.

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Properties:
The properties of these materials comparable to those of cold curing acrylic
resins filling material. They are 1) Stronger and less soluble than other types of cement,
but display low rigidity and visco-elasticity. They have no effective bond to tooth
strength in presence of moisture. They show better bonding with polycorbonate crowns
and resin fillings.
Biologic effects:
Marked pulp reactions occurs.
Applications:
1. Cementation of restorations.
2. Facing.
3. Temporary crown.
Advantages:
1. Relatively high strength.
2. Toughness.
3. Low solubility.
Disadvantages:
1. Short working time.
2. Deleterious effect on pulp.
Modified acrylic resin cement:
 4 META is added in the monomer and additional initiator trybutyl boron.
 This results in greatly improved adhesion to tooth and to base metal alloys.
 The material has been used primarily for the direct bonding of orthodontic brackets.

DIMETHACRYLATE CEMENTS:
The material is based on BISGMA. They are supplied as two viscons liquids, to
pastes or as P/L materials.
Composition:
Powder Liquid
1. Borosillicate or Silica glass 1. BISGMA diluted with
2. Organic peroxide (Initiator) alkyldimethacrylate monomer

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2. Amine
Setting:
On mixing polymerization of the monomer mixture occurs, leading to highly cross
linked composite resin structure.
Manipulation:
The powder is measured volumetrically and correct number of liquid drops are
stirred in it. Paste materials are mixed in the ratio of 1 : 1.
Properties:
Compressive strength  200 to 280 Mpa (30,000 – 40,000 Psi)
Tensile strength  40 – 60 Mpa ( 600 – 8000 Psi
Solubility in water  0.05%
Film thickness  500 m
Working time  4 minutes
Setting time  6 – 7 minutes
These cements exhibit little bonding to enamel or dentin, unless etehed with
phosphoric acid.
Biological properties:
Pulpal sensitivity is due to polymerisation contraction and consequent marginal
leakage. Leakage at the enamel interface may lead to decalcification.
Applications:
Cementation of acid- etched restorations and orthodontic bands.
Advantages:
1. High strength.
2. Low solubility.
Disadvantages:
1. Difficult seating.
2. Pulpal irritation.
3. Sensitivity.

ZINC POLYCARBOXYLATE CEMENT:

Polycarboxylate cement was the first system developed with a potential
adhesion to tooth structure.

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Composition Use of each ingredients

Powder:
ZnO. Principal ingredient.
MgO. Reduces reactivity of ZnO.
Stannic oxide. (substitution for MgO)
Starrous fluoride. Increases strength of cement and
anticariogenicity.
Alumina. Improves strength, modifies setting time.
Liquid:
Aqueous solution of polyacrylic acids
and copolymers.

Chemistry of setting reaction:

When the powder and liquid are combined, the cement forming mechanism is
thought to be a reaction of zinc ions with the polyacrylic acid via the carboxylic groups.
The Zinc can also react with the carboxylic groups of adjacent polyacrylic acid chains,
so that ionically cross-linked structure is formed. Thus the hardened cement consists of
zinc oxide particles depressed in a structureless matrix of zinc polycarboxylate.
Manipulation :-
The usually recommend P-L ratio is 1/1 to 2/1. The material should be mixed on
a surface that will not absorb liquid. A glass slab may afford some advantage over the
treated paper pad. Cooling slows the chemical reaction to some extent & thus provides
some lower working time. Also the working time may be extended to some degree if the
powder is cooled in refrigerator. Under no circumstances should the liquid be cooled,
since the viscosity of the liquid increases when the temperature is decreased.
Polyacrylic acid is highly unstable at low temperatures.
The liquid should not be dispensed prior to mix is made, since it loses water at
the atmosphere, very rapidly. The loss of water markedly increases the viscosity.
The powder is rapidly incorporated into the liquid in large quantities. The mix
should be completed within 30 to 40 seconds. The cement should be used while the
surface is still glossy loss of inspire & a dull stringy, rubber consistency indicate that the
setting reaction has progressed to a extent that the satisfactory film thickness & proper
wetting of tooth structure by the cement can no longer be attained.

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During the setting, cement passes there a rubbery stage. The excess cement
that has extended at the margins of the casting should not be removed, while the
cement is in this stage, since there is danger that some of the cement may be pulled out
from beneath the margins.
Properties:
ANSI / ADA sp. No. 61.
Setting time : 5.5 min
Comp. Strength (24hr) : 55.2 Mpa, 8000 Psi
Film thickness : 21 m
Solubility & disintegration
(By wt %) : 0.06
Tensile strength (24 Hrs) : 6.2 Mpa, 900 Psi
Viscosity :-
The initial viscosity is essentially unaffected by increase in temperature from
180C. The viscosity of zinc polycarboxylate cement 2 minutes after mixing had
increased modestly at all three temperatures, however the increase in viscosity is less
compared to zinc phosphate cement.
Strength:
The compressive strength is inferior compared to zinc phosphate. Reducing the
recommended amount of powder. The mix of polycarboxylate cement by 1/3 reduced
the strength by 5mpa (700psi).
Solubility :-
Solubility is more in presence of organic acids.
Adhesion to tooth structure:
The cement does adhesively bond to tooth structure. The exact mechanism of
adhesion to tooth structure is based upon adherence to appetite crystals by hydrogen
bonding, but as the cement sets the hydrogen bonds are replaced by metal ions
producing metal ion bridge. There is some evidence that cement binds to collagen of
the dentin.
ENAMEL:
Apetite surface …. H+ … - OOC Polyacid chain
(Hydrogen bond wetting)

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….. M2+ … - OOC Ionic bond

(set condition)

DENTIN
Collagen COO - …. M2+ ….. - OOC Polyacid chain
Backbone Ionic bond

side chains
NH2 …. H+ ….. – OOC

A) The diagram suggests mechanism where by fresh mobile cement paste wets &
adheres to enamel appetite surface by Hydrogen bonds provided by free carboxylic
acid groups. As the cement reaction proceeds, most of these hydrogen bonds as
represented by "arrow" are replaced by metal ions to give metal ion bridge that
provide undernate adhesion for the cement to enamel.
B) Collagen contains some branch chains that terminate into carboxylic acid groups &
others terminate into amino groups. The former can link to the cement mass by
metal ion bridging, while the latter groups by hydrogen bridges.
Bond strength :-
Bond strength was evaluated by measuring the tensile stress required to
separate a cylinder of cement from enamel & dentin surfaces. The superiority of bond
attained with Polycarboxylate cement on both enamel & dentin, as compared with Zinc
phosphate cement is obvious. It should be pointed out that values for enamel where no
thermal cycling was involved do not represent the true bond strength. It is actually
higher than this figure, since most of the specimens failed is cohesion rather than
adhesion, at the enamel – cement inter face is the strength of the bond to enamel
exceeded the tensile strength of the cement under the axial loading used in this test
when specimens were thermal stressed by cyling between water baths having a 40 0 c
(700 F) temperature differential, the bond strength between the polycarboxylate cement
& tooth structures decreased. However degrading effect was not so great for zinc
phosphate cement when zinc phosphate specimens were subjected to temperature
stressing, the cement invariably separated cleanly from the tooth during cycling
operation. The fact that the strength of bond of polycarboxylate cement to enamel is
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greater than to dentin, is due to theory of calcium bonding, since there is a higher
appetite concentration is enamel than dentin.
pH & Biological Considerations :-
pH of the cement liquid is 1.7. the liquid is rapidly neutralized by powder. Thus the
pH of the mix rises rapidly as the setting reaction proceeds. The pH of a polcarboxylate
cement is higher with that of zinc phosphate cement at various time intervals.
Despite initial acidic pH, they produce minimal, irritation to pulp. Pulp irritation is less
because, polyacrylic acid molecule form large complex with protein which may result in
its decreased diffusion. It is bio compatible with pulp.
Clinical Considerations :-
The working time with these cements is relatively short. Despite adhesion to
tooth structure., it may not be superior with respect to retention of cast sold restorations.
In case of zinc polycarboxylate cement, the failure usually occurs cohesively or at the
cement – metal interface, not adhesively at the cement – tooth interface. The cement is
unable to bond to the metal in the chemically dirty "as cast or pickled" condition.
Thus it is essential that this chemically dirty surface on the cavity side of the
casing be removed inorder to provide a mechanical retention bond at the cement metal
interface. It has been suggested that adhesive bonding might be attained by
electroplating the casting with tin & there by obtain a bond through the reaction of the
carboxyl groups in the cement.
Applications :
Principal uses
1) Denting agent for restoration.
2) Thermal insulating bases.
Secondary uses :-
1) Luting agent for orthodontic bonding
2) Intermediate restorations.
Advantages:
1) Low irritancy.
2) Adhesion to tooth substance & alloys.
3) Easy manipulation.
4) Solubility& film thickness comparable to those of zinc phosphate cement

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Disadvantages :-
1) Need for accurate proportioning required for optimal properties.
2) Lower compressive strength.
3) Need for clean surfaces to utilize adhesion.
P/L 1.5:1.0
Film thickness 22 m
Solubility 0.1 %
Setting times 7 min
Working time 2 min
Strength Avg.(hr) Psi
Comp 24 8900
Tensile 24 700
Adhesive (tensile)
Metal to metal 3 1300
Metal to tooth enamel 3 800
GLASS IONOMER CEMENT:
COMPOSITION:
Powder Liquid
Silica (19.0%) Ployacrylic acid
Alumina (16.6 %) Acrylic acid- itaconic acid
CaF2 (34.3 %) Acrylic acid – maleic acid
Na3AlF6 (5.0%) acid-3-butane 1,2,3 tricarboxylic acid
AlF3 (5.3 %)
AlPP4 (9.9 %)

According to Wilson and Mclean, the Al 2O3/ SiO2 ratio is 1:2 or more and fluoride
content to 23%
These glasses may be opaque containing CaF 2 or Al2O3. Materials for tooth
restorations may use clear rather than opal glasses to provide improved transparency,
but this may result in intrinsically lower strength. Radiopacity can be achieved by
addition of Sr, Ba or La, by fusing Ag to glass.
Two modifications of these basic glasses are of commercial importance. A longer
working time in the cement and decreased water sensitivity of the set cement can be
obtained by depleting the outer 10 – 100 m of powder particles of calcium by treating
with HCl. The powders glass can be blended or fused with metal powders such as
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silver, silver alloy, gold, platinum. The resulting silver fused and ground product, results
in greater wear resistance.
Liquids:
Itanoic acid is added to reduce viscosity of the liquid and inhibits gelation caused
by intermolecular hydrogen bonding.
The introduction of tricarboxylic acid, prevent gelation of liquid and also provides greater
reactivity of increased carboxyl groups.
Setting reactions:
The setting reaction is very complex and regarded as acid-base reaction
between polyacid liquid and the glass in which calcium and Aluminium ions are released
by attack on the surface of particles and ultimate cross link the polyacid chain into a
network. The ion release is facilitated by tartaric acid which readily forms complexes
with these ions and in turn forms a molecular structure with the polyacrylate chains.
Initial setting (gelation) is regarded as result of chain enlargement as well as weak ionic
cross linking which corresponds with the viscoelastic behaviors of freshly set material.
As the cement matures during first 24 hours and beyond, progressive cross linking
occurs (possibly with hydrated Aluminium ions) as the set cement decreases and the
percentage of bond water and glass transition temperature increases. The final set
structure is a complex composite of the original glass particles sheathed by a silaceons
hydragel and bonded by a matrix phase consisting of hydrated fluorinated Ca ++ and
Aluminium polyacrylates.

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Seating and polymer modifiers:

The viscosity, rate of setting and initial/final properties of the cement are
determined as follows.
a. Adjustment of glass composition and powder particle size.
b. Polyacid composition.
c. Molecular wt, distribution and concentration
d. The water content of the cement is important to hydration and completion of
setting reaction.
Various salts affect the setting rate of polycarboxylate cements, but the positive
isomer of tartaric acid is unique in both prolonging "WORKING TIME and increasing
SETTING RATE" about 10% of this form of tartaric acid is added.
Smith suggested need for tougher materials with reduced water sensitivity.
Apparently, less brittle materials can be produced by in-sites polymerization of water –
soluble polymers or by the addition of compatible polymers to glass ionomers cement
composition. In this context , monomers such as HEMA [hydroxy ethyl methacrylate)
were added with chemical interior system or visible light curing system or both, based
on camphor quinone tert-amino methacrylate. Thus, such hybrid materials have a dual
setting mechanism involving acid-base reaction of polyacid with the glass as well as
polymerisation reaction.
Autonncci and Stansbury found that with both polymerizable systems and added
polymer products with higher strengths could be attained. The test specimen showed
brittle type but some plastic deformation was observed.
CLASSIFICATION OF GIC:
Type I: Luting
Use: Cementation of crowns, bridges, inlays, orthodontic appliances.
Setting rate : Fast set.
Powder liquid ratio : 1.5 : 1.0
Radio opaque : Generally
Film thickness : ≤ 20m

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Type II: Restorative:

Type II 1. Restorative aesthetic
Use :
Aesthetic restoration
Setting rate : Fast set
Powder liquid ratio : 3.0 : 1.0
Radio opaque : Most materials
Type II 2. Restorative reinforced
Use :
Were increases physical properties are required but aesthetics not important.
Setting rate : Fast set
Powder liquid ratio : 3.0 : 1.0
Radio opaque : Always
Type III . Lining or Base
Lining:
Use : In thin section as thermal barrier under metal restorations.
Setting rate : Fast set
Powder liquid ratio : 1.5 : 1.0
Base:
Use : In combination with composite in lamination technique
Setting rate : Fast set
Powder liquid ratio : 3.0: 1.0
Radio opaque : Always
Type-I luting cement:
The chemistry of luting cement, consists of finer sized powdered particles, to
ensure achievement of an ultimate film thickness. This involves compromise with
reduced working and setting time and improved physical properties. Flow properties are
such that, placement of restoration to its full extent is relatively easy.
Reasons for use:
a. The tensile strength of both cements is similar (ZnPO 4)
b. The solubility of GIC is significantly lower.
c. The thixotropic flow properties of the glass ionomer cement allow for easier
placement of the prosthesis without the need to retain pressure during setting.
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d. It is easier, therefore to achieve an acceptable ultimate film thickness.

e. The potential for post cementation sensitivity is the same for both cements (ZnPO 4).
f. There is potential for ongoing fluoride release.
 As quoted in JADA, 1993 Nov 124(11) 38-46
 Pulpal sensitivity at 2 weeks after cementation with ZnPO 4 was 34% where as it was
19% with GIC
 After 3 months, there was no significant difference in sensitivity.
 As quaoted in quint. Int-wt 25, 1994 March 51 patients were selected – of that 45
patients returned 1 week after cementation.
 The patients repeated no statically significant difference in sensitivity between crown
cemented with GIC and those with ZnPO4 cement.
 One patient reported sensitivity to the crown cemented with GIC, but the same
patient reported sensitivity to the other crown cemented with ZnPO 4.
 A total of 4 patients reported extreme sensitivity to the crown cemented with GIC,
whereas 3 patients reported extreme sensitivity to the crown cemented with ZnPO 4
cement.
 40 of the crown cemented with GIC were reported not to be sensitive or to be only
mildly sensitive, where as 39 patient cemented crown with ZnPO 4 were reported to
be either not sensitive or only mildly sensitive.

Sensitivity to GIC resulted from:

a) Acidic properties  may irritate pulp.

b) Dehydration of tooth  high flow characteristics of GIC and it is possible that

they could irritate open DT
c) Water solubility during cementation  cement dissolves during setting
d) Hydraulic pressure created in dentin during cementation.
When comparing GIC and ZnPO4 cement with resin cements, the following factors
should be considered.
a) With the resin cements mechanical adhesion with underlying tooth structure may be
available following etching of the dentin.
b) The tensile strength of resin cements is greater than that of 2 other cements.

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c) Pulp compatibility of resin cement is not fully explored.

d) There is no fluoride release with resin cement.
e) The resin cements are essentially insoluble.
Manipulation: P/L ratio is 1.5 : 1
 A cool mixing slab should be employed. The cool slab delays the setting and allow
maximum incorporation of powder.
 The liquid is not dispensed onto the slab until just prior to mixing in order to avoid
loss of water to atmosphere.
 The powder is divided into large 2 or 3 increments, which are introduced one at a
time into liquid with rapid spatulation.
 The recommended total mixing time is 45 secs.
 An increase in powder content, may reduce working time.
 Reduction of powder content by 10% will reduce ultimate physical properties to a
significant degree and may prolong setting time.
 The pH of the newly mixed cement is normally quite low – approximately pH 1.8, but
with standard mix, it will rise to pH 4.5 in first 30 minutes. In the presence of a
reduced powder content, the pH will remain low for a prolonged period, resulting in
possible post-insertion sensitivity.

Control of setting time:

As influenced by manufacturing process
1. Higher the sintering temperature, the more slowly cement sets.
2. The larger the particle size, less rapid is the reaction, because of decreased surface
content of the powder with liquid.
As influenced by dental assistant
1. Lower the temperature during mixing, longer is the setting time.
2. More slowly powder is added, longer is the setting time.
3. Longer the mixing time within the practical limit, longer is the setting time.
4. More liquid employed is the ratio to powder, slower is the setting rate.
Properties of luting cement:
Setting time  6.5 min
Compressive strength  86.2 Mpa (12500 Psi)

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Film thickness  24 m
Solubility and disintegration  1.25 %
Tensile strength  6.2 Mpa (900 Psi)
Pulp response  mild
Applications:
1. Cementation of crown on vital teeth:
In cementation of full crown, it is possible to develop considerable hydraulic
pressure. So it is undesirable to open up DT to any degree at all. Therefore conditioning
of dentin and removing of smear layer is C/I
If preparation of the dentin is desired, then a solution such as CAUSTON'S SOLN
OR 25% TANNIC ACID should be applied for approximately 2 minutes prior to
cementation. Either of these will seal smear layer onto the surface and cover DT.
CAUSTON'S SOLUTION:
CaCl2 0.20
KCl 0.20
MgCl. 6H2O 0.05
NaCl 8.00
NaHCO3 1.00
NaH2PO4.H2O 0.05
Glucose 1.00
An alternative method is to apply new generation of dentine-bonding agents
which contain poly (alkenoic acid) in particular Maleic acid, because there will form
hybrid layer similar to ionic exchange layer formed by GIC.
2. Cementaion of Non-Vital teeth:
Seating restorations: Tooth is highly air blown. The restoration loaded cement,
should be seated immediately. Significant excess cement should flow out (2 mm) of all
margins and the restoration should receive a vigorous F-L motion to allow trapped
cement to escape. The restoration should be handled tightly in place to ensure proper
load. The "collar" of the setting cement should be left in place, until set to a hard state.
Advantages of GIC as luting agents:
1. Cariostatic activity: because of fluoride release
2. Expansion and contraction characteristics: G.I characteristics are close to that of
tooth str.
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3. Strength properties:
GIC  Comp Strength 17000 Psi [ZnPO4 13000Psi]
GIC  Tensile 1300 Psi [ZnPO4 800 Psi]
4. Chemical bonding to tooth structure.
5. High flow characteristics: Allows easy cementation, whereas polycarboxylate
impedes seating of tight fitted posts.
6. Low solubility

Disadvantages:
1. Tooth sensitivity
2. High water solubility during stages of set
3. Lack of radiopacity
4. Adherence to Gingiva

Clinical use of GIC as luting cement:

1. Patients with teeth that are hypersensitive during tooth preparation.
2. Hypersensitive Patients with low pain threshold.
3. In clinical areas with inadequate moisture control.
Indications:
1. Older Patients receiving crowns or prosthesis over teeth that have had life long
carries.
2. Young adults with high caries activity.
3. Patients with fixed prosthesis requiring cariostatic activity.
Pulpal response to ionomer cements biological characteristics :
When G.I.C. were first introduced, the pulpal responses were classified as mild,
moderate & less damaging than with silicate cement. Many centuries ago
PARACELSUS (1493-1541) wrote that all sub can be remedies or poisons depending
on the dosage and mode of applications.
The dentine and pulp must be considered as one organ pulp-dentin complex.
The DT occupy from 20%-39% of dentin and dental fluid represents about 22% of total
volume of dentin. Dental fluid serves as a medium for relaying injurious agents to the
pulp.
Composition of dentin:
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Dentin has an average of 45,000 – 90,000 tubules per mm near the pulp, 30,000-
35,000 in the middle and 10,000 – 25,000 at the periphery. At the pulp surface, the
diameters of the tubules range from 2.5 – 3.0 m. and at the periphery to less than 1.0
m. This tapering is the progressive result of formation of peri tubular or sclerotic dentin.
Each tubule about 1 m in diameter but 2 - 3 m in length, can be regarded as
microscopic ion exchange columns more than 2000 times as long as their diameters.
Generally, dentin directly under the DEJ is only 1% permeable, but permeability
increases to 7.6% halfway to pulp, and up to 22% at the pulp surface. The rate of
permeation of substances their dentin depends on the molecular size of the product, the
surface area available for diffusion, patency of DT and remaining dentin thickness.
Schroff, Swedlow and Stanley, showed that few 10ths of a mm is the over all
average of the remaining dentin thickness greatly influenced the degree of inflammatory
response.
Meryon has shown that 0.5 mm section of dentin reduces the toxicity level of a
materials to 75% and as 1.0 mm thickness over 90% of the control. Generally acids are
considered as pulpal inflammation could be expected only with a large quantity of free
acid, a great dentin permeability and a large contact area.
86% of the total resistance to fluid-flow across dentin into pulp is the result of
smear layer. As the smear layer is exposed to acids, its permeability increases.
unfortunately strong etching not only removes the smear layer, but also reopens the
tubules partially occluded by sclerosis.
When ZnPO4 cement is used as luting agent, it is quite toxic. Dentists are familiar
with temporary hypersensitivity (phosphoric acid sting) that occurs with luting
consistency of ZnPo4.
This is caused by hydraulic forces caused by biting as the crown is seated.
ZnPO4 cement is irritating because of its low pH and the rapid penetration of low-
molecular weight phosphoric acid into DT and pulp. Since dentin can be penetrated by
phosphoric acid to a depth more than 1 mm, especially is luting procedures, insulating
lines are needed in deep cavities.
Moderate pulpal response using ZnPO 4 as a base after 1 day is seen with dentin
thickness of 0.72 mm. There is also lifting of odontoblastic layer and fever number of
inflammatory cells are seen. After 36 days, moderate reaction is seen with congested

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capillaries, a regarded layer and same reparative dentin with a luting mix of ZnPO 4
cement, hydraulic forces push phosphoric acid into DT and pulp and after 4 days a
tremendous number of neutrophil infiltration is seen.
Smith and Ruse, comparing ZnPO4 cement with a Zn polycarboxylate cement
and several G.I, found a general rise in pH for all cements during first 15 minutes.
ZnPO4 and Zn carboxylate showed pH above to 2.0 at 1 minute after mixing. The initial
setting of G.I was slow and pH reached 2.0 at 5 min and 3 at 10 mins.
Surface contaminants:
Before GIC is placed all surface contaminants must be eliminated to permit ionic
exchange of the cement with tooth structure. Excessive acid-etching creates problem
because of removal of smear layer. Deplete the number of ions necessary for adequate
chemical bonding strength.
Smith monitored the progressive surface degradation of GIC with a solution or
gel of 37% phosphoric acid. Extensive surface porosity developed after 10 secs of
etching, enlargements of the voids after 15 secs, surface cracking after 20 secs with
attended matrix dissolution increased porosity and multiple cracks extending deep after
30 secs and total destruction of surface integrity after 60 secs. He recommended
against etching times in excess of 30 secs.
Pretreatment with 50% citric acid causes a greater response in shorter intervals.
5 secs of citric acid etching removes the smear layer by R. Phillips and 38-40%
polyacrylic acid is too harsh. Phillips prefers cement liquid 10% polyacrylic acid (FUGI
GC) however GARLAPO, recommended scrubbing the surface with either 50%
polyacrylic acid for 10 secs or 25 % solution for 30 secs.

Adhesion of G.I.C to Enamel / Dentin:

Theories:
1. Polyacid molecule chelate with Ca+2 at the tooth surface.
CO2 - CO2 - CO2 - Polyacid chain

Ca+2 Ca+2 Tooth surface

Greater bond strength achieved with enamel than dentine suggested that Ca +2 of
tooth substance which is involved in bond formation.
2. Outer layer of apatite on tooth surface become solubilized in the presence of
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acid. as more apatite dissolves and as the cement begins to set, the pH begins to
rise. This may cause repption of a complex mixture of calcium phosphate (from the
apatite) and the calcium salts of the polyacid onto the tooth surface. Thus the
polyacid chains would be bound to a repelled layer on the outer surface.
In case of dentin there may also be some bonding between carboxylic acid groups of
the cement and reactive groups within colleagues either by hydrogen bonding or by
metallic ion bridging.
Another attempt to improve bond strength to dentine involved artificially
increasing the mineral content of the dentine surface by applying solution from which
CaPO4 or CaSO4 could crystallize to give a surface layer which is potentially more
reactive towards polyacids.

Improved adhesion of G.I to Enamel/ Dentin:

Adhesion has been attributed to ionic forces operating across the interface. More
recently, Wilson etal have shown that polyanions from the cement actually penetrate the
apatite str. With carboxylate groups displacing phosphate groups from apetite matrix.
These mechanism can only operate effectively if intimate intermoleculear contact is
achieved between the adhesive cement and tooth substrate; such interfacial contact is
the first requirement for adhesion. Thus adhesive is required to spread over the
substrate surface displacing contaminants. For this reason effective conditioning is
required. Polyacrylic acid, tannic acid are used. These high molecular weight
substances contain a multiplicity of functional groups. Phenolic hydroxyls in tannic acid
and carboxylic acid groups is polyacrylic acid and hydroxyls and amino acids in dodicin.
These functional groups have the ability to form a multplicity of hydrogen bonds
to enamel surfaces – bonds which promote wetting, cleaning. They also have the
potential to react chemically with dentin collagen.
Tannic acid – a vegetable tanning agent is known to combine with leather
collagen by hydrogen bridging to peptide bonds and it assumed that polyacrylic acid
and dodicin would similarly bond to collapse. None of these reagents disturbed the
smear layer, which is rich in Ca +2 and phosphate and it may well be that this smear layer
is important in assisting adhesion to dentin FeCl 2 which also tans leather, was also quite
effective for treatment of dentin. Here ferric ions will serve to form bridges between
dentin collagen and cement.
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Biocompatibility of GIC to pulp:

GIC is less irritant to pulp because of 2 reasons.
a) Acids used are weaker than phosphoric acid.
b) Polyacids chains are large and form large protein complex, that does not pass
through dentinal tubules.
Their mobility is further decreases by their affinity for Ca +2 in the tooth.
The thermal diffisivity of GIC is similar to that of dentine – hence exhibits thermal
insulating property.
Coefficient of thermal expression GIC  13-16 ppm0C-1
Coefficient of thermal expression of tooth str  8-11 ppm0C-1
Miscellaneous property:
GIC has poor abrasion resistance, which causes change in anatomic form, but
also considerable surface roughening.
GIC is also susceptible to acid errosion factors which affect rate of errosion
include the pH of erroding medium (saliva, fruit drinks, plaque) and the maturity of the
cement at the time it contacts the acid. To reduce the risk of acid errosion, cements are
protected with varnish.

INSTRUCTION FOR DENTAL ASSISTANT:

1. Storage of cement in bottles:
P/L should never be used interchanged because the GIC are water based, they will
always be subjected to further loss or uptake of water. Therefore both powder and liquid
bottles should remain firmly closed at all times.
The liquids should never be stored in the refrigerator, but storage of the powder and
the mixing slab in the refrigerator will marginally lengthen working time.
2. Hand dispensing of P/L:
Powder be fluffed up in the bottle first and level spoonful extracted dispensed
onto the slab.
Make sure that the spoon is full and that there is no excess powder on the back
of the spoon or along the handle.
Scrape the top of the spoon over the lip on the bottle.
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Dispensing of liquid is as follows [polyacrylic acid]

Tip the bottle onto its side first and allow the liquid to run into the spout. If the
liquid is provided in a translucent bottle, this can be readily observed. If the bottle is
opaque, experienced will dictate length of time required. Invert completely before
dispensing a drop.
If liquid is water or dilute tartaric acid.
Apply gentle pressure to the rubbee cuff at the neck of the bottle, since a
vigorous squeeze may produce a squirt rather than a drop.
3. Mixing by Hand:
Do not spread the mix around the slab and do not spatulate heavily. The object is to wet
the surface of each particle of glass powder to develop the matrix-not to dissolve the
entire particles in the liquid.
Divide the powder into 2 parts. Fold in the first half within 10-15 secs, Then add
the second half and incorporate it entirely within the next 15 secs. Keep the mixing to a
small area of the slab only and do not spatulate once the powder is incorporated.
4. Mixing of capsules:
a. If the capsule is activated in a press, apply adequate pressure and maintain the
pressure for 3-4 secs before releasing and placing the capsule in the machine for
mixing.
b. If the capsule is activated by rotating one half against the other, use adequate
force to collapse it totally.
c. Use an ultra-high speed mixing machine, that is, one capable of at least 4000
cycles/min
d. The time for mixing recommended is 10 Secs. Extension beyond 15 Secs will
reduce working time. reduction of mixing time to 7 Secs may extend working time
to about 2.5 minutes, but there is risk of having un-reacted liquid still present.
e. Immediately capsule is removed from the machine.

CORRECT CONSISTENCY FOR HAND MIXING CEMENTS

a. Type I : Luting cements:
P/L ratio 1.5:1 and will therefore string up app 3-4 cm from the slab.
b. Type II 1: Restorative aesthetics:

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Both dual and auto cure cements will string 1 cm off from the slab, but must
retain a "glossy surface"
c. Type II 2: Restorative reinforced: cement will string 1 cm off the slab
d. Type III : Lining cements: For lining amalgam:
P/L ratio 1.5 : 1 for both dual and auto cure cements and cement will string up 3-
4 cm off the slab.
For basing out composite resins: P/L ratio 3:1
If hand mixed, it will string 1-2 cm. Working time will be short for auto cure,
but for dual cure, it will be 3.25 min.

ANALYSIS/DISCUSSION:

1. Zinc phosphate Vs resin cement for crown cementation

Zinc phosphate Resin
Advantages: Low cost Bonds to tooth
Long clinical history Fast softening time
High rigidity Higher strength
Long working time Easy to use
Easy to use

Disadvantages: No bond to tooth High cost

Slow setting time Short working time
Moisture sensitive Difficult to remove excess
During mixings

2. GIC Vs Zinc phosphate.

GIC Zinc phosphate
Advantages: Good seal Good seal
Fluoride release Reasonable cost
Adequate strength Adequate strength
Reasonable cost Little sensitivity
Disadvantages: Occasional sensitivity No fluoride release.

42
Comparison of popular dental cements:

Glass Polycarboxylate Resin Zinc Zinc

ionomer oxide phosphate
eugenol
Compressive Good Good Excellent Good Good
strength
Tensile Poor Poor Fair Poor Poor
strength
Modulus of Good Good Excellent Fair Good
elasticity
Film thickness Good Good Poor Good Good
Solubility Very low Low None Moderate Low
Flow Excellent Good Fair Good Good
Pulp reaction None None Extreme None Moderate
Setting time Fast Moderate Variable Moderate Slow
Ease of use Fair Good Good Fair Good
Colour Fair Fair Excellent Poor Good
(matches
tooth)
Current Moderate Moderate Low but Very low Moderate
clinical use increasing
Main Cariostatic, Low pulp Matches Can be Historical
advantages high flow reaction tooth used in perceptive,
colour moist positive
field
Main Occasionally Thixotropic Pulp Solubility Pulp
disadvantages tooth irritation irritation,
sensitive slow setting
time.
 Comparison of popular dental cements:

Film Setting Strength (MPa) Modulus of

Solubility
Materials thickness time elasticity
(wt. %)
(mm) (mins) (GPA)
Tensil
Compressive
e
Zinc Phosphate 25 – 35 5 – 14 0.2 80 – 110 5–7 13
Zinc Silico
30 – 40 5–7 1.0 140 -170 8 – 13 -
Phosphate
Zinc oxide
eugenol
Unmodified 25 – 35 2 – 10 1.5 2 – 25 1–2 -
Polymer 35 – 45 7–9 1.0 35 – 55 5–8 2-3
reinforced 40 – 60 7 – 30 1.0 55 – 70 3–6 3–6
EBA alumina
Zinc
20 -2 5 6–9 0.06 55 – 85 8 – 12 5–6
Polycarboxylate
GIC 20 – 35 6–9 1.0 90 - 140 6-7 7-8

Polymer based 20 -60 3–7 0.05 70 – 100 25 – 40 4–6

 45

Properties of commonly used luting cements:

45
 46

Type Brand Form Compressiv Tensile Film Solubility

e strength Strengt thickne In water
(Mpa) h (Mpa) ss (%)
All-Bond C&B Paste/ 220 43.4 25 -
luting composite paste
(Bisco)
Biomer Paste/ 186.2 - 10 -0.09
(dentspy/Caulk) paste
C&B Metabond Paste/ 60.1 - - -
Composite
(parkell Sun liquid
resin (auto
Medical
polymerizing
Comspan Paste/ 275.9 30.9 20 0.13
)
(Dentply/Caulk) paste 314.1 46.9
Panavia Paste/ 178.5 45.1 19 1.4
(kuraray) liquid 255 37.2
266.9
Thin film cement Paste/ 117.5 29.4 41.7 -
(Den Mat) paste
Dicor LAC Paste/ 137.7 24 10-20 0.15-0.25
(Dentsply/York) paste 251.7 34.5
Dicor LAV with Paste/ 180 45-48 - -
fluoride paste
Composite (Dentsply/York)
resin Enforce with Paste/ 274.5 42.7 <25 0.08
(dual cure) fluoride paste 293.0 51.0
(Dentsply/Caulk
)
Infinity Paste/ 140.7 23.1 20 -
(Den Mat) paste
Glass Fuji I Paste/ 225 13.6 16 0.06
ionomer (GC America liquid 175
186
Glasionomer Paste/ 122 - <25 0.30
Type I liquid 196
(Shofu)

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 47

Ketac Cem Paste/ 162.1 17.8 9.5 -

(ESPE-Premier) liquid
Ketac Cem Paste/ 124 12.6 20 0.1
capsule liquid 96.8
(ESPE-Premier)

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 48

Type Brand Form Compressiv Tensile Film Solubilit

e strength Strengt thickne y
(Mpa) h (Mpa) ss In water
(%)
Advance Powder 151.7 34.5 20 0-0.07

Hybrid (Dentsply/Caulk /liquid

(Glass )
Fuji Duet Powder 155 24 10 0.07
ionomer +
(GC America) /liquid
resin) Vitremer luting Powder 132.6 23.3 19 0
cement (3M) /liquid
Carboxylon (3 Powder 56 6.0 - -
M) /liquid
Durelon Powder 50.73 10 13 0.1
(ESPE-Premier) /liquid 70 8.1 21
53.3 12.6

Polycarboxyla 65 15.1

te 67.4
Liv Carbo Powder 79.3 - 13 0.01-0.03
(GC America) /liquid
Shofu Powder 55.0 10.8 19 0.04
polycarboxylate /liquid 69.4
Tylok-Plus Powder >69 >6.9 19 -
/liquid
Zinc Fleck's Zinc Powder 117 8.1 10-20 <0.2
phosphate Cement /liquid 56.5
(National 62.1
Keystone
Products/
Mizzy)
Lee Smith Zinc Powder 96.55 – 9.3 25 <0.2
(Teledyne) /liquid 110.3

Modern Tenacin Powder 77.5 4.4 - -

(Caulk) /liquid 89.0

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 49

De Trey Zinc Powder 89150 9.5 - -

Cement /liquid 117 4.3
Improved (De
Trey)
Shofu Zinc Powder 117 - <25 0.05
Phospahate /liquid

49
REFERENCES:
1. Science of dental materials – By Phillip’s 9th edition.
2. Dental materials and their selection–By William J.O.Brein. 2 nd Edition
3. Applied dental materials - By Mccabe and Walls. 2 nd Edition.
4. Notes on dental materials – By E.C.Combe. 3 rd Edition.
5. Notes on Dental Materials – By V. K. Subbarao.
6. Restorative dental materials – By Robert. G. Craig. 3 rd Edition.
7. Introduction to dental materials – By Richard Van Noort. 3 rd Edition.
8. Materials in dentistry – By Jack. L. Ferriacane.
9. Clinical aspects of dental materials – By Marcia Gladwin.
10. Preservation and restoration of tooth structure– By Graham. J. Mount.
11. Rosenstiel SF, Land MF,Fugimoto:Contemporary fixed
Prosthodontics, 3rd edition,St louis, 2001 Mosby.
12. Shillinburg HT, Hobo S, WhitSett LD, Jacobi R, Brackett SE:
Fundamentals of fixed Prosthodontics, 3rd edition, Illinios
Quintessence.
13. WFP Malone, DL Koth, E Cavazos Jr, Da Kaiser, SM Morgano:
Tylman’s Thoery and practice of fixed Prosthodontics, 8 th edition.
Ishiyaku EuroAmerica, inc. publishers. Tokyo. St Louis.
14. Mitchem, J, C and Gronas D.G, continued evaluation of cement
solubility of luting cements, J. Prosthet. Dent 45:289-291, 1981.
15. White SN, Yu Z: Compressive and diametral tensile strengths of current adhesive
luting agents.- By J. Prosthet Dent 1993; 69:568-572.
16. White SN, Yu Z: Kipnis V: Effect of seating force on film thickness of new
adhesive luting agents.- By J. Prosthet Dent 1992; 68:476-481.
17. Smith DC: Dental Cements. Dent Clin North Am 1971; 15: 3-31.
18. Tyas MJ: Clinical studies related to glass ionomers. Oper Dent 1992: 17: 191-
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