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Curr Oral Health Rep

DOI 10.1007/s40496-016-0108-9

DENTAL RESTORATIVE MATERIALS (M ÖZCAN, SECTION EDITOR)

The Role of Silane Coupling Agents and Universal Primers


in Durable Adhesion to Dental Restorative Materials - a Review
Muhammad Zakir 1 & Usman Ashraf 1 & Tian Tian 1 & Aifang Han 1 & Wei Qiao 1 &
Xiaozhuang Jin 1 & Meng Zhang 1,2 & James Kit-Hon Tsoi 1 & Jukka Pekka Matinlinna 1

# Springer International Publishing AG 2016

Abstract One of the most important aspects in the field of Keywords Silane . Coupling agents . Primers . Bonding
dentistry is adhesion. Adhesion can be enhanced through dif- agents . Fillers . Ceramics . Composites . Silica
ferent mechanisms, most commonly by chemical and me-
chanical modifications of dental material surfaces. One exam-
ple of chemical adhesion utilizes primers or bonding agents Introduction
containing coupling agents. Universal primers which are
(mainly organophosphate-based monomers) and silane cou- Adhesion, defined as Bsticking of two surfaces intimately
pling agents are the most effective and most widely used for together,^ is a very important phenomenon not only in den-
unifying dissimilar materials. Other than improving adhesion, tistry but also in daily life. Generally speaking, adhesion is
Silanes have many other applications in dentistry. They have about unifying two or more dissimilar materials which do not
been found also to enhance the mechanical properties of ma- have a natural affinity to each other, with or without the help
terials either by adhesion or by becoming a constituent of of another coupling material. This adhesion mechanism can
dental materials itself. Universal primers, on the other hand, also be broadly divided into two main categories: mechanical
are utilized in bonding between different dental materials such and chemical adhesions. Mechanical adhesion (retention) can
as ceramics, metals, alloys, as well as to resin composites. be established when a material is subjected to surface modifi-
Unfortunately, these primers, coupling agents, and bonding cation, increasing the surface roughness by either forming
agents have, in general, poor hydrolytic stability. They are macro- or micro-porosities. This type of adhesion relies on
susceptible to humid oral environment, which invariably ren- mechanical interlocking to increase retention and provides
der them potentially unstable in the humid oral environment as quite a good, durable form of bonding. As for chemical adhe-
saliva is always present. Improving their hydrolytic stability sion, it involves modification of the surface chemistry. During
should therefore result in stronger adhesion for dental mate- the process of adhesion, two dissimilar surfaces are connected
rials and dental prosthesis with a better clinical survival rate. by a chemically active material, which is usually liquid and
has bonding affinity to both surfaces.
The key to success in dental adhesion involves various
This article is part of the Topical Collection on Dental Restorative
Materials
factors, e.g., contact angle, purity or cleanliness of the bonding
surfaces, and presence of any debris and biofilms on the sur-
* Muhammad Zakir face. Dental adhesion involves both mechanical and chemical
mzakir@hku.hk; zakirnoormohd@gmail.com adhesion aspects. In particular, chemical adhesion is achieved
with the help of coupling agents or primers, which play a very
1
important role in dentistry.
Dental Materials Science, Faculty of Dentistry, University of Hong
Kong, 4/F, 34 Hospital Road, Sai Ying Pun, Hong Kong, SAR,
Numerous coupling agents such as organomettalic com-
People’s Republic of China pound, which includes titanates, zirconates, silanes, phos-
2
Institute of Biomedicine and Biotechnology, Shenzhen Institutes of
phates, zircoaluminates, thiones, and thiols are used in various
Advanced Technology, Chinese Academy of Sciences, industries. Some of them are used (or have been attempted) in
Shenzhen, People’s Republic of China the dental field. In general, coupling agents are synthetic
Curr Oral Health Rep

functional compounds which wet the substrate surfaces, in- promotion or surface functionalization process may also be
creasing the surface-free energy, the adhesive strength of resin achieved by using two-bottle adhesive systems. Interestingly,
cements interfaced with tooth structures, metallic and ceramic in such a system, the non-hydrolyzed silane needs to be mixed
prosthesis and not limited to crown, bridges, inlays, and with the other component, consisting of water, acetic acid, and
onlays. Silane coupling agents (silanes), because of their good ethanol before application on the bonding surface [1•, 2•]. It is
performance and biocompatibility, are the most broadly used noteworthy that such silanes would become murky or milky if
coupling agents in dentistry. Hydrophobic silane monomers they are not used once opened, or if the bottles were left open
need to be dissolved in alcohol-water solvent and, activated by without a cap. This is also why single-bottle silanes (which are
an addition of acid which makes the initially hydrophobic already in pre-hydrolyzed form) should always be stored in
silane molecules hydrophilic, i.e., they will contain silanol, dark and cold. This review gives a brief introduction regarding
−Si–OH. They condense and finally set to form a hydrophobic how and where silanes are used in dentistry.
siloxane (polysiloxane) film having different reactivity de-
pending on the silane.
Chemically speaking, silanes are synthetic organic- Applications
inorganic silicon compounds and can be further divided into
two types: functional and non-functional (Fig. 1). Functional Direct Restorative Materials
silanes have reactive functional groups at both molecular ends
which may react with two chemically dissimilar surfaces. On Particulate Fillers
the other hand, non-functional silanes have only non-reactive
groups which react with, for example, inorganic surfaces. Modern-day dental resin composites are composed of resin
Some non-functional silanes may be used for cross-linking matrix; free radical initiator; inhibitor; filler particles (e.g.,
[1•, 2•, 3]. Organo-silicon compounds contain synthetic direct lithium aluminosilicate, silica, or boron silicate); and silane
≡Si–H and ≡Si–C bonds [1•]. Given this, silanes are one of the coupling agents [14]. A silane coupling agent is used to ensure
mostly broadly and widely studied coupling agents and have a durable bonding between the filler particles and the resin ma-
very wide range of applications. They could be used, inter alia, trix. An experimental resin with silanized filler particles has
to coat building materials, silanize silicon surface for micro- been reported by Lin et al. to have higher diametral compres-
chip fabrication, water and oil repellent coatings, and as opti- sive and tensile bond strength than resin composites with non-
cal coatings. silanized filler particles [15]. Silanization of filler particles
Dental applications of silanes are mainly related to promotes wettability and dispersion, as well as decreasing
hydroxylated (−OH) surfaces, in particular using 3- the viscosity between fillers and liquid resin components;
methacryloxypropyltrimethoxysilane (MPS or y-MPS) to hence, improving the physical and mechanical properties of
coupling reactions. It is one of the most commonly used silane resin composites [16]. Additionally silanization of aluminosil-
due to its reactivity and ability to yield good, durable adhesion icate filler particles results in a stronger resin matrix and filler
between the relevant substrates [4•, 5•, 6••]. An example is bond than without silanization. Some studies further suggest
resin composites, where the silanized coating on the glass that water uptake by silanized filler particles is considerably
filler particles allow chemical bonding with the resin matrix lower than non-silanized filler particles [17].
and thus producing a dental resin composite with improved In various studies, silanization of filler particles with differ-
mechanical properties [5•, 6••, 7•, 8•]. E-glass fibers used in ent silanes like MPS, 3-mercaptopropyltrimethoxysilane
fiber-reinforced resin composites (FRCs) are also silanized. (MEPS), or amino-silanes with different surface modification
Fibers increase the strength and enhance the mechanical prop- methods were contrasted and compared to each other regard-
erties of removable prosthesis and periodontal splints [9, 10]. ing the degree of interfacial bonding using various tests. The
In terms of cementation, adhesive resin cements are used to results showed that MPS had a profound effect against wear
bond primed (acid etched and silanized) porcelain and silica- resistance and hydrolytic degradation of resin composites. On
coated metals. This is also applicable for repairs of fractured the other hand, certain experiments have also shown that the
and chipped ceramics or metals [11••, 12, 13]. Adhesion same surface treatment does not always significantly affect the
wear resistance [18].
O OH
CH3 Fibers as Fillers
X
O P
R (CH2)n Si X
H2C O
X OH In dental fiber-reinforced composites (FRcs), glass, quartz,
a O polyethylene, polyester, carbon/graphite, and polyaramid fi-
b bers have been attempted or used as the fiber filler
Fig. 1 General molecular structures of a silane and b MDP (reinforcement) whereas the polymetric matrix may consists
Curr Oral Health Rep

of various acrylic monomers. Effective reinforcement depends of Fonseca et al. [29], an increase in the flexural and compres-
on good and reliable adhesion between the filler and the ma- sive strength of the composite was observed after heat treat-
trix. The use of fiber fillers can modify the material in terms of ment on the silanized pure glass fibers. Oliveira et al. [30]
improving the mechanical properties such as flexural strength, showed an improved bonding to the glass fiber post with
impact strength, flexural modulus, failure strain, and fracture combined use of silane and adhesive. Thus, silanization of
toughness. However, if their adhesion to the matrix is too glass fibers appears to be a common and standard procedure
weak, the fillers may even weaken the material as the regions to reinforce adhesion interface. Effects of silane in some inor-
with weak adhesion act as stress concentration points. ganic dental materials are shown in Table 1 [2•].
Moreover, such voids at the fiber-matrix interface may accu- Nowadays, in the development of materials in dentistry, the
mulate and absorb water and microorganisms. utilization of other fibers, in particular micro-fibers, as filler
In the situation where direct fiber-matrix bonding is essen- components in composite materials has been suggested. For
tially weak due to their dissimilar nature, silanization is always example, dispersion of carbon nanotubes in the silane could
mandatory. Vallittu summarized the mechanism of increase the interfacial shear strength by 26.3 % [31]. Wang
silanization on different fiber types as forming a Bmatrix-R- et al. have shown that silanized zirconia micro-fibers could
Si-O–fiber^ structure, in which BR^ represents the organo- improve the fracture toughness in bis-GMA-based dental resin
functional groups in the silane molecule, BSi^ the silicon at- composite [32••]. This being said, silanes appear to have great
om, and BO^ the oxygen atom [19]. Alongside with providing potential and wide applications as coupling agents for many
a chemical bond, silanes can re-activate and wet silanized other kinds of fibers other than glass for reinforcement. Given
surfaces, which could enhance the resistance of the interface this, new types of fiber reinforced composites could be
to hydrolysis and protect the fiber filler from damage during invented for clinical use.
handling [20].
It is worth pointing out that a silane selected for adhesion Indirect Restorative Materials
promotion, should chemically and sterically match the types
of fiber and resin to be bonded. For example, polyester fibers Glass Ceramics
react readily with epoxy or melamine groups in the organic
matrix, but if these functional groups are not present in the In addition to being used as a coupling agent to reinforce
matrix, a silane with these functional groups should be applied fillers in resin composites, silanes also plays an important role
as an intermediate to strengthen adhesion. One example is in resin-substrate bonding. Such substrates include ceramic
polyethylene (PE) fibers which are inert and lack reliable ad- restorations and their repair, and silica = coated porcelain-
hesion to the resin matrix at their interface, due to the non- fused metal (PFM) or some other silica-coated metal restora-
polar nature and low surface energy of the PE fibers. This has tions [2•].
been a challenge in dental materials research for years, and Although silane coupling agents are able to promote adhe-
various treatments have been attempted to modify the surface sion between resin cement and ceramics and metals, the bond
conditions of polyethylene fibers, including chemical modifi- it is not 100 % stable over time and is susceptible to moisture.
cation, chemical grafting, oxygen plasma, high energy laser, A study reveals that adhesion is relatively weaker with non-
UV, gamma irradiation, corona discharge, and silane treatment silica-based materials (e.g., alumina, zirconia, and non-silica-
[21–27]. Recently Bahramian et al. used MPS on the corona- coated metal alloy materials) compared to silica-based ce-
treated polyethylene fibers, and obtained good, positive re- ramics [33••]. This implies that a suitable surface pre-
sults in the fiber-matrix adhesion [27]. Therefore, it is impor- treatment protocol is required before silanization in order for
tant that a proper silane with the complementary surface better (more durable) adhesion promotion. Indeed, some pre-
chemistry be chosen for optimal adhesion. treatment methods such as silica-coating before silanization
Bonding of a fiber reinforced composite (e.g., a fiber post) has been proven to improve the adhesion, i.e., significantly
to resin cement greatly relies on the adhesion of fiber to the increased bond strengths have been obtained in vitro [33••, 34,
resin cement. Clinically, etching on the bonding surface of the 35].
composite is always recommended to expose the fibers. In particular, several silane coupling agents have used to
Efforts have been done to improve the efficiency of acid (hydrofluoric acid) etch glass ceramics to enhance the
silanization. For example, Kim et al. [28] proposed applying chemical bonding between resin composite and ceramics
a non-organo-functional cross-linking silane, 1,2-bis(- [36–40]. As aforementioned, MPS is the most commonly used
triethoxysilyl)ethane (BTSE) blended with a normal organo- silane for resin-ceramic bonding. In addition, it was worth
functional silane (such as MPS), whereas Samimi et al. [20] noting that functional silanes such as MPS blended with 1,2-
suggested removing extra silane from the silanized fiber post bis(trimethoxysilyl)ethane (BTSE) could significantly in-
surface with warm water and warm air to achieve a stronger crease the resin to leucite-reinforced ceramic shear bond ad-
and hydrolytically stable bonding to resin cement. In the study hesion strength after thermo-cycling [41]. Thus, silanes and
Curr Oral Health Rep

Table 1 Effect of silane coupling agents with some substrates [2•]

Effect of silane coupling agents with some substrates [2].

Silica

Greater adhesion
Quartz

Glass

Silicon

Titanium, Chromium

Steel

Nickel

Zinc
Less adhesion

Gypsum

their blends are very effective in promoting adhesion for glass satisfactory adhesion, a reduction of the silane coating thick-
ceramics. ness on the ceramic surface is recommended. For example,
Silanes have been shown to reduce the contact angle and heat treatment by using a hot air stream has been shown to
hence, they increase the wettability of glass ceramic surface reduce the silane coating thickness [46••, 47]. This could in-
[42••, 43]. Under normal clinical circumstances, the silane crease the micro-tensile bond strength between leucite-
layer is found to be around 10∼50-nm thick [44••]. If silane reinforced ceramic and resin cement significantly. Heat treat-
layers are successively applied on the surface, cohesive de- ment has been shown to enhance bonding performance of
struction of layers might occur [45••]. As a self-assembled silanes such as 3-methacryloxypropylmethyldimethoxy silane
ultra-thin film, silane has a weaker mechanical strength than (MPS), 3-methacryloxypropyltriethoxysilane (MTES), and 3-
resin and ceramic, and is regarded as the weakest point in the acryloxypropyltrimethoxysilane (ACPS) [48]. Nonetheless,
resin-ceramic joint adhesion system. Thus, in order to achieve another study showed that the heat treatment of silane did
Curr Oral Health Rep

improve the bond strength, but not statistically significantly [19, 60, 65, 66]. While silanization is a well-recognized and
[49]. Thus, to optimize the bond between resin and ceramic, acknowledged pre-treatment step before resin composite ce-
the chemical composition of primer seems to play a greater ment bonding to feldspathic ceramics which contains a large
role than heat treatment [39]. amount of silica. When alumina and zirconia ceramics are
Furthermore, it is not only the silane monomers, but also used, silanization should be carried out only after these high-
other primer ingredients that could have considerable effect on strength ceramics are silica-coated [64] since these ceramics
adhesion [40, 41, 43]. It was suggested that 10- are inherently silica free [67, 68]. This could be achieved by
methacryloyloxydecyl dihydrogen phosphate (MDP) (Fig. 1) grit-blasting the oxide ceramic surface with silica-coated alu-
has the potential to improve bonding between zirconia and mina particles under air compression [69••]. This method pro-
resin composite cement. However, a recent study showed a vides the oxide ceramic surface with an additional silica com-
contrasting result, where glass ceramics treated solely with ponent, so that the procedure of silanization could be facilitat-
silane solutions exhibited better bonding with resin cements ed. The oxide ceramic restoration may then be satisfactorily
than ceramics treated with a primer containing both silane and and reliably cemented using resin composite cement.
MDP [50]. With regards to hydrochloric acid (HCl) addition Several studies have focused on the improvement of silane
to primers, a significant increase in the shear bond strength coupling agent application [71, 79]. It was reported that a
between resin composite and a leucite-reinforced ceramic after silane coupling agent added to an adhesive phosphate mono-
thermo-cycling was observed. It was postulated that HCl mer primer can achieve superior long-term shear bond
might act as an effective accelerator during the hydrolysis strength for zirconia restorations with resin composite ce-
reaction of the methoxy part of the silane [41]. ments [70]. A study by Kitayama et al. revealed significantly
MPS is commonly used in dentistry as pre-hydrolyzed higher bond strengths obtained by using a novel single-
form in a single bottle. One study discovered that when the component silane coupling agent than using a mixture of a
silane was applied to the surface of leucite-reinforced ceramic, dentine primer/and silane coupling agent [71].
there was no significant difference in the tensile bond strength Recently, some researchers have developed several universal
when a pre-activated silane solution was used. It was based on silane primers [72, 73]. A study by Aboushelib et al. applied
MPS, acetic acid, and ethanol, even when they were stored for some novel primers 3-acryloyloxypropyltrimethoxysilane, 3-
up to 1 year at room temperature [51]. However, pre- isocyanatopropyltriethoxysilane, 3-styrylethyltrimethoxysilane,
hydrolyzed silane solutions in a single bottle have relatively and 3-methacryloyloxypropyltrimethoxysilane in combination
short shelf lives. It must be stressed that the solution is no with the selective infiltration etching (SIE) surface pre-
longer usable when it has turned cloudy or milky after opening treatment for resin-ceramic bonding [74•]. Such novel primers
[2•]. contain some organo-functional groups and have the potential of
improving silane monomers function. Matinlinna et al. also
Oxide Ceramics found an increase in the bond strength after these primers were
applied to silica-coated zirconia [75]. Such a blended silane sys-
Oxide ceramics including alumina (Al2O3) and zirconia tem was shown in a laboratory study [42••] to enhance the shear
(ZrO2) are popular in dental restorations due to their superior bond (adhesion) strength between resin and zirconia, especially
esthetic and high-fracture resistance properties [52–56]. A after artificial speeded aging, thermo-cycling. Thus, it seems to
small amount of yttria (Y2O3) is usually added to zirconia to be that blended systems might be a promising solution to en-
improve the properties of fracture toughness, cohesion, flex- hance adhesion, particularly with regards to dental ceramics.
ural strength. and wear resistance, forming yttria tetragonal
zirconia polycrystals (TZP) [57]. Metals and Alloys
Resin composite cements have several advantages,
allowing for shade matching, better marginal adaptation, Along with polymers and non-metallic inorganic ceramics,
higher flexural strength, and fracture resistance. Therefore, metals and alloys have contributed as a major source of ma-
they are widely used for cementation of ceramic restorations terials in dentistry. Far back in the past, ancient people used to
to achieve strong adhesion [58, 60]. Both micro-mechanical replace tooth structures with ivory and gold. It is evident that
interlocking and chemical bonding are required [58, 60, 61]. metals and their alloys nowadays have outstanding functional
A silane coupling agent is often used on the ceramic sur- performance, with appealing properties in brittleness, hard-
face before resin composite cement application. One function ness, wear resistance, etc. [76]. Along with their consistent
of silane coupling agent is to increase the surface-free energy and reliable biocompatible properties, a variety of metals
of the ceramic surface [2•, 9, 59, 62–64]. Also, they are capa- and metal alloys are involved in a wide range of applications
ble of forming a siloxane (polysiloxane) network (film) with in dental and medical restorations and appliances. In practice,
the silica phase in ceramics and, simultaneously, co- they are mainly casted for prosthetic uses. Their application is
polymerizing with the organic matrix of the resin composite not limited to onlays, inlays, partial crowns, full crowns,
Curr Oral Health Rep

bridges, endodontic posts, partial dental framework, arch vinylbenzyl)propylamino]-1,3,5-triazine-2,4-dithione


wires, brackets, and implant abutments. Different metallic (VBATDT) and 10-methacryloyloxydecyl dihydrogen phos-
dental materials are named according to the abbreviation of phate (MDP). Monomers for bonding metal alloys with resin
the principal components in that alloy. A general catalog of composite are bi-functional in structure. The base metal alloy
popular alloys may be Co–Cr, Ni–Cr, Ni–Ti, dental silver surfaces are bonded to phosphoric acid group of MDP and resin
amalgam, commercially pure Ti, Au–Pd–Ag, Pd–Ag–Sn, composite is bonded to the double bonds on the other end of the
stainless steel, and so on. MDP molecules. For bonding to noble metal alloys, one end of
The type of bonding between the atoms characterizes the VBATDT (Fig. 1) contains a methacrylate (or similar groups) for
properties of metals. Here, the average bond length of metallic resin bonding, whereas, the mercampto(thiol) groups (−SH) on
bond is 0.4 nm. This being said, the average bond energy for the other end of the primers are for bonding to metal alloys.
metallic bond is ca. 250 kJ/mol. Unlike covalent bonds in Additionally, MDP enhances the reaction between VBATDT
polymers, mobility is achieved by the outer shell of metal and precious metals. It is available for bonding resin composite
electrons. Thus, large amounts of electrons transfer and move cement to dentine and ceramics, as well as bonding metals with
within the metal matter. This accounts for some special metal- methylmethacrylate (MMA), a denture base material [79].
lic properties such as ductility, metallic luster, and thermal and Hydroxyethylmethacrylate (HEMA) also enhances resin-metal
electrical conductivity. Longevity and biocompatibility are bonding. In some commercial brands, N-methacryloyl-5-
ideal for many metals in use in dentistry. aminosalicylic acid (5-NMSA) and polymerization accelerators
In dentistry, bonding to metals is an essential step to utilize are added into the commercial primer contents [80]. Also, 4-
them along with their said benefits [77••]. Though soldering methacryloxyethyl trimellitate anhydride (4-META) is a mono-
and welding are common bonding procedures in industry, they mer commonly used with methyl methacrylate (MMA)-tri-n-bu-
are less practical for permanent restorations in the oral cavity. tyl borane (TBB) resin, yielding the 4-META/MMA-TBB resin
Here, mechanical and chemical adhesions assume much great- cement for bonding metals [81].
er importance. Application of metal primers, metal condi- Silanes act as coupling agents similar to metal primers, for
tioners, and coupling agents, e.g., silane is beneficial in adhe- bonding resin composites to silica-coated metals. Many
sion promotion to (in case of silanes, silica-coated) metals and available products contain methacrylate silane such as
alloys. The technique of grit-blasting significantly optimizes 3-methacryloxypropyltrimethoxysilane (MPS) [4•].
the bonding outcome by pre-treating the surface of metals. Commercial MPS-based silanes usually contain ca.
The airborne particles could clean, roughen, or coat the metal 1–2 wt% of silane dissolved in ethanol and water. A novel
surface with silica particles. Common particle sizes include acrylate silane system with a functional silane, i.e., (3-
30, 50, and 110 μm. Alumina or silica-coated alumina is the acryloxypropyl) trimethoxysilane (ACPS) and a cross-
main component of the particles. Through the silica-coating linking silane 1, 2-bis(triethoxysilyl)ethane (BTSE) have also
the particles can be linked to silane coupling agent, thus achieved appealing bonding ability. This is called a novel
achieving a desirable bonding outcome. As grit-blasting is silane system (NSS) [82].
suitable for noble and base metal alloys, both can be treated
and cemented [78••]. Alloy surfaces are cleaned and silica- Others
coated, followed by silane application with a fine, clean brush
and are allowed to dry. At this point, the interface is ready for Acrylic polymers are among the most commonly used dental
further immediate application of resin composite cement, restorative materials for decades. The reason for their popu-
methyl methacrylates, and opaquer. In addition to the tribo- larity in fabricating artificial teeth, denture base, and tempo-
chemical method (silica-coating), acid etching, and rary crowns is their ease of handling, satisfactory esthetics,
electrolytical coating are possible alternatives to surface treat chemical stability, and affordability. De-bonding of acrylic
before bonding. The optimal parameters for acid etching, in- teeth from the denture base is reported as the most common
cluding etching time, acid type, concentration, and density type of failure in acrylic resin denture. Laboratory investiga-
may vary among the different metals. For electrolyte coating, tions have demonstrated that the application of silane coupling
tin crystal structures could form on the metal surface by tin- agent could significantly increase the bonding strength of
plating after the grit-blasting. These are commendable ap- acrylic denture base to acrylic teeth [83] or gingival shade
proaches, yet contamination is possible at the interface with resin composite [84]. Silane coupling agents were also found
both alternatives and the treated alloy surface does not differ to be effective as the pre-treatment for bonding between auto-
much from untreated cases, which is in contrast to grit- polymerizing repair resin and nylon polymer denture base
blasting [47]. material [85]. It was hypothesized that a silane coupling agent,
Akin to other bonding agents, an alloy primer usually when used with dichloromethane, might result in morpholog-
contains key components that could function and promote ical change of the denture base resin and the coupling of resin
adhesion between dissimilar materials, e.g., 6-[N-(4- composite to the filler particles [84]. On the other hand, when
Curr Oral Health Rep

used as the pre-treatment for the bonding between acrylic resin compared to other coupling agents, such as zirconates, tita-
denture base and silicone-based soft liner, silane coupling nates, phosphates, thiols, and zircon-aluminates. Silanes have
agents failed to achieve a significant improvement in the been introduced into dentistry after an extensive usage in in-
bonding strength [86]. This was not a surprise as silicones dustrial applications—and they will remain in dentistry, prob-
are hydrophobic. ably with expanding, new applications.
Polyether ether ketone (PEEK) has been recognized as a fa- It has been seen in previous studies that silanes form a
vorable restorative material due to its notable mechanical prop- weaker bond with non-silica-based ceramic materials. This,
erties, tooth color, biocompatibility, and stability [87, 88]. The along with the relatively low long-term hydrolytic stability
applications of PEEK include implant abutments, implant- of the silanes might be a concern. This might be improved
supported bar/clamp, and fixed dental restorations [89]. by different surface conditioning methods or utilizing other
However, sufficient bonding strength of PEEK to titanium, zir- functional groups in silanes. These improvements could fur-
conia, and resin composites cannot be achieved easily because it ther expand their applications in dentistry and possibly in oth-
is resistant to surface modification by various mechanical and er fields as well.
chemical treatments [90, 91]. Recent studies have showed that
the application of a primer containing methacrylate silane, phos- Acknowledements The authors would like to acknowledge and thank
phoric acid methacrylate, and sulfide methacrylate resulted in Ms. Madeline Yon for proof reading the article.
significantly enhanced tensile bond strength of resin composites
Compliance With Ethical Standards
on air-abraded PEEK [88, 92]. In contrast, a primer containing 3-
methacryloxypropyltrimethoxysilane, MDP, and ethanol did not Conflict of Interest All the authors of this review article declare that
contribute to the bonding strength at all [88, 93]. The author they have no conflict of interest.
attributed this phenomenon to the occupied functional groups
Human and Animal Rights and Informed Consent This article does
of the bi-functional MDP monomer by the phosphate groups, not contain any studies with human or animal subject performed by any
which impeded their further chemical reaction with the PEEK of the authors.
substrate or the resin composites [88].
Companies like Kuraray and Ivoclar-Vivadent have al-
ready introduced silane primers into the dental market.
These primers contain the most commonly used phosphate
coupling agents MDP and MPS in a combination. MDP bonds References
well with oxide ceramics and silanes bond well with silica-
based ceramics. They can be referred to as universal primers Papers of particular interest, published recently, have been
as well in a way that they bond with most, if not all, types of highlighted as:
ceramics, including zirconia, porcelain, alumina, leucite, and • Of importance
lithium di-silicate.
It can be said that MDP and MPS in a one-bottle system,
play a very important factor in resin-zirconia bonding [94]. 1.• C.Y.K. Lung and J.P. Matinlinna, Silanes for adhesion promotion
The presence of a functional monomer (MDP) and bi- and surface modification, in Silane Chemistry, Applications and
Performance, K. Moriguchi and S. Utagawa (Eds.), pg., 87–109.
functional monomer (silane, MPS) give good adhesion results Nova Science Publisher, Hauppage, NY (2013). Gives basic un-
for both etchable and non-etchable ceramics in dentistry. derstanding of primers.
Some well-known commercial silane primers produce durable 2.• Lung CYK, Matinlinna JP. Aspects of silane coupling agents and
adhesion for short and long terms when bonding zirconia with surface conditioning in dentistry: an overview. Dental Mater.
2012;28:467–77. Gives ample information of primers in
resin composite cement [95]. The combination of such uni-
dentistry.
versal primers (chemical modifiers) alongside with modifica- 3. Plueddemann EP. Silane coupling agents. 2nd ed. New York:
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Many different types of primers are available for bonding grit-blasting effect on zirconia followed by silanization.
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Curr Oral Health Rep

7.• Ho GW, Matinlinna JP. Insights into ceramics as dental materials 28. Kim YK, Son JS, Kim K-H, Kwon T-Y. A simple 2-step silane
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46.•• Matinlinna JP, Mittal KL, Adhesion aspects in dentistry. Leiden, 69.•• Ozcan M, Matinlinna JP. Surface conditioning protocol for the ad-
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