d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28

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Review

Silane adhesion mechanism in dental applications

and surface treatments: A review

Jukka Pekka Matinlinna ∗ , Christie Ying Kei Lung ∗ , James Kit Hon Tsoi
Dental Materials Science, Applied Oral Sciences, Faculty of Dentistry, The University of Hong Kong, Hong Kong, China

a r t i c l e i n f o a b s t r a c t

Article history: Objective. To give a current review of silane adhesion chemistry, applications of silane cou-
Received 1 September 2017 pling agents and related surface pretreatment methods in contemporary dentistry.
Accepted 4 September 2017 Methods. Silane coupling agents are adhesion promoters to chemically unify dissimilar mate-
rials used in dentistry. Silanes are very effective in adhesion promotion between resin
composites and silica-based or silica-coated indirect restorative materials. It is generally
Keywords: accepted that for non-silica-based restorations, surface pretreatment is a mandatory pre-
Silane liminary step to increase the silica content and then, with help of silane, improve resin
Adhesion chemistry bonding. This review discusses the silane-based adhesion chemistry, silane applications in
Dental restorative materials dentistry, surface pretreatment methods, and presents the recent development of silane
Bonding coupling agents.
Resin composites Results. A silane coupling agent is considered a reliable, good adhesion promoter to silica-
based (or silica-coated) indirect restorations. Surface pre-treatment steps, e.g., acid etching
for porcelain and tribo-chemical silica-coating for metal alloys, is used before silanization
to attain strong, durable bonding of the substrate to resin composite. In clinical practice,
however, the main problem of resin bonding using silanes and other coupling agents is the
weakening of the bond (degradation) in the wet oral environment over time.
Significance. A silane coupling agent is a justified and popular adhesion promoter (adhesive
primer) used in dentistry. The commercial available silane coupling agents can fulfil the
requirements in clinical practice for durable bonding. Development of new silane coupling
agents, their optimization, and surface treatment methods are in progress to address the
long term resin bond durability and are highly important.
© 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Contents

1. Introduction: silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2. Silane coupling agents in dentistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. Silane chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

∗
Corresponding authors at: Dental Materials Science, Applied Oral Sciences, Faculty of Dentistry, The University of Hong Kong, 1/F, Prince
Philip Dental Hospital, 34 Hospital Road, Sai Ying Pun, Hong Kong, China. Fax: +852 2548 9464.
E-mail addresses: jpmat@hku.hk (J.P. Matinlinna), yklung@graduate.hku.hk (C.Y.K. Lung), jkht@hku.hk (J.K.H. Tsoi).
https://doi.org/10.1016/j.dental.2017.09.002
0109-5641/© 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
14 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28

3.1. Silane hydrolysis and activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

3.2. Factors affecting silane hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3. Silane adhesion mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4. Functional silanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.5. Non-functional silanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4. Surface treatments methods for indirect restorations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.1. Grit blasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.2. Pyrochemical silica coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.3. Tribochemical silica-coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4. Chemical treatments by acids and bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. Other surface treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.1. Selective infiltration etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.2. Nano-structured alumina coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.3. Chemical vapour deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.4. Laser treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.5. Internal coating method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.6. Sol-gel coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.7. Plasma fluorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.8. Nano-silica coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.9. Silicone-based coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6. Applications of silanes in dentistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.1. Dental ceramic restorations and repairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.2. Glass fibre-reinforced composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.3. Resin composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
6.4. Titanium, base metal and noble metal alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7. Development of coupling agents in dentistry: present and future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

ever, silicon can form indefinitely long chains, but with oxygen
1. Introduction: silicon atoms to form a siloxane linkage ( O Si O )n because of a
very strong Si O bond energy (368 kJ/mol) [1].
Silicon (Si) belongs to the main Group 14 (formerly IVA) with
That said, silicon compounds are more reactive than car-
carbon (C), germanium (Ge), tin (Sn), and lead (Pb) on the peri-
bon compounds because of the presence of vacant 3d orbital.
odic table and it has four valence electrons. There is another
Silicon tetrachloride (SiCl4 ) hydrolyses instantly to yield sili-
four valent group of elements, Group 4 (IVB), transition metals
cic acid, Si(OH)4 , but carbon tetrachloride (CCl4 ) would not
such as titanium (Ti), zirconium (Zr), hafnium (Hf), and ruther-
undergo hydrolysis. We may say that organosilicon chemistry
fordium (Rf) also with four valence electrons for the elements.
is, in general, easier to manage than all-carbon chemistry.
The difference between the two groups is a partial filling elec-
Organosilicon compounds are widely found in adhesives,
tron configuration of 3d–5d orbitals in Group 14 4. The empty
coatings, caulks, and sealers. Other remarkable uses include
3d orbital of Si makes it chemically different from other Group
both plant and agricultural control chemicals (fungicides and
14 elements, in terms of structure, reactivity and thereby phys-
herbicides).
ical and chemical properties.
On the other hand, Si has several drawbacks as a viable
Carbon (6 C) is a typical non-metal and silicon (14 Si) is a met-
alternative to C. Silicon interacts with very few other types of
alloid, semi-metal (a semiconductor). The metallic character
atoms because it is lacking the ability to form chemical bonds
increases down the group with tin and lead as the metals.
with diverse types of atoms required for metabolism. This is
Carbon occurs as graphite and diamond (allotropes), silicon is
because of its atomic size. Elements forming organic func-
found as silica (silicon dioxide, SiO2 ) and numerous silicates
tional groups with carbon include hydrogen, oxygen, nitrogen,
and alumino-silicates in earth. The electronic configuration
phosphorus, sulfur, and metals, such as Fe, Mg, and Zn [2,3].
of C is 1s2 2s2 2p2 and for Si 1s2 2s2 2p6 3s2 3p2 3d0 . They have, in
By strict definition, silane can refer to SiH4 , a group 14
some aspect, similar unique properties that distinguish them
hydride (analogous to methane, CH4 ), used as a precursor to
from the other element group members. Both C and Si have
elemental Si. Nevertheless, silane refers in aprticular to a vast
catenation property which decreases dramatically down the
amount of compounds with four substituents on Si. They are
group. Carbon can form “endlessly” long chains with other
saturated compounds (i.e., no Si Si bond) with one or more Si
carbon atoms ( C C )n . Silicon can also bond to other sili-
atoms linked to other elements. A silane contains a synthetic
con atoms ( Si Si )n but with farshorter chain length (only
silicon to carbon ( Si C ) bond. This bond is very strong and
up to 2–3 units) and such compounds are, in contrary, unsta-
stable [4].
ble. This is owing to the C C bond energy (356 kJ/mol) which
Organosilanes are synthesized from SiO2 , silica (silicon
is much higher than the Si Si bond energy (226 kJ/mol). How-
dioxide) one of the most abundant materials in the earth,
 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
through a series of reaction. Silica is reduced to silicon which
reacts with hydrogen chloride to yield trichlorosilane, HSiCl3 .
Then, trichlorosilane reacts with alkene and finally followed
by alcoholysis, i.e., reaction with alcohol, to form the func-
tional silanes [5]:

SiO2 + C→Si + CO2

Si + 3HCL−−−−−−→HSiCl3 + H2
Cu catalyst
HSiCl3 + LCH = CH2 −−−−−−→LCH2 CH2 SiCl3
Pt catalyst
LCH2 CH2 SiCl3 + 3ROH → LCH2 CH2 Si(OR)3 + 3HCl
Adhesion between resin composite cement to indirect den-
tal restorations is a vital factor for clinical success.
A silane coupling agent is very effective to bond silica-
based restorative materials such as resin composite luting
cement to acid-etched porcelain. However, bonding to non-
silica based materials such as zirconia using silane alone is not
adequate. To improve adhesion to non-silica based materials,
a selected, specific surface pretreatment is the most effective
way to tackle the problem.
The indications of silane coupling agents in dentistry
include (but are not limited to) cementation of indirect
ceramic and metallic restorations [6–10], ceramic laminates,
and ceramic repairs [11,12], E-glass fiber reinforced resin com-
posites [13], and filler reinforced resin composites (cements
and filling materials) [14].
In this review, we are discussing and summarizing the
silane adhesion chemistry, recent advances in silane appli-
cations in dentistry, and relevant surface treatment methods
[15].
2. Silane coupling agents in dentistry
Commercially available silane coupling agents
in dentistry contain trialkoxysilane, such as 3-
methacryloxyproyltrimethoxysilane (MPS) as the reactive
key component. It is diluted and dissolved in ethanol and
water and the pH adjusted at ca. 2–6 for hydrolysis (activation).
The silane concentration can vary between ca. 1–10 vol% in
different commercial products (Table 1). For one bottle pre-
hydrolysed (pre-activated) silane primers, the solution may
turn hazy over time after the first opening of use and cannot
be used anymore. This is due to the excess formation of
siloxane oligomers/polymers that are inactive. Alternatively,
two-bottle silane system have been introduced to prolong the
shelf life and increase the initial reactivity. The one bottle can
contain unhydrolysed silane monomer dissolved in ethanol
and the other one contains aqueous acetic acid. They are
mixed immediately before immediate use to allow silane to
hydrolyze.
15
3. Silane chemistry
3.1. Silane hydrolysis and activation
A silane coupling agent, which is a trialkoxysilane, contains
two functional groups at the ends of its molecular back
(1) bone, and which connect an unpolymerized resin matrix
and an inorganic substrate (surface). A general formula
for such bifunctional silane is L-(CH2 )k -Si-(OR)3 , where L is
(2) an organofunctional group (e.g., methacrylate, acrylate, iso-
cyanato, epoxy), (CH2 )k is a linker (spacer) group that
separates the organofunctional group and the Si atom and
(3) OR is ahydrolysable alkoxyl group (methoxy, ethoxy). At
ambient temperature, silane is activated by acid (acetic acid)
to form silanol ( SiOH) before they can bond to the inorganic
substrate [16].
(4)
The hydrolysis mechanism consists of a series of reac-
tion steps. The first step is fast and reversible protonation
of the alkoxy group at pH 4. It is followed by a bimolecu-
lar nucleophilic substitution (SN 2) reaction at the central Si.
The nucleophile, water H O H, attacks from the backside to
the Si atom (electrophilic centre). A very short-term penta-
coordinate trigonal bipyramidal transition state is formed.
Next, a new bond is formed with water (nucleophile) and
a bond is cleaved between the alcohol (leaving group) and
the silicon atom. This gives the hydrolyzed product with an
inversion of configuration. The hydrolysis process stepwise
continues until all alkoxy groups are substituted (Fig. 1) [17].
The hydrolysis of some silanes, e.g., chlorosilane, is very
useful in the production of silicones, important polymers used
as biomaterials in medicine and dentistry. The elemental sili-
con produced from the reduction of quartz (Eq. (1)) is used to
prepare dichlorosilane. This is followed by hydrolysis to pro-
duce a disilanol and finally polycondensation takes place to
yield polydimethylsiloxane [18]:
250−550 ◦ C
Si + 2CH3 Cl−−−−−−→(CH3 )2 SiCl2 (5)
Cu catalyst
(CH3 )2 SiCl2 + 2H2 O → (CH3 )2 Si(OH)2 + 2HCl (6)
(CH3 )2 Si(OH)2 −−−−−−−→ [Si(CH3 )2 O]x + H2 O (7)
acid catalyst
3.2. Factors affecting silane hydrolysis
The rate of silane hydrolysis depends among others on the
silane molecular structure, its concentration, pH, tempera-
ture, humidity, and solvent system. Ethanol is usually a part
of the solvent system as silanes dissolve easily in ethanol but
not in water.
The bulkiness of alkoxy groups would affect the rate
of hydrolysis. For silane coupling agents with bulky alkoxy
groups, the steric repulsion of water moving towards to the
silicon atom is increased (Fig. 2) [19]. This said, the hydrolysis
rate decreases with the large size of alkoxy groups: pen-
toxy < butoxy < propoxy < ethoxy < methoxy.
The silane hydrolysis is strongly pH dependent. The silane
hydrolysis rate is fast at acidic and alkaline medium but it
reaches a minimum at neutral pH for alkoxysilanes (Fig. 3).
 16
Table 1 – Examples of commercial silanes used today in dentistry (updated from Ref. [15]).
Name Manufacturer Effective silane (%) pH Solution and Indication Date of information
concentration (%)
Bisco porcelain primer Bisco, Schaumburg, IL, ‘A silane’, 1–5 5.9 Alcohol 30–50 Porcelain, composite February 2016
USA Acetone 30–50
Bisco bis silane (a Bisco, Schaumburg, IL, 3- 4 Ethanol 50–75 Porcelain, composite April 2015
two-bottle system) USA (Trimethoxysilyl)propyl-

d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
2-methyl-2-propenoic
acid, 5–10
Calibra silane coupling Dentsply, Ausrralia ‘Silane’, N/A 5.5 Acetone 50–100 Repair of ceramics, November 2016
agent metals
Ceramic bond VOCO, Cuxhaven, ‘Silane’, N/A 5.5 Acetone 50–100 Repair of ceramics, December 2016
Germany metals
Cimara VOCO, Cuxhaven, MPS, 3 5.5 Propan-2-ol 50–100 Repairs of ceramics February 2017
Germany
Clearfil ceramic primer Kuraray, Osaka, Japan MPS < 5, MDP N/A 3 Ethanol > 80 Porcelain, ceramics, May 2016
resin-based materials
Clearfil porcelain bond Kuraray, Osaka, Japan MPS 40–60 2.3 Hydrophobic aromatic Porcelain, porcelain May 2016
activator dimethacrylate repair
ESPE Sil ESPE Dental, Seefeld, ‘MPS’ < 3 4.5 Ethanol > 97 Metals, ceramics, February 2016
Germany Methyl ethyl ketone < 2 composites
ESPE RelyX ceramic 3M ESPE, St. Paul, MN, ‘MPS’, <2 4.6 Ethanol, 70–80 Ceramic primer, February 2016
primer USA Water, 20–30 laminates
Pulpdent silane bond Pulpdent, Watertown, A silane, N/A 6.3 Ethanol, 92 Porcelain, composites July 2015
enhancer MN, USA Acetone, 7
Ultradent silane Ultradent Products, MPS < 10 5.3 Propan-2-ol < 95 Porcelain, Resin February 2015
South Jordan, UT, USA composites
VITASIL VITA Zahnfabrik MPS, <2.5 N/A Ethanol, 25–50 Ceramic and resin July 2015
composite
 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
Fig. 1 – Silane hydrolysis mechanism in an acidic medium. Note: OR is an alkoxy group and Z is an organofunctional group
(modified from Ref. [16]).
Fig. 2 – Ball and stick model showing the steric effect of
alkoxy groups: methoxy vs. pentoxy groups. The
nucleophile, water, encounters greater steric repulsion
from pentoxy groups.
Fig. 3 – pH profile for the hydrolysis of alkoxysilane
(modified from Ref. [20]). Note: color change shows the
slope changes from negative to minimum to positive.
The H+ and OH− ions act as a catalyst to speed up the silane
hydrolysis by forming an activated pentavalent intermediate
to facilitate the nucleophilic attack by water [20].
17
Temperature is an important parameter: the hydrolysis
reaction rate increases with temperature that follows the
Arrhenius law. A plot of log rate constant as a function of
1/temperature gives a straight line (the Arrhenius equation:
Ea
log k = log A − 2.303RT where k = rate constant, A = Arrhenius
frequency factor, Ea = activation energy, R = gas constant and
T = temperature, in K) [21].
The hydrolysis rate is dependent on the nature of co-
solvent in the solvent mixture. The hydrolysis rate depends
on the hydrophilicity of the solvent. As the hydrophilic-
ity decreases from methanol, ethanol, and propan-1-ol, the
hydrolysis rate decreases. This is due to the ability to isolate
“the free” water molecule from the bulk water state (hydrogen-
bonded network structure), see Eq. (8) [22]. The “free” water
molecule then participates in the silane hydrolysis reaction.
However, methanol is toxic and ethanol is used as the co-
solvent.
H2 O(bulkH-bonded) → H2 O(free) (8)
3.3. Silane adhesion mechanism
The adhesion strength of silane varies with different mate-
rials. The strongest adhesion is attained with silica, glass
and quartz which form strong siloxane ( Si O Si ) linkages
through the condensation with surface hydroxyl groups on
the substrate. Mild adhesion is obtained with pure metals
and metal alloys by forming Si O M linkages. For gypsum,
graphite and carbon black, a negligible concentration of sur-
face hydroxyl groups, OH, makes it difficult to form bonding
with silane (Fig. 4) [23].
There are the two critical steps of resin substrate bonding
formation with silane coupling agents: (1) silane and substrate
bond formation — activated by acid, and (2) resin and silane
bond formation — activated by light curing.
Silane is activated by acid to form silanol groups which
react with the substrate surface hydroxyl ( OH) groups
by a condensation reaction (Si-OH + HO-substrate ⇒ Si-O-
substrate) when it is applied onto a surface treated, e.g. a silica
coated substrate.
The reaction between the organofunctional groups of
silane (with a C C bond), and functional groups of the resin
18 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28

Fig. 5 – Adhesion mechanism of resin bonding to silica coated substrates by an application of silane coupling agent (using
3-methacryloxypropyltrimethoxysilane as an example).

resin monomer or in the silane molecule to generate reac-

Fig. 4 – Relative adhesive strength of silane to different
materials (modified from Ref. [16]).
tive free radicals. Reaction of these free radicals between resin
monomers and silane molecules forms a new C C sigma bond.
As a result, resin composite and the substrate surface are con-
nected by the silane coupling agent [24]. A suggested reaction
scheme of the whole process is shown in (Fig. 5).
The formation of a functional silane monolayer on the sur-
face of restorative materials is one of the factors critical to
the adhesion. This minimizes the formation of physisorbed
silanes, i.e., a weakly bonded multi-layer coating that affects
the adhesive strength. The thickness of a self-assembled
monolayer of functional silane films can be measured by opti-
cal ellipsometry. The monolayer is formed by liquid deposition
by immersing silicon wafers into the two functional silane
solutions at different times followed (Table 2) [25]. The thick-
ness of some silane films measured is close to the theoretical
silane chain length of ca. 1.0 nm [25].

3.4. Functional silanes

monomers containing C C bond is induced by the reac-
tive free radicals generated by photo-activation of initiator
components in the resin matrix. The initiator in the resin com-
posite decomposes into high-energy and reactive free radicals
upon irradiation with visible blue light ( = 400–500 nm). The
reactive radical species react with the C C bond in the
By definition, bi-functional trialkoxy silanes contain two
different functional end groups, alkoxy and C C, that can
connect to inorganic and organic materials, respectively. This
makes silane a mediator to promote adhesion between the
organic resin matrix and inorganic material. Matching of
the organic functional group in silanes with the functional

Table 2 – Functional silane film thicness at different immersion times.

3-Acryloxypropyltri- 3-Methacryloxypropyltri-
methoxysilane methoxysilane
Immersion time (h) 5 22 5 22
Film thickness (nm) 1.16 1.00 1.22 0.85
 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
Fig. 6 – Extensive siloxane network formed by cross-linking silane monomers, bis-1,2-(triethoxysilyl) ethane (BTSE), with
functional silane, 3-acryloxypropyltrimethoxysilane.
groups of resin monomers in commercial resin composites
can obtain excellent bonding [26].
Various functional silanes have been evaluated in
adhesion promotion for resin bonding to silica coated
zirconia and titanium, both of which are materials of
choice in prosthetic and implant dentistry [27–38]. Some
silanes studied are 3-acryloxypropyltrimethoxysilane
[27–31,34,36–38], 3-glycidoxypropyltrimethoxysilane (an
epoxy silane) [29,36], 3-isocyanatopropylytriethoxysilane
[27,31,32,37], 3-isocyanatopropyltrimethoxysilane [27,32],
3-methacryloxypropyltrimethoxysilane [27,29–31,34,36,37], 3-
mercaptopropyltrimethoxysilane [29], N-[3-(trimethoxysilyl)
propylethylenediamine] [29,34], styrylethyltrimethoxysi-
lane [27,36,37], tris-(3-trimethoxysilylpropyl)isocyanurate
[33], bis-[3-(triethoxysilyl)propyl]polysulfide [34], and 3-(N-
allylamino)propyltrimethoxy-silane [35,36]. The adhesion
strength measured varied with the functional groups of
silanes. This could be due to e.g., different reactivity of the
said silane coupling agents, the different resin composites
tested, and different artificial aging conditions and adhesion
testing method.
3.5. Non-functional silanes
Non-functional silanes do not possess reactive groups to react
with organic resin monomers. They may contain alkoxy ( OR)
functional groups that form silanol groups after hydrolysis
and the silanol groups react with surface hydroxyl groups
of inorganic substrates. Such a cross-linking (dipodal) silane
molecule which is also called a bis-functional silane (or briefly
bis-silane) has two silicon atoms, each silicon atom with
three hydrolysable alkoxy groups. It can form an extensive
cross-linking network with functional silanes and stabilize the
siloxane films for hydrolytic attacks.
These cross-linking (cross linker) silanes were first applied
in the steel and tyre industries to replace carcinogenic
Cr(VI)-based primers [39]. Also water-soluble, harmless
19
amino-silanes have been used successfully for coating appli-
cations in the industries.
In the oral environment, bonding between resin composite
and zirconia and titanium is gradually degraded after a long
period of time. This is, in part, due to the hydrolytic cleav-
age of siloxane bond at the interfacial siloxane (polysiloxane)
layer (film) [40–42]. A system with a functional silane com-
bined with a cross-linking silane might improve the bonding
and hydrolytic stability of the interfacial siloxane linkages
between resin composite and zirconia [43]. Cross-linking
silanes can form an extensive three dimensional network
with each other and interconnect with functional silanes [44],
see Fig. 6. Therefore, more energy is required to break down
the network bonding. As the siloxane cross-linking density
increases, i.e., cross-links per a unit volume, the free volume is
reduced. That means, the diffusion of water molecules into the
siloxane network becomes more difficult [45]. Given this, the
number of water molecules inside the siloxane cross-linking
network is decreased. This, in turn, improves the hydrolytic
stability of resin bonding in water.
Several studies have reported that a combination of a func-
tional silane with a cross-linking silane increases the bond
(adhesion) strength of resin to substrate [31,45–52]. Some
cross-linking silanes studied include bis-1,2-(triethoxysilyl)
ethane (BTSE) [45–49,51,52], bis-[3-(trimethoxysilyl)
propyl]amine [49], bis-1,2-(trichloroxysilyl)ethane (BISET),
bis-1,6-(trichloroxysilyl)hexane (BISHEX), and bis-1,8-
(trichloroxysilyl)octane (BISOCT) [50]. The results suggested
that resin bonding was degraded after aging in water but
incorporation of a cross-linking silane can improve the
hydrolytic stability of the bond. However, in some cases,
the resin bonding is not significantly affected by use of
cross-linking silanes added [49,50].
In summary, the silanization performance is affected by:
(1) silane concentration, (2) silane functional groups (match-
ing with the resin monomer functional groups), (3) blending
20 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
with cross-linking silanes, (4) pH, (5) hydrolysis time, (6) tem-
perature, and (7) nature of the solvent mixture.
4. Surface treatments methods for indirect
restorations
Surface treatment of indirect dental restorative materials
(such as metals, metal alloys, ceramics, and resin compos-
ite), followed by (silica coating and) silanization, is a critical
step that should activate the substrate surface for durable
adhesion with resin composites. Several surface treatment
methods have been attempted in dental laboratories. We shall
discuss the details in the following section (but omit bonding
to tooth tissues).
4.1. Grit blasting
In dental laboratories, the routine procedure for surface
pre-treatment of some indirect restorative materials is grit-
blasting with alumina powder with a particle size of e.g.,
110 ␮m under a constant air pressure of 380 kPa for around
10–15 s at a perpendicular short distance from the nozzle to
the surface of ca. 1 cm2 [53]. This cleanses and in particular
increases the surface roughness that enhances the bonding by
micro-mechanical interlocking (retention) [54]. However, the
surface may be contaminated with alumina powder particles
during grit blasting [55]. A thin layer of alumina coating may
be formed onto the substrate surfaces after grit-blasting. The
amount of alumina deposited is directly proportional to the
blasting pressure applied [56]. After silanization, Al O Si
linkages can be formed. The linkages are, however, somewhat
weaker than -Si-O-Si- and more susceptible to hydrolysis [57].
A drawback of the method is an induction of subsurface dam-
age causing surface micro-crack formation during the impact
of the powder particles. This might compromise the mechan-
ical strength at the surface layer which in turn affects the long
term clinical performance [58,59].
4.2. Pyrochemical silica coating
The basic principle of the pyrochemical silica-coating is the
chemical reactions of silane at high temperature to form silica
® ®
[60]. Silicoater Classical, Silicoater MD and Siloc (Heraeus-
Kulzer, Wehrheim, Germany) systems were used since 1984.
Base metal alloys, noble metal alloys and porcelain had been
silica-coated by this method [61].
®
In the Silicoater system, tetraethoxysilane, Si(OCH2 CH3 )4 ,
TEOS, is injected into a flame. A series of pyrochemical reac-
tions take place which can be summarized as follows [62]:
Si(OCH2 CH3 )4 (g) → SiO2 (s) + aCO2 (g) + bH2 O(g)
The processing temperature is 150–200 ◦ C. The reactive
silane intermediates, Si(OH)m C (where m = 1, 2, 3) deposit
on the substrate surface [63]. After cooling, a silane coupling
agent is applied onto the silica coating to react. An opaquer is
applied onto the surface and light-cured [64]. This method is,
however, no longer used in dental technology [61].
®
A modification of the Silicoater technique was introduced
® ®
subsequently as Silano Pen or PyroSil Pen (Bredent, Senden,
Germany) for extra-oral use in dental laboratories. It was
applied by a hand-held device with a flame treatment. Not
much has been reported on this approach [65].
4.3. Tribochemical silica-coating
The method was introduced in 1989 as an improvement of
®
the pyrochemical silica coating. A tribochemical Rocatec Sys-
tem (3M ESPE, Seefeld, Germany) was designed for surface
conditioning of dental restorative materials such as ceramics,
metals and metal alloys. The substrate surface is grit-blasted
under compressed air using silica-coated alumina powder
(alumina particles act as the carrier). The impact of the pow-
der particles which produces a very high temperature causes
the melting of the surface microscopically. The melting zone
area is related to the kinetic energy of the powder particles,
i.e., the pressure applied [66]. The impact of the powder parti-
cles not only changes the surface topography but also causes
embedding onto the substrate surface. A silica coated surface
is followed by silanization and finally flowable resin compos-
ite cementation. The achieved bond strength is affected by
the blasting pressure applied [67,68]. It was recently reported
that the grit blasting angle affects the resin bonding but no
significant effect with the change of sandblasting distance is
®
provided [69]. The CoJet system is a chair-side version of the
®
Rocatec System, and available for dentist offices and used
for intra-oral repairs with resin composite using 30 ␮m silica
coated alumina powder [70].
4.4. Chemical treatments by acids and bases
At ambient temperature, there are surface hydroxyl groups
formed on the surface of ceramics and metals. The hydroxyl
groups promote the interaction with silane coupling agents
through the hydrogen bond formation. This is followed by con-
densation to form a siloxane linkage. After a treatment with
concentrated mineral acids and bases, the density of hydroxyl
groups increases and a rough surface is created as some micro-
pits are formed [71,72].
For porcelain restorations, a micro-porous and micro-
retentive surface is produced after etching with 9–10%
hydrofluoric acid, HF, gel. When HF gel is applied on the porce-
lain surface, a soluble hydrofluorosilicic acid, H2 SiF6 is formed
and the surface glassy matrix is dissolved [73–75]. The overall
reaction can be summarized as [76]:
SiO2 (s) + 4HF(aq) → SiF4 (g) + 2H2 O(l) (10)
(9)
4SiF4 (g) + 3H2 O(l) + 2HF(aq) → 3H2 SiF6 (aq) + H2 SiO3 (aq)
(11)
However, HF is hazardous and very corrosive. An alterna-
tive 35–37% phosphoric acid gel has been attempted used but
the bond strength was lower compared to etching with HF [77].
 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
However, enamel and dentin surfaces are etched with
phosphoric acid gel to create a micro-retentive surface for
resin tag formation and bonding. For dentin, smear layer (dem-
ineralization) is removed and dentinal tubuli are opened for
resin infiltration [78,79].
5. Other surface treatment methods
Traditional surface treatment methods discussed above are
applied in dental laboratories. Research on other surface treat-
ments is ongoing in an attempt to improve adhesion and its
durability in the oral cavity.
5.1. Selective infiltration etching
In this relatively new approach, the zirconia surface is coated
with a thin layer of a glass-conditioning agent. The coating is
fired above the glass transition temperature and the molten
glass particles penetrate into the surface grain boundaries.
Surface tension is developed which causes the surface grains
movements: an inter-grain porosity is created. After treat-
ment with hydrofluoric acid, the glass particles are removed.
Thus, a highly reactive and retentive zirconia surface is formed
[80,81]. Resin zirconia bonding is significantly improved with
the selective infiltration etching treatment followed by a silane
application [82,83]. On the other hand, it is not clear whether
Si O Zr linkages (i.e., chemical adhesion) for enhanced
adhesion are formed.
5.2. Nano-structured alumina coating
Alumina nanoparticles are formed from the hydrolysis of
aluminium nitride (AlN) powder heated at 75 ◦ C, resulting
nano-boehmite (␥AlOOH) particles deposited on e.g., zirco-
nia surface. When the coating is thermally treated in air at
900 ◦ C, the boehmite undergoes a series of phase transfor-
mation to ␦-alumina [84]. An increase in the surface area
enhances the micro-mechanical interlocking for resin bond-
ing. Interestingly, improvement in resin zirconia bonding is
obtained after water aging even without a silane application
[85].
5.3. Chemical vapour deposition
In molecular vapour deposition system, a mixture of tetra-
chlorosilane (SiCl4 ) and water is heated. The vapour is passed
onto zirconia surface in a vacuum chamber. Silane undergoes
hydrolysis to form hydroxylated silica and HCl gas as a byprod-
uct is produced. A silica seed-layer (Six Oy ) is formed on the
zirconia surface. The coating thickness can be adjusted by the
deposition time. The silica seed coating is reported to form
durable bonding to zirconia with an application of silane cou-
pling agent [86].
5.4. Laser treatment
There are three types of laser used in dentistry for clinical use
and surface treatment: (1) erbium: yttrium-aluminum-garnet
(Er: YAG), neodymium: yttrium-aluminum-garnet (Nd: YAG),
21
and carbon dioxide (CO2 ) [87]. The substrate surface is irra-
diated with a laser beam. The laser energy is absorbed and
converted into heat energy. The heat energy causes the melt-
ing of the substrate surface and produces surface irregularities
[88,89]. Surface topography changes take place and enhanced
adhesion promotion was observed.
5.5. Internal coating method
Silica coating on the zirconia surface is achieved by thermal
fusion. Porcelain powder is mainly composed of silica with
small percentage of Al2 O3 , Na2 O, and K2 O. The zirconia surface
is grit-blasted with alumina powder. The porcelain powder is
mixed with distilled water to form a paste and applied onto
the grit-blasted zirconia surface. It is then fired at 800 ◦ C in vac-
uum. This can be followed by silanization and resin bonding
[90].
5.6. Sol-gel coating
The basic principle of this method is the hydrolysis of silicon
certain precursors, in most cases, tetraethoxysilane to form
silica sol gel in an acidic or alkaline medium. Hydrolysis of
tetraethoxysilane produces silica and ethanol as a by-product.
The silica sol gel deposits on the substrate surface through the
surface hydroxyl groups and forms silica coating [91,92].
5.7. Plasma fluorination
A highly reactive coating is formed on the zirconia surface
by using plasma spray technique. Zirconia surface is exposed
to a continuous flow of sulphur hexafluoride (SF6 ) gas at a
constant pressure in an inductively coupled plasma reactor.
Under plasma irradiation, the sulphur hexafluoride molecules
are converted to reactive species and react with zirconia after
deposition on the surface. This forms a zirconium oxyfluoride
thin surface layer on zirconia. When silane coupling agent is
applied onto the reactive surface, surface silanation occurs
[93].
5.8. Nano-silica coating
Other silica precursors can react to form silica by hydroly-
sis but in more demanding reaction conditions. In a recent
study, silica coating was formed on zirconia by the hydrolysis
of silicon nitride (SiN) nanoparticles under a strong alkaline
medium with heating. The silicate species are formed from
a suspension of SiN nanoparticles in concentrated sodium
hydroxide solution and heated to 90 ◦ C. The hydrolysed sil-
ica nanoparticles deposit on the zirconia surface. After drying,
the coating is heated to 1400 ◦ C to form the silica coating by
condensation of the hydroxylated silica species (Fig. 7) [94].
5.9. Silicone-based coating
Silicone polymers such as polydimethylsiloxane which con-
tains a repeating unit of siloxane can form silica upon thermal
oxidation and decomposing in air [95]. When a thin layer of
polydimethylsiloxane gel is applied onto a titanium surface,
a silica coating is formed by thermal oxidation at high tem-
22 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
Fig. 7 – Formation of three dimensional silica network from hydrolysis of silicon nitride.
perature (Fig. 8). Resin titanium bonding was evaluated using
the said silicone coating technique. The results suggested that
the bond strength is significantly improved when the ther-
mal treatment temperature is higher than 1000 ◦ C - after water
aging and thermo-cycling [96].
6. Applications of silanes in dentistry
The above briefly introduced methods render new ways to
increase the silica content on indirect restorative materials.
On the other hand, they might be synthetically demanding
and cumbersome in practice, but bring new chemical thinking
into the surface pretreatment discussion. Even so, application
of silane coupling agents on silica rich material surfaces in
dentistry aims at promoting adhesion to meet the demands
for durable restorations [97]. In the sections below different
aspects of silane coupling agents in dental applications will
be discussed in details.
6.1. Dental ceramic restorations and repairs
Yttria partially stabilized tetragonal zirconia polycrystalline
(TZP), glass-infiltrated alumina, feldspathic porcelain and
leucite-reinforced ceramics are used as indirect restorative
materials as they have excellent biocompatibility, superior
aesthetic appearance and good marginal adaptation. Studies
have reported that surface pre-treatment by grit blasting fol-
Fig. 8 – Thermal oxidation of polydimethylsiloxane to silica.
lowed by silane coupling agents application yielded durable
resin bonding [73,98].
Fracture of dental ceramics is still the major problem in
restorative dentistry because ceramic dental materials have
high compressive strength but low tensile strength, i.e., they
are brittle. Micro-defects in the material, impact and fatigue
load, imperfect design, mastication, parafunction and intrao-
ral occlusal forces create repetitive dynamic loading are the
main reasons for the ceramic fracture [99]. Ceramic repair,
at least in some cases, might be an economic and time-
saving solution than repeating the whole ceramic restoration
intervention. Generally, it involves five steps of treatment: (1)
polishing and roughening, (2) Grit blasting, (3) acid etching
with hydrofluoric acid, (4) Silanization, and (5) cementation
[100].
6.2. Glass fibre-reinforced composites
Resin matrices reinforced with E-glass fibres exhibit improved
mechanical strength, and at least somewhat reduced dimen-
sional changes caused by polymerization shrinkage [101–103].
E-glass fibre-reinforced resin composites, FRCs, are contem-
porarily used as endodontic fibre posts, fixed partial dentures,
removable prosthodontics, periodontal splints, (in principle
in) dental implants, and retention splints [12,104]. Surface
treatment of glass fibres with a silane coupling agent is
mandatory as it enhances bonding with the resin matrix and
fibres [105,106]. This further contributes to enhanced physical
 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
and mechanical integrity of fibre-reinforced resin composites
[107,108]. Furthermore, increasing the chain length of linker
group of the silane can improve the hydrolytic stability of
such resin composite [109]. Several other types of fibres have
been attempted, such as quartz, polyethylene, graphite, and
aramid, but they have drawbacks in adequate adhesion to the
matrix (or other reasons).
6.3. Resin composites
Modern commercial dental resin composites, a gold stan-
dard in dentistry, contain the following five key components:
resin matrix, free-radical initiator andinhibitor/stabilizer, dyes
(pigments), fillers and silane coupling agent. The incorpora-
tion of the filler particles (the size, shape, and load of which
vary) enhances the mechanical properties and reduce the
polymerization shrinkage after curing the resin composites
[110]. Adhesion between the filler particles and resin matrix
needs to be strengthened by adding a silane coupling agent.
During light curing, the organofunctional group of silane cou-
pling agent reacts with the functional group of the uncured
resin monomers to form a chemical bond, such as C C
[111,112]. Studies have indeed reported that incorporation of
silanized filler particles in the resin matrix improves the phys-
ical and mechanical properties of resin composites in terms
of mechanical strength and hydrolytic stability [113–116].
6.4. Titanium, base metal and noble metal alloys
In dentistry, titanium has been mainly used as a dental sub-
gingival implant fixture (and an abutment) but also in fixed
and removable partial dentures, crowns, orthodontic wires,
in OMFS and brackets [117]. Surface pre-treatment of metals
and metal alloys by grit blasting is important before applying
Fig. 9 – Reaction scheme of long chain silane synthesis (modified from Ref. [128]).
23
silane coupling agents and thereafter resin composite cement
to obtain clinically durable bonding [118–122]. After silica coat-
ing, a thin layer of silica is formed on the substrate surface so
that a chemical O Si O M linkage is formed at the interfa-
cial region. Given this, a (Si O Si) O M siloxane to metal
linkage is, in principle, formed after silane is applied. However,
the formation strongly depends on the metal (alloy), its sur-
face chemistry and requires intensive studies. In addition to
using silane coupling agents, some other so-called metal and
alloy primers can also be used for bonding resin composite to
noble metals/noble metal alloys. The adhesion performance
of such metal primers is sometimes reported to be as good as
or even better than silane coupling agents, at least in the labo-
ratory conditions [123,124]. The metal or alloy primers usually
contain (for example) two reactive primer components: (i)
phosphate esters, carboxylic acids or acid anhydrides for base
metal alloys, and (ii) thione or thiol ( SH) for noble metal alloys
[125].
7. Development of coupling agents in
dentistry: present and future
Today, silane coupling agents are still the gold standard
adhesion promoters used in dentistry for most indirect
restorations. However, the bond degradation over time in oral
cavity is still the major concern [27,41,126,127]. An approach
to improve the bond durability is: (1) modification of silane
molecules (synthesis) [128], or (2) development of other cou-
pling agents (such as multifunctional blends) [129].
It is noteworthy that long-chain functional silanes (with
a long linker part) have some special properties when com-
pared with short-chain functional silanes. The silanes with a
long chain linker part are more hydrophobic than short chain
24 d e n t a l m a t e r i a l s 3 4 ( 2 0 1 8 ) 13–28
silanes. Such a long chain can improve the bond hydrolytic
stability towards degradation. Recently, a long chain silane
coupling agent was sucessfully synthesized [128]. It is pre-
pared from a long chain alkenyl alcohol. Two metal complexes
are used in the coupling reaction (Fig. 9).
The mechanical strength tests showed that there was
improvement of flexural strength of bis-GMA/TEGMA
resin composite compared with a short chain 3-
methacryloxypropyltrimethoxysilane after 24 h water aging
at 37 ◦ C [128]. The increase in the chain length of functional
silanes can improve hydrolytic stability of the resin com-
posite. However, resin bonding adhesion peformance of this
novel long chain silane is not yet evaluated.
Some other functional non-silane coupling agents such
as oleic acid, n-octadecan-9-enoic acid, 2-hydroxyethyl
methacrylate, itaconic acid, and zirconates have been
attempted and evaluated [30,130,131]. They all contain the
C C and OH or −COOH functional groups. The adhesion
strength test results suggested that moderate bond strength
of resin zirconia bonding was obtained after water aging and
thermo-cycling. However, they might be applicable for bond-
ing in less load bearing orthodontics attachments.
Organophosphate ester primers such as 10-
methacryloxydecyl dihydrogen phosphate (MDP) have
been previously developed. The adhesion performance of an
organophosphate ester primer is reported comparable or even
superior to a silane coupling agent when it is applied to zir-
conia restorations [132]. Recently, another organophosphate
ester coupling agent, dipentaerythritol penta-acrylate phos-
phate (PENTA), was evaluated for resin zirconia bonding [133].
This coupling agent has already been used commerically for
resin dentin bonding. The adhesion strength performance of
the PENTA was reported better than MDP.
Mixing a silane coupling agent with other adhesive
primers is another approach to improve the adhesion.
Resin titanium bonding by using adhesive primers con-
taining silane and 2-hydroxyethyl methacrylate (HEMA) was
assessed [134]. The results showed no significant differ-
ence in bond strength with incorporation of HEMA which
was, perhaps interestingly, in contrast to some other reports
[135–137].
In some commerical adhesive primers, a mixture of silane
and phosphoric acid/ester primers is used to improve the resin
adhesion and hydrolytic stability. The adhesion performance
of resin zirconia bonding has been reported superior than with
a silane primer alone [138,139].
For noble metals and noble metal alloys, thione and
thiol coupling agents (containing the −SH group) are
used for durable resin bonding. Recently, resin bonding to
noble metal alloys with a silane primer system contain-
ing the thiol silane, 3-mercaptopropyltrimethoxysilane, and
3-methacryloxypropyltrimethoxysilane was evaluated. The
adhesion strength measured was comparable to commerical
thiol primers after water aging [140,141].
8. Conclusions
Adhesion is vital in restorative dentistry. Silane coupling
agents are still the most important adhesive primers used
in clinical practice. Surface pretreatment (silica coating) and
silanization belong to routine dental laboratory practice in
indirect restorations. But improvements are needed. The long
term resin bond hydrolytic stability is still a concern. Devel-
opment of new functional silane coupling agents and novel
surface treatment methods to address the problem is in
progress. We can foresee that with the advance of new synthe-
sized silane coupling agents and surface treatment methods
developed, versatile (new) silanes will still be dominant in
adhesive dentistry and biomaterials science as precursors for
silicone synthesis.
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