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Year: 2012

Adhesion concepts in dentistry: tooth and material aspects

Özcan, Mutlu ; Dündar, Mine ; Erhan Çömlekoğlu, M

Abstract: Adhesion concepts require understanding of substrate material properties, surface conditioning
methods and chemical interactions, formation of interfaces/interphases between different material com-
binations, changes at interfaces with time, failure mechanisms and failure modes of the interfaces as a
consequence of aging phenomenon. In dentistry, different methods are being used to test adhesion of
resin-based materials to various biological and artificial substrates that require individual conditioning
protocols. Variations among specimen configurations, material properties and chemical compositions of
adhesives, test methods and test conditions all have effect on adhesion of similar or dissimilar substrates.
Selection of the test, its proper execution, as well as the interpretation of the data through chemistry
of the materials involved is of importance. Although adhesion to enamel is not a major concern today,
effective adhesion to dentin requires several steps where failure in any of these consecutive events might
result in failure of the whole system after long-term clinical use. Test methodologies used for assessment
of mechanical behavior of materials in engineering may not directly apply to tooth–material combina-
tions in dentistry. The objective of this review on adhesion in dentistry is to summarize current materials
and methods used in dental materials testing and to summarize the current state-of-the-art in adhesion
durability and quality with respect to the material type.

DOI: https://doi.org/10.1080/01694243.2012.691038

Posted at the Zurich Open Repository and Archive, University of Zurich

ZORA URL: https://doi.org/10.5167/uzh-75611
Journal Article
Accepted Version

Originally published at:

Özcan, Mutlu; Dündar, Mine; Erhan Çömlekoğlu, M (2012). Adhesion concepts in dentistry: tooth and
material aspects. Journal of Adhesion Science and Technology, 26(24):2661-2681.
DOI: https://doi.org/10.1080/01694243.2012.691038
 Adhesion Concepts in Dentistry: Tooth and Material Aspects

Mutlu Özcan,1,* Mine Dündar,2 and M. Erhan Çömlekoğlu2

1
University of Zurich, Dental Materials Unit, Center for Dental and Oral Medicine,

Clinic for Fixed and Removable Prosthodontics and Dental Materials Science, Zürich,

Switzerland.
2
Ege University, Dental School, Department of Prosthodontics, 35100 Bornova,

Izmir, Turkey.

Running Heads: Review on Adhesion in Dentistry

Corresponding author:
Prof. Mutlu Özcan, Dr.med.dent., Ph.D
University of Zürich
Dental Materials Unit
Center for Dental and Oral Medicine
Clinic for Fixed and Removable Prosthodontics and Dental Materials Science
Plattenstrasse 11
CH-8032 Zürich, Switzerland
Tel: +41 44 634 5600; Fax: +41 44 634 4305
e-mail: [email protected]

1
Abstract

Adhesion concepts require understanding of substrate material properties, surface

conditioning methods and chemical interactions, formation of interfaces/interphases

between different material combinations, changes at interfaces with time, failure

mechanisms and failure modes of the interfaces as a consequence of aging

phenomenon. In dentistry, different methods are being used to test adhesion of resin

based materials to various biological and artificial substrates that require individual

conditioning protocols. Variations among specimen configurations, material

properties and chemical compositions of adhesives, test methods and test conditions

all have effect on adhesion of similar or dissimilar substrates. Selection of the test, its

proper execution, as well as the interpretation of the data through chemistry of the

materials involved is of importance. Although adhesion to enamel is not a major

concern today, effective adhesion to dentin requires several steps where failure in

any of these consecutive events might result in failure of the whole system after long

term clinical use. Test methodologies used for assessment of mechanical behaviour

of materials in engineering may not directly apply to tooth-material combinations in

dentistry. The objective of this review on adhesion in dentistry is to summarize

current materials and methods used in dental materials testing and to summarize the

current state-of-the-art in adhesion durability and quality with respect to the material

type.

Keywords

Adhesion, adhesives, biodegradation, bond strength testing, ceramics, composites,

metals, minimal invasive dentistry

2
1. Introduction

Adhesion constitutes the attraction between similar or dissimilar materials by several

mechanical and physical processes and intermolecular forces. The adhesive

interface comprises an “adhesive” that is placed on a “substrate (adherend)”. When

an adhesive is used to attach one substrate to the other, two interfaces are formed

between the adhesive and the substrates [1]. Without any adhesion promoter,

although physical as well as chemical adhesion is present in all dental material

applications, the resultant bond strength is weak or negligible when compared to

mechanical bonding. Mechanical interlocking of the adhesive into the substrate

irregularities contributes the most to the bond strength at the interface in almost all

situations [2,3].

In most of the dental applications, two different substrates are bonded with an

adhesive. The adhesive has to seal the interface between the cavity and the

restorative material, thus reducing the risk of leakage, post-operative sensitivity,

marginal staining and recurrent caries [4]. Adhesion in dentistry has two aspects,

namely the adhesion to tooth and the restorative material where the quality of

adhesion varies depending on the tooth and material properties. Therefore the aim of

this article is to review the current information concerning these aspects. From the

dental perspective, there are numerous substrates such as enamel, dentin, cement,

post-core, remaining dental amalgam on tooth or a dental implant abutment, dental

composite resin, cast or all-ceramic inlay/onlay/crown, veneer, resin-bonded fixed

dental prosthesis or an orthodontic bracket.

1.1. Developments in the Field of Adhesion in Dentistry

Some fifty years ago, clinicians had to drill extensively not only the infected but also

the healthy tissues to obtain mechanical retention for the restorative materials [5].

3
One of the leading innovations of recent times is the discovery of enamel and dentin

etching with phosphoric acid that was first introduced by Buonocore [6]. With this

phenomenal discovery, it has become possible to adhere synthetic resins to the tooth

tissues. The rationale behind this requirement is that the loss of tooth substance by

caries or trauma cannot be repaired by living materials and, therefore, should be

restored by synthetic materials.

From the restorative materials perspective, the popularity of chemically cured

dental methacrylates diminished during the mid-1950s due to their poor physical

properties and negative effects on pulp tissue that stem from polymerization

shrinkage and monomer leaching [7]. Polymerization here, refers to the cross-linking

of monomers to form long chain polymers to improve material strength where

contraction stresses cannot be avoided. Bowen improved the mechanical and

adhesive properties of resinous restorative materials using epoxy resin (diglycidyl

ether of bisphenol A) mixed with silica particles [8]. However, the resin was initially

not ideal as the presence of moisture compromised the polymerization process of the

epoxy resin. Bowen converted epoxy resin to a dimethacrylate by linking methyl

methacrylate groups to the epoxy resin [9]. A mixture of silicon dioxide, boron oxide,

aluminum oxide, or strontium oxide particles was used in this formulation. The

resultant resin was called 2,2 - bis-[4-(methacryloxypropoxy)-phenyl]propane (bis-

GMA), or “Bowen’s resin” [7]. This resin matrix is usually cured by photoinitiated free

radical polymerization. bis-GMA is one of the most commonly used monomers. Since

bis-GMA resin is highly viscous, a low viscosity monomer, such as tri(ethylene

glycol)dimethacrylate (TEGDMA), is usually added to the resin. Today, the bis-

GMA/TEGDMA system is one of the most widely used dental resin systems. The

function of bis-GMA is to limit the volumetric shrinkage induced by

4
photopolymerization and to enhance resin reactivity, while TEGDMA provides for

increased degree of conversion [10]. During the synthesis of bis-GMA monomer, iso-

bis-GMA monomer is produced as a by-product.

The combination of bis-GMA based resins with the acid-etching technique led to

new perspectives in dentistry. Adhesion concept shifted from macro-mechanical to

micro-mechanical and surface chemistry approaches and this provided new

treatment possibilities in orthodontics and minimally invasive interventions.

1.2. Minimally Invasive Dentistry

Operative treatment concepts can be based on non-invasive, minimally invasive or

invasive strategies using various materials. Dentistry utilizes a variety of materials

ranging from polymers, metals and metal alloys to resin based composites and

ceramics for restorative procedures. Developments in polymer and ceramic fields

have largely eliminated the use of metals and thus have reduced the possible

corrosion products in the mouth.

Since polymeric, ceramic or metallic materials present different material properties

and preparation techniques for their application that may vary from non-invasive to

minimal, moderate or more invasive treatment options, from the ethical point of view

it is almost impossible to conduct clinical trials to compare different treatment

modalities or materials in the same mouth. Despite all the recent developments, no

material to date is flawless. Survival rates of restorative materials inevitably decrease

over years.

Adhesion to enamel and dentin is not a clinical concern anymore after the

discovery of acid etching and adhesives. Dental composite resin materials are cost-

effective and less invasive compared to other available materials and their direct

intraoral applications are routine. Current problems for direct composite resin

5
applications are rather related to the hydrolytic instability of adhesives and shrinkage-

related problems after composite resin polymerization and its consequences such as

internal cracks in the composite, shear forces directed to cusps thus causing possible

cusp fractures, microleakage through the margins of the composite restorations,

which can cause caries and pain. The dilemma in the dental profession is the choice

between the polymeric materials versus dental ceramics (feldspathic, glass and oxide

ceramics) in minimally invasive applications. If ceramic materials are to be chosen

over resin composites, evidence-based studies should be evaluated with caution

[11,12]. In a clinical study conducted at a university, 28% of glass-ceramic laminate

veneer restorations (0.5-0.8 mm in thickness), a minimally invasive treatment

modality, needed repair after 10 years, indicating that refinishing, repolishing or

repair of chipping and fracture using composites was necessary. On the other hand,

practice-based evidence reported that 53% of glass-ceramic laminates survived

without re-intervention for 10 years. These two studies clearly emphasize the need

for optimization of the materials and the application techniques.

1.3. Classification of Dental Adhesive Systems

In order to achieve a stable bonded interface to dental tissues, adhesive systems

have to include three crucial application steps, i.e. etching, priming and bonding.

Etching with an acidic solution, such as 35-37% orthophosphoric acid, demineralizes

both enamel and dentin surfaces producing roughness and increasing their surface

free energy [4]. With priming, wettability of the tooth surface is increased and

hydrophilic monomers and solvents in the primer composition provide substitution of

the water on the substrate with the resin monomers. In the bonding step, after

penetration and polymerization of monomers into the etched enamel surface or

exposed collagen network in dentin, micromechanical interlocking occurs [4]. Even

6
though all adhesives possess etching, priming and bonding abilities, their

compositions, contemporary adhesive systems are named as: etch-and-rinse, self-

etch, and self-adhesive, based on the number and combination of the steps used in

the system [13,14]. Self-etching refers to the acid etching and priming of dentin at the

same time with acidic monomers without rinsing resulting in a modified smear layer to

form the hybrid layer between the dentin and resin, whereas etch-and-rinse approach

refers to acid etching of the enamel/dentin surfaces and after this treatment the

surfaces are rinsed in order to eliminate the smear layer and then primer, bond and

resin application to form the hybrid layer [11].

The etch-and-rinse approach can be further divided into two subgroups of 3-

component and 2-component systems. While the former one is characterized by the

sequential and separate application of etching, primer and bonding agent, in the

simplified 2-step approach, the primer and bonding agent present in a single bottle

are applied on the tooth surface immediately after removal of etching material

[15,16].

The major complication for the etch-and-rinse systems is the potential

incomplete penetration of resins into exposed collagen mesh [16-19]. In order to

overcome this problem self-etch adhesives have been improved. With the self-etch

adhesives, acidic monomers (self-etching primer) that simultaneously demineralize

and prime tooth surfaces are applied and dried on the tooth surface. Then, a bonding

agent from a separate bottle is used. These systems can also be further divided into

subgroups based on their self-etching capacity; strong (pH < 1), intermediately strong

(pH ≈ 1.5), mild (pH ≈ 2), and ultra-mild (pH ≥ 2.5). The arbitrary pH scale depends

on the substrate to be treated. When working on enamel surface, intermediately

strong to mild and for dentin surfaces mild to ultra-mild acids are used. Bonding

7
agent is a flowable, less inorganic content bearing resin that is applied as an

intermediate layer before composite resin application [13].

Taking the self-etch approach one step further, one-component, so-called

‘self-adhesive’ systems have been developed. With this technique, acidic monomers

(esters generating from the reaction of a bivalent alcohol with methacrylic acid and

phosphoric/carboxylic acid derivatives) that etch, prime, and bond simultaneously are

applied on the tooth surface as a single solution. These monomers possess

functional acidic groups to demineralize hard tissues and copolymerize with bonding

resins sequentially [16-19]. Self-etch adhesives contain specific functional monomers

which determine their adhesive performance.

2. Adhesion to Dental Tissues

For better understanding of surface reactions of the current bonding systems with

dental hard tissues, a brief discussion regarding tooth substrates would be helpful.

While a tooth can be divided macroscopically into 2 fragments i.e., as a crown and a

root, its structural composition consists of three hard tissues: enamel, dentin and

cementum. Enamel that covers the crown is completely acellular and it is the most

mineralized hard tissue in the body. The other outer part of the tooth is cementum by

which the root is totally covered. The third hard tissue, dentin, underlies the enamel

and cementum layers and forms the bulk of the tooth [20,22].

2.1 Adhesion to Enamel

Compositionally, enamel consists of 96% inorganic hydroxyapatite crystallites

[Ca10(PO4)6(OH)2] by weight, the rest of the matrix being water (4%) and proteins

(collagens) (1%) [22]. Structural form of enamel is characterized by a higher order

structure that consists of rods that are organized in a repetitive pattern [23].

8
 While micromechanical retention of resin tags on roughened surfaces is still

the best bonding mechanism on enamel [4,6], chemical bonding to hydroxyapatite

can also be accomplished through chelation reaction with the calcium ions or with the

phosphate or the hydroxyl groups [24]. For the micromechanical adhesion,

demineralization of the surface enamel layer is required and the multi-step etch-and-

rinse approach with highly concentrated phosphoric acid (35-37% by weight, pH=1.0)

is regarded as ‘gold standard’ for this purpose. Acid etching of enamel selectively

dissolves enamel rods and provides micro-roughness on the surface with increased

surface energy that is essential for micromechanical adhesion [25]. Several etching

agents such as maleic, citric, phosphoric, and nitric acid with different concentrations

have also been tried on enamel. However, phosphoric acid is apparently preferred

due to its known advantage in efficiently etching enamel to an operator identifiable

frosty appearance known for good adhesion to enamel [26]. When the surface

topography is created on the surface, the monomers in primers and bonding agents

can penetrate into the porous substructure to form extensions (tags) at the enamel-

restoration interface, become polymerized and with the application of subsequent

resin layers micromechanical interlocking which provides most of the bond strength is

provided. The in vitro shear bond strength of composite and luting resins to etched

enamel has been reported to vary from 17.7 to 49.2 MPa depending on the test

method and aging (thermocycling) conditions used, corresponding approximately to 5

years clinical service. The results revealed mostly interfacial failure between the

composite and/or luting resins and etched enamel [27-30].

With the self-etching technique, an acidic monomer is used to demineralize

enamel surfaces. Self-etching primers with lower pH values can etch enamel surface

more aggressively. On the other hand, milder systems can provide a better etching

9
pattern [31]. Both on intact and ground enamel, higher bond strength values can be

achieved with etch-and-rinse systems compared to self-etching systems [32-34].

Besides micromechanical bonding, chemical interaction between resin and

enamel apatite can occur through the treatment of enamel by polyalkenoic acids.

This occurs through ionic bond formation between the carboxyl groups of the

polyalkenoic acid with calcium of hydroxyapatite [34]. Thus, the chelation of carboxyl

groups that are derived from polyalkenoic acid with the calcium in apatite can be

obtained as represented below:

Polyalkenoic acid R-COO-H3O+ + Hydroxyapatite (OH-) àCa+2 +PO43-

The use of polyalkenoic acids clean and roughen the enamel surface but the long-

term durability of the achieved bond strength is still not ideal [34,35].

2.2 Adhesion to Dentin

Dentin is a tissue with physical and chemical properties that resemble that of bone. It

is 70% mineralized with hydroxyapatite crystals and its organic phase, about 20% by

weight, is mostly collagen while the remaining 10% is water. The water in dentin is

trapped in the collagen fibers during dentin formation and this is bonded to

hydroxypyroline ends inside the collagen fibers [35-37]. Morphologically, dentin

contains dentinal tubules, formed by the deposition and mineralization of a predentin

matrix. The permeability of this tissue is a direct consequence of the presence of

tubules [38]. Between the tubules the intertubular dentin is composed of a dense

matrix of collagen fibrils, ranging from 50 to 200 nm in diameter, surrounded by

hydroxyapatite mineral and the more mineralized peritubular dentin immediately

adjacent to the tubules contains less collagen. Type I collagen, the most abundant

collagen of the human body, accounts for 90% of the total protein in the organic

matrix of bone and dentin [38].

10
 It has been demonstrated that the nucleated apatite crystals grow mineral

platelets that are highly organized within the collagen fibrils [39]. Type I collagen

matrix does not have the capacity to induce matrix-specific mineral formation.

Ordered mineralization of apatite on collagen fibrils has been shown to require

additives such as phosphoproteins, glycoseaminoglycans and proteoglycans.

Therefore, the non-collagenous proteins (NCPs) that are tightly bound to the collagen

fibrils in mineralized tissues are important for understanding the mechanism of

hybridization and mineralization. Bone and/or dentin-specific NCPs are mostly acidic

in nature and are rich in glutamic acid, aspartic acid, and phosphoserines. They

possess high calcium binding capacity and hydroxyapatite affinity. In vitro

mineralization analyses suggest that these NCPs can greatly influence the apatite

deposition rate and morphology of crystals, thus they can be considered as

nucleators or inhibitors of mineralization [40].

Bonding of 4-methacryloxyethyl trimellitate anhydride together with tri-n-butyl

borane in the presence of poly(methyl methacrylate) (4-META / PMMA TBB resin) to

dentin via hybridization of impregnated monomers was first described by

Nakabayashi et al, in 1982 [41]. The mechanism of bonding by hybridization applies

to almost all bonding systems. Etching dentin removes the smear layer and the

hydroxyapatite mineral phase from the tissue surface, creating a network of exposed

collagen fibrils as the underlying substrate. The hybridization process is achieved by

the infiltration of the primer into the open spatial network in the collagen matrix

exposed by dentin demineralization, and its polymerization. Hybrid layer formation on

the surface and within the subsurface of dentin depends on both the permeability of

dentin and the diffusion of applied monomers [15,41]. Due to the hydrophilic nature of

the matrix, Nakabayashi et al. [41] proposed that a methacrylate with both hydrophilic

11
and hydrophobic groups could improve the diffusion of a monomer mixture and

enhance its impregnation into appropriately conditioned dentin substrates. The

hydrophilic groups may facilitate permeation of the monomer into the collagen matrix

leading to the formation of a collagen-resin hybridized layer. This procedure

significantly improved bonding and sealing at the resin-dentin interface [42,43]. The

bond strength of composites and luting resins to dentin varies over a wide range

depending on the adhesive system used, type of materials bonded and test

methodologies. However, due to the ultrastructure at micro and/or nanolevel and

collagen-rich composition of the dentin tissue, bond strength to dentin is lower than

that to enamel.

As the structure of bulk and surface dentin are different, the resin-dentin

bonding mechanism changes. While the dentin surface is dominated by intertubular

dentin, the bulk dentin is dominated by dentin tubules. Therefore, the bonding

mechanism depends on dentin tubules in bulk dentin and on intertubuler dentin in

dentin surface [44-47].

It has been observed that leaving the conditioned dentin slightly moist by mild

air drying the dentin surface during bonding improved the bond strength, and this

procedure became identified as ‘wet bonding’ to dentin [48]. Drying of dentin exposed

after acid demineralization may lead to a volume change, which is described as the

structural collapse of the collagen matrix that results in incomplete penetration of

monomers into the matrix. The prevention of collapse is made possible by

maintaining conditioned dentin in the wet state [49,50]. In wet bonding, the monomer

replaces the water within the exposed collagen scaffold. Thus hydrogen bonding, van

der Waals, and electrostatic interactions between the monomer and the collagen

molecules (proteoglycans, glycosaminoglycans and phosphoproteins) may be

12
facilitated. Therefore, both monomer and solvent molecules should be compatible

with the moist environment of the collagen matrix. Hydrophilic resin monomers are

often dissolved in volatile solvents, such as acetone and ethanol. The inclusion

of these volatile solvents helps in the displacement of water from the dentine

surface, easing penetration of the resin monomers into the microporosities of the

exposed, acid-demineralized collagen network [51]. In order to form an effective

hybrid layer, hydrophilic monomers carried in water, ethanol, or acetone, are used as

primers [25]. Following primer/bonding agent application, carrier solvent is

evaporated by slight air drying, leaving the resin material within the collagen mesh.

The bonding agent co-polymerizes with the primer, a base material for wetting the

dentin surface and easing further penetration of the monomers. Some commonly

used comonomer blends resin restorative composites or in resin based luting agents

are: bis-GMA: bisphenol A diglycidyl ether dimethacrylate; bis-GMA-E: ethoxylated

bisphenol A diglycidyl ether dimethacrylate; CQ: camphorquinone; EDMAB: ethyl

N,N-dimethyl-4-aminobenzoate; HEMA: 2-hydroxylethyl methacrylate; DMABA:

dimethylaminobenzoic acid; TEGDMA: triethyleneglycol dimethacrylate; TCDM:

di(hydroxyethylmethacrylate) ester of 5-(2,5-dioxo tetrahydrofurfuryl)-3-methyl-3-

cyclohexene-1,2-dicarboxylic anhydride [52]. Ideally, all solvents and water should

be completely eliminated from the adhesive before light-curing of the resin, as they

may have an adverse effect on polymerization of the adhesive resin monomers. This

is achieved by allowing an evaporation time between application and curing of the

adhesive resin. However, the monomer to water ratio increases as water evaporates

from the adhesive and lowers the vapour pressure of water, reducing the ability of

water and solvents to evaporate from the adhesive. It is likely that residual water and

solvent will be trapped within the adhesive resin upon curing and this may

13
compromise the overall bonding and the mechanical properties of the cured resin

[53].

Acidic etchants remove the mineral phase of the dentin layer depending on the

individual dentin quality, quantity and applied pH, but the collagen component is not

totally dissolved by phosphoric or citric acids [54]. Resin diffusion into and within the

demineralized intertubular dentin matrices occurs via 20-30 nm wide interfibrillar

spaces. These narrow interconnecting channels contain noncollagenous

macromolecules such as proteoglycans, proteins, and glycosaminoglycans that

remain within the matrix and decrease monomer permeability after acid conditioning

of the dentin [54,55]. Therefore, to avoid collagen collapse and maintain large

interfibrillar spaces permitting monomer diffusion within the exposed collagen mesh,

etch-and-rinse systems should be applied on wet dentin [48].

First adhesive approach for dentin bonding was etch-and-rinse technique.

Thereafter, self-etch and self-adhesive systems became widespread. Regardless of

the number of steps involved, the complete diffusion and interaction of the hydrophilic

monomer within the porous tissue substrate to form a hybrid layer at the tissue-resin

interface was found to be the key factor in durable dentin-adhesive bonding [55]. The

primer and bonding agents contain a mixture of resin monomers and initiators with

light-, chemical- or dual- curing modes and some other additives. The priming agents

consist of hydrophilic monomers that can be copolymerized with the methacrylate

monomers used in restorative applications. On the other hand, self-etching primers

are characterized by the hydrophilic monomers of acidic nature to etch the

mineralized tissue. However, monomers in the self-adhesive systems are more acidic

(pH=1) than those in self-etching systems (pH 1.9-2.4). Self-adhesives use acidic

bonding agents that contain methacrylate phosphate esters or methacrylate

14
carboxylate esters with non-reactive fillers [15,56]. Unlike etch-and-rinse systems,

multifunctional phosphoric acid methacrylates in self-etch and self-adhesive systems

chemically react with the hydroxyapatite of the hard tooth tissue (dentin) through

adsorption of the acid anions onto hydroxyapatite and covalent bond formation [57].

2.2.1 Biodegradation

Biodegradation of the non-encapsulated collagen fibrils that are the main cause of

degradation of the hybrid layer and thus of adhesion between the tooth and the

restoration [54]. Biodegradation occurs in the hybrid layer in vivo and involves

consecutive processes. The first stage of biodegradation begins when dentin is acid-

etched for removal of the smear layer, exposing the underlying collagen fibril matrix

for hybrid layer formation. The second stage involves extraction of the resins that had

infiltrated the dentin matrix through water-filled nanometer-sized voids within the

hybrid layer. The third stage involves enzymatic attack of the exposed collagen fibrils,

leading to depletion of collagen fibrils [16]. It has been demonstrated that exposure

of collagen matrix by acid etching activates matrix metalloproteinases (MMPs) [58],

that are known to cause collagenolysis in the presence of water. The trend in current

research has, therefore, shifted to the recovery of exposed (denuded) collagen fibrils.

However, the mechanism regarding the origin of initiation of biodegradation in the

hybrid layer is complex. Incomplete penetration of resin into exposed collagen matrix

as well as intrinsic enzymatic activity in the dentin result in resin-dentin bond

breakdown. However, from which side of this trilayered complex (adhesive- hybrid

layer-dentin) the degradation begins remains unclear. Fundamental research in this

area would help the researchers to reinforce this site, thereby maintaining or

enhancing the durability of the bonded interfaces.

15
 Breakdown of the inorganic polymer phase within the adhesive and the hybrid

layers or collagen fibrils in the hybrid layer (between the dental tissues and the

adhesive-primed and conditioned-) may cause degradation. Hydrolysis, which is a

chemical process that breaks covalent bonds between the polymers by addition of

water to ester bonds (methacrylate phosphate esters or methacrylate carboxylate

esters with non-reactive fillers) results in loss of the resin composite mass over time.

As a consequence, resin degradation within the hybrid layer occurs [59].

Incompletely cured adhesive resin or ester groups in the polymer chains within the

adhesive or hybrid layer due to inadequate monomer impregnation into wet dentin

substrate, result in lower degree of polymerization of adhesive resin as well as

salivary enzymes are reported to cause hydrolysis [60]. As the resin degradation is

related to water sorption within the hybrid layer, the degree of water sorption of self-

etch adhesives has been studied [61,62]. The acidic groups reacting with the main

inorganic component, which is hydroxyapatite, of the dental hard tissue form ionic

bonds.

With the incorporation of hydrophilic and ionic resin monomers into the

bonding agent in self-etch adhesives, no hydrophobic resin layer can be formed at

the bonded resin-dentin interface, irrespective of the etch-and-rinse or the self-etch

strategy. This leads to the creation of hybrid layers permitting movement of the water

present in the dentin as a consequence of dentin’s 10% water content by weight

throughout the bonded interface even after the adhesive is polymerized [63]. Resin

adhesives containing more acidic hydrophilic monomers, and higher amounts of

water to improve monomer impregnation into wet dentin substrate result in lower

degree of polymerization of adhesive resin. These factors may also result in

increased degradation [64-66].

16
 Hybrid layer degradation might also stem from resin matrix degradation itself

due to the differing monomer compositions of some currently used adhesive systems,

besides breakdown of the hybrid layer as a consequence of intrinsic enzymatic

activitiy. Since current adhesives used in combination with resin cements are

composed of different meta-monomer matrices (methacrylate, metharylamide-vinyl,

styryl, allyl), variation in degradation levels can be expected. Methyl methacrylate

(MMA) is one of the oldest monomers and is widely added to adhesives. Its function

in adhesives is to dissolve other monomers [67]. Hydroxyethyl methacrylate (HEMA)

is a type of small monomer that is widely used in dentistry. HEMA monomer is water

soluble with low viscosity which enhances the solubility of the polar and non-polar

adhesive components and the wetting behaviour of the liquid adhesive on the

dental hard tissue. HEMA has also been described to be able to evaporate from the

adhesive solutions, though only in very small amounts. Another important

characteristic of HEMA is its hydrophilicity that makes it an excellent adhesion-

promoting monomer by stabilizing the collagen fibril network and improving dentinal

permeability and monomer diffusion. On the other hand, HEMA is not hydrolytically

stable and concentrated solutions could promote its hydrolysis. Uncured HEMA

(boiling point 198°C) is a fluid that is soluble in water, ethanol (boiling point 78°C)

and/or acetone (boiling point 56-57°C) and thus an uncured monomer might cause

allergic reactions. By enhancing wetting of dentin, HEMA significantly improves bond

strength. Nevertheless, both in uncured and cured states, HEMA absorbs water [68].

bis-GMA, urethanedimethacrylate (UDMA) and triethylene glycol

dimethacrylate (TEGDMA) are most frequently used cross-linkers in adhesive

systems. Unlike mono-methacrylate monomers in adhesives, dimetacrylates’

hydrophobic behaviour results in their limited solubility in water. This feature will also

17
prevent substantial water uptake after curing, with a consequence of discoloration of

the adhesive resin [69]. On the other hand, adhesives that contain 10-

methacryloxydecyl dihydrogen phosphate (10-MDP) as a bi-functional etching

monomer can readily adhere to residual hydroxyapatite in the hybrid layer due to the

dihydrogenphosphate group [68]. This bond was reported to be very stable [57,70].

Besides self-etching effect on dentin, specifically functional monomer 10-MDP has

also chemical bonding efficacy by forming strong ionic bonds with calcium due to the

low dissolution rate of the resulting Ca-salt in its own solution [57,68].

Although a complete encapsulation of the exposed collagen fibrils by resin is

essential for a durable dentin bonding [71], primer and adhesive resin may

incompletely penetrate the demineralized collagen network following etching in etch-

and-rinse systems [72]. The discrepancy between depth of dentin demineralization

following acid-etching and depth of resin infiltration results in incompletely infiltrated

zones along the bottom of hybrid layer that contain denuded collagen fibrils [73,74].

Sano et al [73], described ‘’nanoleakage’’ as the penetration of any substance into

20- to 100-nm-sized spaces present in the adhesive and/or tooth substrate

throughout the hybrid layer and/or adhesive resin, and found that the location of

defects under or within the hybrid layer at the resin-dentin interface could be the

pathway for degradation of resin/dentin bonds over time. Silver nitrate is mainly used

as a tracer for nanoleakage observation, and silver occupies nanometer-sized

spaces around collagen fibrils, where resin fails to infiltrate, or where residual water

has not been displaced by adhesive resin [72,75]. Transmission Electron Microscopy

(TEM) images demonstrated that water can pass from dentin, around resin tags, to

form water-filled channels that project from the hybrid layer into the overlying

adhesive [63,76]. Different types of nanoleakage (spotted, reticular, water-treeing)

18
were decribed in in vitro aged specimens [15]. When these water-filled channels are

stained with silver, they often look like microscopic trees termed as ‘water-trees’ that

might act as potential sites for hydrolytic degradation of resin/dentin bonds. Thus far,

all marketed products have permitted certain amount of nanoleakage and water-tree

formation. Ideally, nanoleakage at the resin/dentin interface should be minimized or

eliminated completely. Some techniques may be efficient in preventing nanoleakage.

With ethanol-wet dentin bonding approach [77], by replacing ethanol with water in the

primer, bisGMA/TEGDMA mixtures have been shown to infiltrate dentin, thus

reducing nanoleakage and producing high bond strengths [78]. Self-etch adhesives

do not require smear layer (which consists of bacteria, prepared tooth tissue particles

that cannot be washed away, microbial dental plaque, saliva, etc.) removal by acidic

conditioners and due to simultaneous etching and priming processes no discrepancy

between the depth of demineralization and the depth of resin infiltration occurs [74].

However, it has been demonstrated that self-etch adhesive systems are also

susceptible to nanoleakage within the hybrid layer [15]. If biodegradation of resin

bonded dentin is to be avoided, complete penetration and polymerization of adhesive

are essential. Additionally, the adverse effects of host-derived enzymes (esterases

and matrix metalloproteinases) at the resin/dentin interface should be prevented [16].

Although phosphoric acid etching is effective in lowering collagenolytic activity

by partial denaturation of the enzymes, some residual enzymatic activity still remains.

If the resin poorly infiltrates, or if it slowly hydrolyzes and leaches from the hybrid

layer, the intrinsic MMP activity of the dentin matrix can be expressed, causing it to

dissolve [16,76]. This process weakens the hybrid layer, leading to shrinkage of

dentin following cementation due to demineralization and dehydration processes and

it eventually propagates biodegradation of hybrid layer leading to

19
nanoleakage/microleakage. Moreover, with occlusal forces loss of collagen and resin

increases due to excessive fluid shear forces occuring in the voids under the

compromised hybrid layer. On the other hand, once the collagen fibrils are

completely covered by the resin, the effect of collagenolysis can be diminished [79].

The studies aiming to prevent biodegradation have focused on the use of

MMP inhibitors in or with primers [80]. In 2005, Hebling et al [81] reported the anti-

collagenolytic activity of chlorhexidine on host-driven enzymes (MMPs) in dentin. The

authors suggested chlorhexidine use to inhibit the MMPs and to stop the self-

destruction of the collagen matrices. In 2006, Tay and coworkers [82] conducted

another study to test the inhibiting ability of chlorhexidine in collagen degradation and

concluded the same results as Hebling et al, indicating that chlorhexidine was

effective in inhibiting the collagenous enzymatic activity in dentin [81].

Hiraishi et al, conducted a study aiming to investigate the effect of

pretreatment by chlorhexidine on the microtensile bond strength of resin cements

and nanoleakage at the resin-dentin interfaces. They concluded that pretreatment

with chlorhexidine affected the integrity of dentin bonding and that decreased the

microtensile bond strength of resin cements at the resin-dentin interface [83]. Another

study [84] investigating the effect of 0.2% and 2% chlorhexidine used as a

therapeutic primer on the long-term bond strengths of two etch-and-rinse adhesive

systems found increased nanoleakage during in vitro aging (thermocycling for

simulating intraoral conditions, cyclic loading,etc.) in controls, but reduced silver

deposits were found in chlorhexidine-treated specimens. The authors suggested that

since no bacterial growth was present in the aging conditions and endogenous

factors (MMP activitiy) thought to degrade the interface could be inhibited by

chlorhexidine application on prepared dentin surfaces [84].

20
 There are newer strategies for the elimination/minimization of nanoleakage at

the resin/dentin interface by introducing some new chemical agents such as caffeic

acid phenylethyl esther (CAPE), an active ingredient of propolis; however this

material is still under further development stage for routine clinical use [85].

More recently, the influence of a new synthetic MMP inhibitor named ‘galardin’

was evaluated on the proteolytic activity of dentinal MMPs and on the morphological

and mechanical features of hybrid layers after aging. Galardin is a synthetic MMP-

inhibitor with potent activity against MMP-1, -2, -3, -8 and -9 [84]. It has a collagen-

like structure to facilitate binding to the active sites of MMPs and a hydroxamate

structure (R–CO–NH–OH, where R is an organic residue) that chelates the zinc ion

located in the catalytic domain of MMPs. However, the use of galardin was found to

reduce the amount of nanoleakage, but failed to completely block biodegradation

[84].

From a clinical point of view, resin-based adhesive luting cements require full

penetration and polymerization, otherwise degradation will occur in time, causing

nanoleakage in dentin and possibly caries formation under or around the margins of

fixed-dental-prosthesis (FDP) as well as adhesively bonded restorations. However,

degradation is a time-dependent phenomenon depending on the destruction of both

collagen and hybrid layer, which makes time-dependent studies highly important from

clinical point of view.

3. Restorative Materials

3.1 Metals

A dental alloy, either base or noble, must fulfill certain minimum requirements for

strength, stability, castability, corrosion/tarnish resistance, burnishability, polishability,

21
and biocompatibility to be considered successful. Metal-ceramic (ceramics supported

by metal framework) alloys have additional requirements that are not usually

essential for alloys used for full cast-metal restorations. Although esthetics may be

supplied by the ceramic part of a metal-ceramic restoration, the success of the entire

prosthesis depends largely on the physical properties of the metal substructure [86].

Higher melting temperature (over 1000°C), thermal compatibility with ceramics, oxide

formation, and sag resistance are, therefore, required for a metal framework.

The gold-platinum-palladium (Au-Pt-Pd) alloys were the first to be used

successfully for metal-ceramic restorations; however, their use decreased after more

economical alloys (base and/or semi-precious, titanium metal alloys) were developed

with significantly better mechanical properties and sag resistance. If the alloy

contains more palladium than platinum, it is referred to as a gold-palladium-platinum

alloy [87]. Alloys in which palladium has been eliminated are referred to as gold–

platinum alloys. Because of their low sag resistance, the use of these alloys should

be limited to crowns and three-unit fixed dental prosthesis (FDP). The Au-Pd alloys

were developed to address the two main problems associated with silver-containing

alloys: porcelain discoloration and a high coefficient of thermal expansion [87].

Due to low silver content in these alloys, porcelain does not discolor, castability is

improved, and the coefficient of thermal expansion is increased [88]. Pd-Ag alloys

were specifically developed to offer an economical alternative to more expensive

gold-based alloys [89]. Pd-Ag alloys (coefficient of thermal expansion approximately

ranging between 14.6-17.1X10-6/°C) typically contain approximately 60% palladium,

with the balance being silver and small amounts of indium and tin to facilitate the

metal’s oxide formation. High-palladium alloys were introduced in the 1980s, and

were primarily developed for decreasing the material costs of noble alloys, to address

22
biocompatibility concerns of nickel-based casting alloys since nickel might cause

allergic reactions, and to minimize the possibility of porcelain discoloration seen with

Pd-Ag alloys [89]. For metal-ceramic use, base-metal alloys (nickel based and cobalt

based) have been reported to have better castability than noble-metal alloys, but they

tend to form thicker, darker oxide layers that may present esthetic problems [89].

Alloys in both systems contain chromium as their second largest constituent for

corrosion resistance. They exhibit the highest modulus of any alloy type used for cast

restorations [89].

The medical use of commercially pure titanium (cp Ti) and titanium alloys has

increased significantly over the past 20 years. The successful use of titanium dental

implants due to their biocompatibility has generated considerable interest in other

dental uses for pure titanium and titanium alloys, including all-metal and metal-

ceramic prostheses, as well as partial denture frameworks [91]. Titanium is

considered to be the most biocompatible metal for a dental prosthesis [92].

3.2 Ceramics

Ceramics, depending on their chemical composition, can be classified in three main

categories: glass-ceramic, particle-filled glass, and polycrystalline [93].

3.2.1 Glass-ceramic

Dental ceramics that have high glass content best mimic the optical properties of

enamel and dentin. Manufacturers use small amounts of filler particles to control

optical effects such as opalescence, color and opacity. Ceramics containing high

concentrations of leucite and lithium disilicate crystals are examples of glass-

ceramics that are processed by injection-moulding.

The density change that occurs during firing of conventional feldspathic (a mineral

with sodium, potassium or calcium content) porcelains or during the ceramming

23
procedure for castable glass-ceramics leads to undesired dimensional changes that

result in inaccurate fit. Ceramming is a controlled crystallization (devitrification) of the

glass that results in the formation of tiny crystals that are evenly distributed

throughout the body of the glass structure. The size of the crystals, as well at the

number and rate of growth is determined by the time and temperature of the

ceramming heat treatment. There are two parts to the ceramming process; crystal

nucleation and crystal growth. Each phase happens because the glass body is held

at a specific temperature for a specific length of time. Press ceramic systems were

attempted to overcome this effect by using glass-ceramic ingots. Pneumatic pressure

injection of the molten glass-ceramic into a heated mold requires a special furnace

capable of high temperatures. The dimensional change that occurs during

solidification of the molten glass-ceramic is compensated by accurately matched

expansion of the investment material. Pressable glass-ceramic systems, that replace

the place left in the investment material after wax elimination, may be used for

laminate veneers and complete crowns on anterior teeth and inlays, onlays, partial-

coverage crowns and complete crowns on posterior teeth [94]. The flexural strength

of a pressable glass-ceramic has been reported to increase subsequent to the high-

temperature injection molding process, as well as following the glaze and/or enamel

porcelain firing. The strength of this glass-ceramic material allows its use as an inlay,

onlay and single crown restorative material [95].

3.2.2 Particle-filled glass

Manufacturers add filler particles (silica, alumina, leucite, magnesia, etc.) to the base

glass composition to improve mechanical properties, such as strength and thermal

expansion and contraction behaviour. These fillers are usually crystalline, but they

also can be particles of high-melting glasses that are stable at the firing temperatures

24
of the ceramic. The glassy matrix is selectively etched during hydrofluoric acid

etching to create micromechanical retentive features enabling bonding. Particles can

be added mechanically during manufacturing as powder or be precipitated within the

starting glass by special nucleation and growth heating treatments; in the second

case, such materials are termed "glass-ceramics" [96].

Another type of particle-filled glass is an alumina-based ceramic system where a

two-phase core material is produced during a slip casting process and subsequently

strengthened during a glass infiltration firing process [93]. The filler is alumina,

magnesium aluminate spinel or a mixture of 70% alumina and 30% zirconia. Such an

alumina based ceramic has been recommended for single anterior and posterior

crowns, as well as for anterior three-unit FDPs [93].

The core is trimmed and built to anatomical contour using conventional techniques

with dentin and enamel porcelain. The superior fit of alumina-based ceramic crowns

is attributed to low-temperature sintering of the core material, which results in minimal

volumetric shrinkage and excellent marginal adaptation [88]. Although the alumina

core has high strength, it is characteristically opaque. Incorporating magnesium

aluminate spinel rather than aluminum oxide, results in improved optical properties

characterized by increased translucency with only small reduction in flexural strength

[93,97].

3.2.3 Polycrystalline ceramics

Polycrystalline ceramics do not contain glass; the matrix is aluminum oxide or

zirconium oxide, and the fillers are not particles but modifying atoms called "dopants."

All of the atoms are packed into regular crystalline arrays, preferably tetragonal,

through which it is much more difficult to drive a crack than in atoms in the less dense

and irregular network found in glasses; therefore, polycrystalline ceramics generally

25
are much tougher and stronger than glass-based ceramics. Highly esthetic dental

ceramics with improved colour and translucency have high glass content, and higher-

strength substructure ceramics generally are crystalline. The historical development

of substructure ceramics has involved an increase in crystalline content ranging from

approximately 55% crystalline to fully polycrystalline [98].

At the beginning of the 1990s oxide ceramics that contain only little or no silica

were introduced into restorative dentistry. Oxide ceramics (e.g. zirconium dioxide and

aluminum oxide) contain less than 15 wt% silica and only a small or no glass phase

[99]. Dental oxide ceramics were first glass-infiltrated or densely sintered alumina

ceramics, followed by zirconia reinforced glass-infiltrated alumina ceramic, and since

then, several densely sintered zirconia ceramic systems have been introduced [100].

Current dental oxide ceramics consist mostly of alumina, magnesia, zirconia or yttria.

Because of their high strength, oxide ceramics are used as frameworks and for

replacing alloys not only in crowns but also in multiple-unit FDPs. In addition,

because of their high strength, adhesive luting techniques are not required for oxide

ceramic dental restorations as the abutment teeth provide adequate mechanical

retention (ideally 6-8° axial taper of the prepared tooth) for conventional cements.

Nevertheless, adhesive luting techniques for oxide ceramics, because of the strength

of both the adhesive and the ceramic, can provide significant clinical advantages

over conventional cementation of dental restorations [99]. Adhesive luting with light-

curing, dual-curing or self-curing cements can provide sealed restoration margins,

minimizing microleakage and, thereby, reducing secondary caries risk [96]. Esthetics

might also be improved by using tooth colored and/or transparent resin luting agents

as compared to opaque conventional cements, and tooth colored restorative

26
materials, like ceramics or composite resins, can be bonded to the teeth without

visible cementation line [101].

Computer-aided systems use a 3D data set representing either the prepared tooth

or a wax model of the desired framework. Such systems use this 3D data set to

create an enlarged die upon which ceramic powder is condensed or to machine an

oversized part for firing by machining blocks of partially sintered ceramic powder [96].

All-ceramic restorations combining esthetic veneering porcelains with strong

ceramic cores (such as zirconia, lithium disilicate, alumina) have become popular.

Veneering porcelains typically consist of a glass and a crystalline phase of

fluoroapatite, aluminum oxide, or leucite. Veneering a lithium disilicate, aluminium

oxide, or zirconium oxide core with glass allows dental technicians to customize

these restorations in terms of form and esthetics. The most commonly reported major

clinical complication resulting in failure of all-ceramic restorations is the fracture of the

veneering porcelain and/or the framework [102]. The success of these systems

depends on preventing failure by retarding crack propagation by arresting the cracks

induced by masticatory loading inside the inherently brittle ceramic material through

reinforcement with high-performance core (framework) ceramics such as alumina,

zirconia and lithium disilicate. The use of all-ceramic systems for FDPs has

limitations. A minimum FDP connector height of 3 to 4 mm from the interproximal

papilla to the marginal ridge is a prerequisite for most systems. When there is

reduced interocclusal distance, short clinical crowns, deep vertical overlap or an

opposing supraerupted tooth, cantilevers, periodontally involved abutment teeth, and

patients with severe bruxism or parafunctional activity, their use is contraindicated

[103]. The primary cause of failure varies from fracture of the connector for aluminium

oxide/lithium disilicate FDPs to cohesive fracture of the veneering porcelain for

27
zirconia FDPs [104]. However, metal-ceramic FDPs mainly fail due to tooth fracture

and caries [94,105].

Due to high content of silica in silica-based ceramics, organosilanes have been

successfully used to promote the bond between the silica ceramic and the resin-

based luting cement usually after roughening the ceramic surface by hydrofluoric

acid etching or airborne particle abrasion. Organosilanes are organofunctional

trialkoxysilanes or silane esters containing a non-hydrolysable organic group and a

hydrolysable group and they have a dual reactivity. The non-hydrolysable functional

group with a carbon-carbon double bond polymerizes with monomers containing

double bonds. The hydrolysable alkoxy group reacts with the ceramic surface rich in

hydroxyl groups. [96,106-109].

Adhesion among the prepared tooth surface, composite luting resin and the

restoration assembly requires adhesive bonding of each surface to each other. This

can be achieved through surface modifications of the tooth and restoration surfaces

and using an adhesive luting cement to combine these dissimilar materials. Adhesive

bonding of oxide ceramics allows the introduction of new non-invasive treatment

choices for tooth replacement by resin bonding all-ceramic FDPs. Conventional

mechanically retentive tooth preparation can be considered invasive since sound

tooth structure is usually removed [99]. Adhesive luting, on the other hand, does not

require such a mechanical retention, and adhesion through chemical bonding is

sufficient. However, bonding methods used for conventional silica-based dental

ceramics are not suitable for dental oxide ceramics. Densely sintered alumina and

zirconia ceramics offer similar bonding substrates in a way that they are both

completely free of glassy phase with grains sintered into a dense and homogeneous

structure. Chemically, their surfaces consist mainly of either aluminum oxide or

28
zirconium dioxide to which specific bi-functional monomers bond well [110,111].

Oxide ceramics cannot be efficiently etched with hydrofluoric acid for resin bonding

[100,112] and although the most often used coupling agent for silica-based ceramics,

3-methacryloxypropyltrimethoxysilane (MPS), might help in surface wetting of oxide

ceramics, it does not promote adequate bonding to alumina or zirconia ceramics

[99,113]. The silanes should be first hydrolysed (pre-activated) for formation of

silanols that are adsorbed, deposited and polymerized on the substrate surface

followed by hydrogen bond and covalent Si-O-Si bond formation, called silanization.

This process promotes the adhesion between the etched silica containing dental

ceramic surface (hydroxyl group) and the composite resin through silanes. Therefore,

alternative bonding techniques must be developed for dental oxide ceramics.

Adhesion to mainly non-precious dental metal surfaces, especially in resin-bonded

FDPs, where major retention has been achieved through metal ‘’wings’’ covering the

palatal surfaces of the teeth together with a resin composite luting cement, can also

be enhanced by silica coating and subsequent silanization of the cementation

surfaces [114].

3.3. Composites

The physical, mechanical and esthetic properties and the clinical behaviour of

composites depend on their structure. Dental composites are composed of three

chemically different materials: the organic matrix (organic phase), inorganic matrix,

filler or disperse phase, and an organosilane or coupling agent to bond the filler to

the organic resin. This agent is a molecule with silane groups at one end, and

methacrylate groups at the other for covalent bonding with the resin. Basically, the

organic matrix of the composite resins is made up of a system of mono-, di- or tri-

functional monomers; a free radical polymerization initiation system, which in

29
photocurable composite resins is an α-diketone (camphoroquinone) used in

combination with a tertiary aliphatic amine reducing agent (4-N,N-dimethylamino-

phenyl-ethanol, DMAPE). In chemically-curing systems, initiation system is a benzoyl

peroxide, used in combination with an aromatic tertiary amine (N,N-dihydroxyethyl-p-

toluidine) and an acceleration system (dimethylaminoethyl methacrylate or DMAEM,

ethyl-4-dimethylaminobenzoate or EDMAB, or N,N-cyanoethyl-methylaniline or

CEMA), which acts on the initiator, allowing curing to take place. In addition, a

stabilizer or inhibitor system such as hydroquinone monomethyl ether maximizes the

shelf-life of the product before curing and increases its chemical stability. The

absorbers of ultra-violet wavelengths below 350 nm, such as 2-hydroxy-4-

methoxybenzophenone, provide colour stability and eliminate the effects of UV light

on the amine compounds in the initiator system that can cause discoloration in the

medium to long term because of its inherent color instability due to temperature

changes and storage conditions [115].

The monomer system (bis-GMA) can be viewed as the backbone of the composite

resin system, although not the major component. bis-GMA is still the most used

monomer for fabricating composites; whether alone or in conjunction with urethane

dimethacrylate, it constitutes around 20% (v/v) of composite resin composition. It is

accepted that the lower the mean molecular weight of the monomer or monomer

combination, the higher the percentage of shrinkage.

Since bis-GMA is highly viscous, it is diluted with other low-viscosity monomers

(low molecular weight) which are considered viscosity controllers, such as bisphenol

A dimethacrylate (bis-DMA), ethylene glycol dimethacrylate (EGDMA), triethylene

glycol dimethacrylate (TEGDMA), methyl methacrylate (MMA) or urethane

dimethacrylate (UDMA) to facilitate the fabrication process and clinical handling

30
[116]. bisphenol-A, a component in composite resins, alone might be toxic; however

no free, unreacted BPA in bis-GMA or bis-DMA has been reported in dental

composite resins. Besides, to liberate the BPA from these resins, temperature

exceeding several hundred degrees is required. Moreover, measurements on

exposure to BPA from dental resins revealed potential doses that are hundreds or

thousands of times less than any known toxic level [117]. The disperse phase of

composite resins is made up of an inorganic filler material that basically determines

the physical and mechanical properties of the composite. The nature of the filler, how

it is obtained and how much it is added largely decide the mechanical properties of

the restoration material. The filler particles are added to the organic phase to improve

the physical and mechanical properties of the organic matrix, so incorporating a high

percentage of filler as much as possible is a fundamental objective. The filler reduces

the thermal expansion coefficient and overall curing shrinkage, provides radio-

opacity, improves handling and optical properties of resin composites [118,119].

The filler particles used vary widely in their chemical composition, morphology and

dimensions. The main filler is silicon dioxide; boron silicates and lithium aluminium

silicates are also commonly employed. In many composites, the quartz is partially

replaced by heavy metal atoms such as barium, strontium, zinc, aluminium or

zirconium, which are radiopaque as well. Current materials involve calcium

metaphosphate, that is less hard than glasses and, therefore, cause less wear on the

opposing tooth [120].

Nanotechnology has led to the development of new composite resins containing

nanoparticles approximately 25 nm and nanoaggregates of approximately 75 nm,

which are made up of zirconia/silica or nanosilica particles (filler). The aggregates are

treated with silane for binding to the resin [121].

31
4. Adhesion Test Methods in Dentistry

In dentistry, the strength of a material and the strength of the union of dissimilar

materials are tested through various adhesion test methods. Two main types of

strengths have been reported: tensile and shear that result from pure loading modes.

Other test systems are combinations of these two methods. [122].

Some fundamental aspects of adhesion were investigated in a recent review

article [123], and these aspects were related to dental adhesion studies. The results

of that research revealed that the meaning of the overall adhesion strength value as

usually defined in dentistry does not conform to the meaning in fields such as

mechanical engineering and physics. Adhesion studies in dental medicine should

approach the problem from fracture mechanics and fatigue points of view rather than

from an overall strength point of view. If no strong evidences correlating clinical

success with any particular adhesion test method are present, in vitro tests should

not be used as predictors of clinical performance [123].

Current approach in dental materials testing is to load multiple test specimens

from each tooth in either a tensile (microtensile bond strength) or shear (microshear

bond strength) bond strength testing configuration. Results generated from primarily

shear and microtensile tests are commonly used when different products are being

marketed, so this might misleadingly give an impression that higher bond strength

results in better clinical performance.

Smaller sized test specimens are deemed stronger than larger sized specimens

due to the lower probability of having a critical sized defect present and aligned in a

crack opening orientation relative to the applied load [124].

32
4.1. Microshear Bond Strength Test

Shear bond strength (SBS) test with bonded cross-sectional areas of 1 mm2 or less is

referred to as microSBS (µSBS) [125]. This relatively simple test permits

conservation of extracted tooth tissues by controlled, slow cross-sectioning process

under cooling. Moreover, regional bond strength depending on the orientation of

dentin tubuli is achieved through small cross-sectional area bond strength testing. A

significant advantage over microtensile (µTBS) methods is that the µSBS specimen

is prestressed before testing only by mould removal. However, the use of the mould

for placement can lead to the introduction of flaws and different stress concentrations

resulting from shear loading, similar to macroSBS methods [123]. µSBS tests are

suitable for substrates such as glass ionomers or enamel, in terms of specimen

preparation effects and test conditions of µTBS testing.

4.2. Microtensile Bond Strength Test

The microtensile bond strength is calculated as the tensile load at failure divided by

the cross-sectional area of the bonded interface. However, this is valid only if a state

of uniform, uniaxial stress is present [126,127] with the maximum tensile stress

present and homogenously distributed in the region of the bonded area [128].

Advantages of µTBS test are conservation of teeth, evaluation of regional bond

strengths [129,130], evaluation of intra- and inter-tooth variability, more uniform

loading due to less bending offset relative to conventional tensile testing, fewer

cohesive failures in substrates, higher bond strengths than those from conventional

tensile and shear bond strength tests due to the decreased number of defects in the

substrate or at the bonded interface [131], possibility to evaluate very small surface

areas when necessary, minimizing the shear effect by tensile testing a relatively

flatter region of tooth. However, limitations of µTBS test method include: technique

33
sensitivity, difficulty in measuring very low bond strength (<5 MPa), ease of

dehydration and damage of extracted tooth specimens, loss or damage of specimens

when removing from active jigs that use glue and difficulty in fabrication with

consistent geometry [124].

Specimen geometry and preparation effects as well as test speed are also

parameters contributing to the variations in test methodologies [112]. No agreement

has been reached favoring a particular strength test method regarding its clinical

correlation, yet. Too many variables are involved in bond testing, and because of

interactions between these variables, it is difficult or impossible to compare results

from different studies. Even when the same batches and the same experimental

conditions are used, significant variations still exist among findings of same

researchers [132]. Considering all these variations it can be stated that bond strength

data resulting from different groups or individuals are far from being reproducible

[133,134]. The reason is that the measured bond strength values neglect the true

stress distribution [135] and that the results are highly affected by defects introduced

during sample preparation [132-136]. It is suggested that fracture mechanics

approaches should be used instead of using strength testing approaches, and using

fracture mechanics the impact of crack formation and crack propagation on the

clinical behavior should be investigated. Neither microtensile nor shear bond test

uses fracture mechanics to solve the adhesion testing problem. However, when

tensile and shear tests are compared, there is a distinct difference between these two

methods in that the application of the force affects the opening mode of the joint.

Even though it might seem that the failure occurs instantaneously over the entire

bond area when the adhesive joint fails, the crack starts propagating from an edge

and rapidly propagates along the interface [123,124-128]. Factors such as stress

34
concentration at the crack tip and the rate with which energy stored in the stressed

system recovers are the main factors that should be considered. Fracture mechanics

tests, in contrast to strength tests, consider localized stress concentration factor, and

the energy release rate [124]. An extensive review of methodologies for adhesion

tests used for teeth and restorative materials in dentistry could be helpful for the

reader [137].

5. Future Perspectives and Expectations

The initiation of hybrid layer degradation, whether from the adhesive or the dentin

side, remains unclear. No matter where biodegradation starts, our main approach

should be, with today’s knowledge, to use non-hydrolysing polymers and inhibit

enzymatic activity in dentin.

While technique-sensitive adhesive systems are being simplified in terms of

application steps, no compromise should be made in terms of pivotal properties for

stable adhesion.

In order to meet increased esthetic demand in recent years, with the necessity for

minimally invasive treatment modalities, durable materials should be adopted in a

conservative treatment approach.

Adhesion research on dental substrates and materials requires long-term clinical

data and standardization of test methods.

6. Conclusions

1. With etch-and-rinse as well as self-etch adhesive systems, durable adhesion

can be achieved on enamel due to its high mineral content and less organic matrix.

35
2. The long-term durability of dentin bonding is of vital importance for clinical

success, besides the initial bond strength of an adhesive to dentin. Focus should be

on the preservation of the hybrid layer and inhibition of biodegradation.

3. Nanotechnological developments in ceramics, polymers, dental resin

composites and metals would enhance the physical, chemical and optical properties

of materials as well as their malleability and would save time for chairside and/or

laboratory fabrication procedures.

4. Traditional strength test methodology lacks true interpretation of adhesion data

in dental science, and in vitro tests alone should not be used as predictors of clinical

performance. If we can develop new dynamic test methods for correlating results on

long-term performance of new materials in dentistry, only then in vitro test methods

will have a practical meaning.

5. Optimal bond strength related to local stress distributions generated during

adhesion testing of dental materials should be well understood before bond strength

testing can be standardized.

36
References

1. S.J. Marshall, S.C. Bayne, R. Baier, A.P. Tomsia and G.W. Marshall. Dental

Mater. 26, 11-16 (2010).

2. D.C. Smith, In: iomaterials Science: An Introduction to Materials in Medicine,

B.D. Ratner, A.S. Hoffman, F.J. Schoen, J.E. Lemons (Eds.). p. 319 San

Diego: Academic Press (1996).

3. R.E. Baier, Oper Dentistry. 5, 1 (1999).

4. B. Van Meerbeek, J. De Munck, Y. Yoshida, S. Inoue, M. Vargas, P. Vijay, K.

Van Landuyt, P. Lambrechts and G. Vanherle, Oper Dentistry. 28, 215 (2003).

5. G.V. Black. The Pathology of the Hard Tissues of the Teeth. ed 3.: Medico-

Dental Publishing, Chicago (1917).

6. M.G. Buonocore, J Dental Res. 34, 849 (1955).

7. K.J. Söderholm, M. Phil and A. Mariotti, J. Am. Dent. Assoc. 130, 201 (1999).

8. R.L. Bowen, J Dental Res. 35, 360 (1956).

9. R.L. Bowen, J. Am. Dent. Assoc. 66, 57 (1963).

10. M. Mahmoodian, AB. Arya and B. Pourabbas, Dental Mater. 24, 521(2008).

11. M. Peumans, J. De Munck, S. Fieuws, P. Lambrechts, G. Vanherle and B. Van

Meerbeek, J Adhesive Dentistry. 6, 76 (2004).

12. J.H. Chen, C.X. Shi, M. Wang, S.J. Zhao and H. Wang, J Dentistry. 33, 3

(2005).

13. K.L. Van Landuyt, J. Snauwaert, J. De Munck, M. Peumans, Y. Yoshida, A.

Poitevin, E. Coutinho, K. Suzuki, P. Lambrechts and B. Van Meerbeek,

Biomaterials. 28, 3757 (2007)

14. N. Nakabayashi and K. Takarada, Dental Mater. 8, 125 (1992).

15. F.R. Tay and D.H. Pashley. J Can Dental Assoc. 69, 726 (2003).

37
16. H. Sano, J Dental Res. 85, 11 (2006).

17. K. Hikita, B. Van Meerbeek, J. De Munck, T. Ikeda, K. Van Landuyt and T.

Maida, Dental Mater. 23, 71 (2007).

18. F. Monticelli, R. Osorio, C. Mazzitelli, M. Ferrari and M. Toledano, J Dental

Res. 87, 974 (2008).

19. Y.Yoshida, K. Nagakane, R. Fukuda, Y. Nakayama, M. Okazaki, H. Shintani,

S. Inoue, Y. Tagawa, K. Suzuki, J. De Munck and B. Van Meerbeek, J

Dental Res.83, 454 (2004).

20. I. Radovic, F. Monticelli, C. Goracci, Z.R. Vulicevic and M. Ferrari, J Adhesive

Dentistry. 10, 251 (2008).

21. A.R. Ten Cate, Oral Histology: Development, Structure, and Function, Mosby-

Year Book, 5th edition, p.1, Mosby, St. Louis (1998).

22. S. Habelitz, S.J. Marshall and G.W., Marshall Jr., Arch Oral Biol. 46, 173

(2001).

23. M. Di Renzo, T.H. Ellis and A. Domingue, J Adhesion. 47, 115 (1994).

24. A.J. Gwinnet and A. Matsui, Arch Oral Biol. 12, 1615 (1967).

25. B. Vaidyanathan and J. Vaidyanathan, J Biomed Mater Res B 88, 558

(2009).

26. W.W. Barkmeier and R.L. Erickson, Am J Dentistry 7, 175 (1994).

27. A. Usumez and F. Aykent, J Prosthet Dentistry 90, 24 (2003).

28. B. Van Meerbeek, M. Peumans, A. Poitevin, A. Mine, A. Van Ende, A. Neves

and J. De Munck, Dental Mater. 26, 100 (2010).

29. B. Gökçe, E. Çömlekoğlu, B. Özpınar, M. Türkün and D.A. Kaya, J Dentistry.

36, 780 (2008).

30. Pashley and F.R. Tay, Dental Mater. 17, 430 (2001).

38
31. J. Perdigao and S. Geraldeli, J Esthet Restor Dentistry. 15, 32 (2003).

32. P.A. Miguez, P.S. Castro and M.F. Nunes, J Adhesive Dentistry. 5, 107

(2003).

33. J. Perdigao, G. Gomes and S. Duarte Jr, Oper Dentistry. 30, 492 (2005).

34. R. Fukuda, Y. Yoshida, Y. Nakayama, M. Okazaki, S. Inoue, H. Sano, K.

Suzuki, H. Shintani and B. Van Meerbeek. Biomaterials. 24,1861 (2003)

35. S. Inoue, Y. Abe and Y. Yoshida, Oper Dentistry. 29, 685 (2004).

36. A.R. Ten Cate, In: Oral Histology, Development, Structure and Function, A.R.

Ten Cate (Ed), p. 45, 4th edition. Mosby, St. Louis (1994).

37. C.D. Torneck, In: Oral Histology, Development, Structure and Function, A.R.

Ten Cate (Ed), p. 169, 4th edition. Mosby, St. Louis (1994).

38. J.P. Gage, M.J.O. Francis and J.T. Triffitt, Collagen and Dental Matrices, p.52,

Butterworth-Heinemann, London, (1989).

39. G. He and A. George, J Biol Chem. 279, 11649 (2004).

40. G.K. Hunter, P.V. Hauschka, A.R. Poole, L.C. Rosenberg and H.A. Goldberg,

Biochem J. 317, 59 (1996).

41. N. Nakabayashi, K. Kojima and E. Masuhara, J Biomed Mater Res. 16, 265

(1982).

42. D.H. Pashley, B. Ciucchi, H. Sano and J.A. Horner. Quintessence Int. 24, 618

(1993).

43. N. Nakabayashi, In: Biomedical Applications of Polymeric Materials, T.

Tsuruta, T. Hayashi, K., Kataoka, K. Ishihara and Y. Kimura (Eds.) CRC

Press, Boca Raton, FL, p. 220 (1993).

44. M. Toledano, R. Osorio, L. Ceballos, M.V. Fuentes, C.A. Fernandes, F.R. Tay

and R.M. Carvalho, Am J Dentistry 16, 292 (2003).

39
45. Y. Yuan, Y. Shimada, S. Ichinose, A. Sadr and J. Tagami, J Dental Res. 86,

1001 (2007).

46. Y. Yuan, Y. Shimada, S. Ichinose and J. Tagami, J Dentistry. 35, 664 (2007).

47. Y. Yuan, Y. Shimada, S. Ichinose and J. Tagami, Dental Mater. 24, 584

(2008).

48. J.A. Kanca, J Am Dental Assoc. 123, 35 (1992).

49. A.J. Gwinnett, Dental Mater. 10, 150 (1994).

50. J.A. Kanca, Am J Dentistry. 9, 273 (1996).

51. F.R. Tay, J.A. Gwinnett and S.H. Wei. Dental Mater. 12,236 (1996)

52. C.K.Y. Yiu, E.L Pashley, N. Hiraishi, N.M. King, C. Goracci, M. Ferrari,

R.M.Carvalho, D.H. Pashley and F.R. Tay, Biomaterials. 26, 6863 (2005)

53. R.M. Carvalho, J.S.Mendonca, S.L. Santiago, R.R. Silveira, F.C. Garcia, F.R.

Tay and D.H. Pashley, J Dental Res. 82, 597 (2003)

54. P. Spencer, Y. Wang, M.P. Walker and J.R. Swafford, J Dental Res. 80, 1802

(2001).

55. H.A. Wege, J.A. Aguilar, M.A. Rodriguez-Valverde, M. Toledano, R. Osorio

and M.A. Cabrerizo-Vilchez, J Colloid Interface Sci. 263, 162 (2003).

56. N. Nakabayashi and D.H. Pashley, Hybridization of Dental Hard Tissues,

Quintessence Publishing, Chicago (1998).

57. K.L. Van Landuyt, J. De Munck, J. Snauwaert, E. Coutinho, A. Poitevin, Y.

Yoshida, S. Inoue, M. Peumans, K. Suzuki, P. Lambrechts and B. Van

Meerbeek, J Dental Res. 84, 183 (2005).

58. Y. Yoshida, K. Nagakane, R. Fukuda, Y. Nakayama, M. Okazaki, H. Shintani,

S. Inoue, Y. Tagawa, K. Suzuki, J. De Munck and B. Van Meerbeek, J Dental

Res. 83, 454 (2004).

40
59. S. Sauro, F. Mannocci, M. Toledano, R. Osorio, D.H. Pashley and T.F.

Watson, J Dentistry. 37, 279 (2009).

60. F.R. Tay, D.H. Pashley, B.I. Suh, N. Hiraishi and C.K. Yiu, Oper Dentistry. 30,

561 (2005).

61. B.A. Lin, F. Jaffer, M.D. Duff, Y.W. Tang and J.P. Santerre, Biomaterials. 26,

4259 (2005).

62. S. Ito, M. Hashimoto, B. Wadgaonkar, N. Svizero, R.M. Carvalho and C. Yiu,

Biomaterials. 26, 6449 (2005).

63. J. Malacarne, R.M. Carvalho, M.F. de Goes, V. Svizerd, D.H. Pashley and

F.R. Tay, Dental Mater. 22, 973 (2006).

64. F.R. Tay and D.H. Pashley, J Adhesive Dentistry. 4, 91 (2002).

65. N. Nakabayashi and K. Hiranuma, Dental Mater. 16, 274 (2000).

66. P. Spencer, Y. Wang, M.P. Walker, J.R. Swafford, J Dental Res. 80, 1802

(2001).

67. M. Hashimoto, H. Ohno, M. Kaga, H. Sano, K. Endo and H. Oguchi, J Dental

Res. 81, 74 (2002).

68. H. Andreasson, A. Boman, S. Johnsson, S. Karlsson and L. Barregard, Eur J

Oral Sci. 111, 529 (2003).

69. K.L. Van Landuyt, J. Snauwaert, J. De Munck, M. Peumans, Y. Yoshida, A.

Poitevin, E. Coutinho, K. Suzuki, P. Lambrechts and B. Van Meerbeek,

Biomaterials. 28, 3757 (2007).

70. I. Sideridou, V. Tserki and G. Papanastasiou, Biomaterials. 23, 1819 (2002).

71. L. Breschi, A. Mazzoni, A. Ruggeri, M. Cadenaro, R. Di Lenarda and E. De

Stefano Dorigo, Dental Mater. 24, 90 (2008).

41
72. M. Hashimoto, H. Ohno, H. Sano, M. Kaga and H. Oguchi, Biomaterials. 24,

3795 (2003).

73. H. Sano, T. Takatsu, B. Ciucchi, J.A. Horner, W.G. Matthews, D.H. Pashley,

Oper Dentistry. 20, 18 (1995).

74. S.R. Armstrong, J.C. Keller and D.B. Boyer, Dental Mater. 17, 268 (2001).

75. P. Spencer, Y. Wang, M.P. Walker, D.M. Wieliczka and J.R. Swafford, J

Dental Res. 79,1458 (2000).

76. H. Sano, T. Shono, T. Takatsu and H. Hosada, Oper Dentistry. 19, 59 (1994).

77. M. Hashimoto, J. De Munck, S. Ito, H. Sano, M. Kaga and H. Oguchi,

Biomaterials. 25, 5565 (2004).

78. F.T. Sadek, C.S. Castellan, R.R. Braga, S. Mai, L. Tjäderhane, D.H. Pashley

and F.R. Tay, Dental Mater. 26, 380 (2010).

79. Y. Nishitani, M. Yoshiyama, A.M. Donnelly, K.A. Agee, J. Sword and F.R. Tay,

J Dental Res. 85, 1016 (2006).

80. D.H. Pashley, F.R. Tay, C. Yiu, M. Hashimoto, L. Breschi, R.M. Carvalho and

S. Ito, J Dental Res. 83, 216 (2004).

81. J. Hebling, D.H. Pashley, L. Tjäderhane and F.R. Tay, J Dental Res. 84, 741

(2005).

82. M.R.O. Carrilho, R.M. Carvalho, M.F. Goes, V. di Hipolito, S. Geraldeli and

F.R. Tay, J Dental Res. 86, 90 (2007).

83. N. Hiraishi, C.K. Yiu, N.M. King and F.R. Tay, J Dentistry. 37, 440 (2009).

84. F.R. Tay, D.H. Pashley, R.J. Loushine, R.N. Weller, F. Monticelli and R.

Osorio, J Endodontics. 32, 862 (2006).

85. M. Dündar, M. Özcan, M.E. Comlekoglu, B.H. Sen. J Dental Res. 90 93-98

(2011).

42
86. L. Breschi, F. Cammelli, E. Visintini, A. Mazzoni, F. Vita, M. Carrilho, M.

Cadenaro, S. Foulger, G. Mazzoti, F.R. Tay, R. Di Lenarda and D. Pashley, J

Adhesive Dentistry. 11, 191 (2009).

87. M. Yamamoto, Metal-Ceramics. Principles and Methods of Makoto Yamamoto,

p. 15, Quintessence, Chicago, IL (1985).

88. K.J. Anusavice, Phillips' Science of Dental Materials, p. 582,

Saunders/Elsevier, St. Louis (2003).

89. W.J. O’Brien, Dental Materials and Their Selection, p. 204-207, Quintessence,

Chicago, IL (2002).

90. D.W. Berzins, B.K. Moore and D.G. Charlton. J Prosthodont. 18, 188 (2009).

91. A.B. Carr and W.A. Brantley, Int J Prosthodont. 4, 265 (1991).

92. ADA Council on Scientific Affairs, J Am Dental Assoc. 134, 347 (2003).

93. H.W. Roberts, D.W. Berzins, B.K. Moore and D.G. Charlton, J Prosthodont.

18, 188 (2009).

94. J.W. McLean. J Prosthet Dentistry. 85, 61-66 (2001).

95. R.J. Cronin and D.R. Cagna. J Am Dental Assoc.128, 425 (1997).

96. J.K. Dong, H. Luthy, A. Wohlwend and P. Scharer. Int J Prosthodont. 5, 9

(1992).

97. J.R. Kelly, Dental Clin North Am. 48, 513 (2004).

98. L. Probster. Int J Prosthodont. 6, 259 (1993).

99. J.R. Kelly, J Am Dental Assoc. 139, 4 (2008).

100. M. Kern. J Adhesion Sci Technol. 23, 1097 (2009).

101. I. Denry and J. R. Kelly, Dental Mater. 24, 299 (2008).

102. X.-H. Gu and M. Kern, Int J Prosthodont. 16, 109 (2003).

43
103. M. Dündar, M. Özcan, B. Gökçe, E. Cömlekoğlu, F. Leite and L.F. Valandro.

Dental Mater. 23, 630 (2007).

104. P. Spencer, Y. Wang and J.L. Katz, J Adhesive Dentistry. 6, 91 (2004).

105. P. Pospiech, Clinical Oral Investig. 6, 189 (2002).

106. R.J. Cronin and D.R. Cagna. J Am Dental Assoc. 128, 425 (1997).

107. J.R. Kelly, I. Nishimura and S. D. Campbell, J Prosthet Dentistry. 75, 18

(1996).

108. A.J.E. Qualtrough and V. Piddock, J. Dentistry. 25, 91 (1997).

109. J.P. Matinlinna and P.K. Vallittu, J Oral Rehabil. 34, 622-630 (2007)

110. M.B. Blatz, A. Sadan and M. Kern, Compend Contin Educ Dentistry. 25, 412

(2004).

111. R. Friederich and M. Kern, Int. J. Prosthodont. 15, 333 (2002).

112. B. Yang, H.C. Lange-Jansen, M. Scharnberg, S. Wolfart, K. Ludwig, R.

Adelung and M. Kern. Dental Mater. 24, 508 (2008).

113. B.K. Kim, H.E. Bae, J.S. Shim and K. W. Lee, J. Prosthet Dentistry. 94, 357

2005).

114. T. Derand, M. Molin and K. Kvam, Dental Mater. 21, 1158 (2005).

115. G.M. Brauer, J.W. Stansbury and J.M. Antonucci, J Dental Res. 60, 1343

(1981).

116. M. Dündar, M. Özcan, E. Çömlekoğlu and M.A. Güngör, Int J Prosthodont. 23,

151 (2010).

117. G.M. Richardson. Human and Ecological Risk Assessment, 3, 683-697 (1997)

118. A.H. Garcia, M.A.M. Lozano, J.C. Vila, A.B. Escribano and P.F. Galve, Med

Oral Patol Oral Cir Bucal. 11, 215 (2006).

119. D. Holter, H. Frey and R. Mulhaupt. Polymer Preprints 38, 84 (1997).

44
120. R. Labella, P. Lambrechts, B. Van Meerbeek and G. Vanherle. Dental Mater.

15, 128 (1999).

121. H.H. Xu, J Dental Res. 78, 1304 (1999).

122. S. Geraldeli and J. Perdigao, J Dental Res. 81, 1276 (2003).

123. B.W. Darvell, J Adhesion Sci Technol. 23, 935 (2009).

124. K.-J.M. Söderholm. J Adhesion Sci Technol. 23, 973 (2009).

125. S. Armstrong, S. Geraldeli, R. Maia, L.H.A. Raposo, C.J. Soares and J.

Yamagawa, Dental Mater. 26, 50 (2010).

126. S. Phrukkanon, M.F. Burrow and M. Tyas, Dental Mater. 14, 120 (1998).

127. A.A. El Zohairy, A.J. de Gee, N. de Jager, L.J. van Ruijven and A.J. Feilzer, J

Dental Res. 83, 420 (2004).

128. C. Goracci, F.T. Sadek, F. Monticelli, P.E. Cardoso and M. Ferrari, Dental

Mater. 20, 643 (2004).

129. C.J. Soares, P.V. Soares, P.C. Santos-Filho and S.R. Armstrong, J Dental

Res. 87, 89 (2008).

130. A. Poitevin, J. De Munck, K. Van Landuyt, E. Coutinho, M. Peumans and P.

Lambrechts, J Adhesive Dentistry. 10, 7 (2008)

131. Y. Shono, T. Ogawa, M. Terashita, R.M. Carvalho, E.L. Pashley and D.H.

Pashley. J Dental Res. 78, 99 (1999).

132. A.D. Loguercio, N. Uceda-Gomez, M.R. Carrilho and A. Reis. Dental Mater.

21, 224 (2005).

133. K.-J. Söderholm, M. Guelmann and E. Bimstein, J Adhesive Dentistry. 7, 57

(2005).

134. G. Leloup, W. D’Hoore, D. Bouter, M. Degrange and J. Vreven, J Dental Res.

80, 1605 (2001).

45
135. F.J.T. Burke, A. Hussain and G. Fleming, J Dental Res. 82, 715, (2003).

136. R. Van Noort, S. Noroozi, I. C. Howard and G. Cardew, J Dentistry. 17, 61

(1989).

137. J.P. Matinlinna and K.L. Mittal (Eds.) Adhesion Aspects in Dentistry, VSP/Brill,

Leiden (2009).

46