Surface Pretreatment Methods and Silanization: Christie Ying Kei Lung and Jukka P. Matinlinna

Chapter 11
Surface Pretreatment Methods and

Silanization
Christie Ying Kei Lung and Jukka P. Matinlinna

Faculty of Dentistry, Dental Materials Science, University of Hong Kong,
Prince Philip Dental Hospital, 34 Hospital Road, Sai Ying Pun,
Hong Kong SAR, People’s Republic of China
cyklung@hku.hk
The clinical success of dental restorations depends on the adhesive

strength and bonding between dental restorative materials and
tooth structure. Adhesion occurs when two dissimilar materials are
close in a molecular level and contact to form bonds. In general, the
adhesion and affinity between dissimilar materials, for example,
inorganic and organic materials may be very weak. Adhesion can be
significantly increased by application of a mediator, such as a silane
coupling agent, that contains different functional groups to react
and form a linkage to connect them. After surface pretreatment,
the surface is more reactive for bond formation. Therefore, the
surface treatment of some indirect dental restorative material is an
important step in restorative dentistry. This chapter covers (1) the
introduction of surface science, (2) basic theories of adhesion and
surface characterization, (3) a discussion of several common surface
Handbook of Oral Biomaterials

Edited by Jukka P. Matinlinna
Copyright © 2014 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4463-12-6 (Hardcover), 978-981-4463-13-3 (eBook)
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360 Surface Pretreatment Methods and Silanization
treatment methods, (4) some other new surface treatment methods

currently under investigation, and (5) explanations for different
types of mechanisms for various surface treatments to understand
how they achieve the surface modification in question.
11.1 Introduction
In dental indirect restoration, surface pretreatment, also called
surface conditioning, of dental materials is a vital preliminary
step to enhance the adhesion between a luting resin composite
Downloaded by [Cornell University] at 06:18 26 October 2016
and the restoration (resin composite materials are discussed

comprehensively in Chapter 6). It is defined as one or a series of
steps such as cleaning, removal of loose particles, and modification
of a surface to which an adhesive is then applied for bonding.
The purpose of surface treatments is to:
(1) remove or prevent the formation of any weak surface layer on
the substrate such as greases and dust particles
(2) maximize the molecular interaction at the interfacial layer
between two different substrates, that is, increase the surface
free energy
(3) optimize the adhesion at the interface such that sufficient
adhesive strength can attain the required strength during the
service
(4) create special surface microstructures for retention [1].
In this chapter, some basic principles of surface science, the theory
of adhesion, surface characterization, and surface pretreatment
methods currently used in dentistry are discussed. Some other new
surface treatment methods with application of different techniques
are also discussed. The underlying principles of these surface
pretreatment methods will be further explained. Dentin bonding is
discussed in Chapter 1.
11.2 Surface Science
11.2.1 Interface and Surface Tension

In a system, a surface or an interface (interface = a surface forming
a common boundary between two regions) exists when there is a
Surface Science 361
change in the system properties with distance. Properties that show

change at the interface are chemical composition, crystal structure,
and density [2]. The interfacial particles differ in energy from the
bulk of each phase because they are at the boundary region and
interact with the particles of the other phases [1].
All molecules in the liquid state are held together with attractive
intermolecular forces. The overall attractive force for each molecule
in the bulk is zero. However, the resultant force of the molecules at
the surface is not zero compared to the bulk liquid molecules. The
force, F, required to increases the surface by a unit length, L, is called
surface tension [3]:

F
g = (11.1)
dL
More specifically, surface tension can also be defined as the
energy required to increase the surface area by a unit of area. This
energy is called the surface free energy of that liquid to resist the
extension of a free surface per unit area [1].
Surface tension is strongly affected by temperature. The
intermolecular forces of molecules are weakened when temperature
increases. An equation for the relationship between the surface
tension of the liquid and temperature is given by Guggenheim’s
equation:
11
Ê Tˆ 9
g = g 0 Á1 - ˜ (11.2)
Ë Tc ¯
where γ0 is the surface tension at absolute zero temperature and Tc
is the critical temperature of the liquid [4].
11.2.2 Contact Angle

When liquids are in contact with solid surfaces, wetting occurs at the
interface. The contact angle, α, is defined as an equilibrium of a liquid
drop on a solid surface under an effect of three surface tensions, as
shown in Fig. 11.1 [5].
At equilibrium, the surface tension at the solid–vapor interface is
balanced by the sum of surface tensions at the solid-liquid and liquid-
vapor interfaces. This relationship is given by Young’s equation [6]:
γsv = γsl + γlvcos α (11.3)
Figure 11.1 Contact angle of a liquid drop in contact with a solid surface.
The ability of a liquid to keep in contact with a solid surface is

called wetting. The degree of wetting depends on the adhesive force
between liquid and solid surfaces and the cohesive force within the
liquid molecules. It can be determined by the equilibrium contact
angle, γ. For, γ = 0, it is complete wetting of the liquid on the solid
surface. For, 0 < γ < 90°, the wetting of the liquid on the solid surface
is high. For 90° < γ < 180°, the wetting of the liquid on the solid
surface is low [3].
11.2.3 Critical Surface Tension

In the early 1950s, Zisman and Fox studied the contact angle of
various liquids on different solid surfaces and measured the surface
tension of the liquids. From the plot of cos α against γlv, a straight
line is always obtained for homologous liquids and a curved line is
obtained for nonhomologous liquids, as shown in Fig. 11.2 [6].
From the plot of cos α against γlv, the extrapolation of cos α to
1 gives the value of the critical surface tension (γc) of the solid
(Fig. 11.2). It varies with different solid surfaces. Therefore, from
Eq. 11.3, when cos α = 1, γc = γsv – γsl. An explanation for this
curvature of the Zisman plot is the interactions such as hydrogen
bonding between the liquid and the solid surface.
NB: We have two terms, an interface (see above) and an
interphase. An interphase is defined as a region between the
unambiguous boundaries of two phases and characterized by distinct
properties—actually it is a third phase [7].
11.3 Theories of Adhesion

Some theories are used to explain the mechanisms of adhesion
[1, 7–9]. In most of the cases, adhesion between the adhesive and the
Theories of Adhesion 363
substrate surface is a combination of different mechanisms.

Figure 11.2 Zisman plot of contact angle and surface tension. Modified
from Ref. [6].
Currently, there are six dominating theories of adhesion to

describe the nature of adhesion [1, 7–9]:
1. Mechanical interlocking theory
2. Wetting theory
3. Diffusion theory
4. Weak boundary layer theory
5. Electrostatic theory
6. Chemical bonding theory
11.3.1 Mechanical Interlocking Theory

For an irregular and rough substrate surface, the adhesive penetrates
the cavities and pores. After hardening, the adhesive locks
mechanically (micromechanically) to the substrate surface, provided
that good wetting is achieved with the rough surface. Otherwise, the
presence of voids at the interface lowers the adhesion. In general,

adhesive bonds form better in a more irregular and porous surface
than a smooth surface. The increase in surface roughness of a
substrate enhances adhesion by mechanical interlocking.
11.3.2 Wetting Theory

This theory is based on the fact that adhesion occurs through
molecular interaction and surface forces developed between the
adhesive and the substrate surface. First, interfacial forces are
developed between the adhesive and the substrate. Then, the process
of continuous contact, that is, wetting, is established. To have good
wetting of the adhesive on the substrate surface, the surface tension
of the adhesive should be lower than the critical surface tension of
the substrate surface.
11.3.3 Diffusion Theory

This theory applies to adhesion with long-chain-length polymer
molecules. It involves the interdiffusion of polymer molecules across
the interfacial layer. The interdiffusion occurs when the temperature
is above the glass transition temperature such that the polymer
chains are mobile. Adhesion by means of diffusion can be described
by this relationship:
Ecoh
d= (11.4)
V
where δ is the solubility parameter, Ecoh is the energy required to
separate the molecules to infinite separation, and V is the molar
volume. High adhesion is achieved when solubility parameters
between the adhesive and the substrate are similar. This theory
applies to adhesion of the same polymer or chemically very similarly
polymers because of the same solubility or similar mutual solubility.
An example of diffusion bonding is solvent welding of
thermoplastics. The solvent lowers the glass transition temperature
of the polymer, and interdiffusion of polymer molecules across the
interfacial layer takes place. The interdiffusion also increases at an
elevated temperature, which leads to increased adhesive strength.
Theories of Adhesion 365
11.3.4 Weak Boundary Layer Theory

In this theory, weak boundary layers are present in the adhesive or
the substrate surface and the adhesion is weakened. When failure
takes place, breaking at the weak boundary layers occurs first.
The presence of weak boundary layers at the interface is due to
the substrate surface being exposed before adhesion and so being
contaminated, for example, by dust or grease. Moreover, if the
adhesive does not wet the substrate surface completely, air is trapped
at the interface. This causes the decrease of adhesive strength.
Therefore, surface pretreatments before bonding are necessary to

remove surface contamination.
11.3.5 Electrostatic Theory

The basis of this theory is that free charges exist to a different extent
in any material. There is an electrochemical potential difference
between two different materials when in contact. A charge transfer
takes place, and free-charge carriers move across the interfacial
region. An electric double layer is formed. This theory is used to
explain the polymer–metal adhesion where charge transfer occurs
between polymer and metal and an electric double layer is formed
in the interfacial layer.
11.3.6 Chemical Bonding Theory

This theory states that a chemical bond is formed between the
adhesive and the substrate surface. Examples of chemical bonds are
covalent, ionic, ion–dipole, dipole–dipole, and hydrogen bonds and
van der Waals (aka London) forces. Covalent and ionic bonds are the
strongest chemical bonds that can be formed between the adhesive
and the substrate surface. Other weak chemical bonds include
hydrogen bonds, dipole–dipole attraction, van der Waals forces. In a
real situation, the adhesion between the adhesive and the substrate
surface involves a combination of other adhesion mechanisms:
mechanical interlocking (retention), wetting, or diffusion. This
depends on the functional groups of the adhesive, the chemical
composition, and the surface properties of the substrate surface.
11.4 Surface Characterization Techniques

The importance of surface characterization is that it can provide
valuable information of surface topography, chemical composition,
and the amount of trace impurities. Some common surface
characterization techniques used in dental materials research are
discussed concisely in this section [1, 10, 11].
11.4.1 Infrared Spectroscopy

All molecules are capable of vibrating above 0 K, that is, –273.15°C,

and the more complicated a molecule is, the more the amount of
different possible modes is. In general, the molecular vibration
modes are stretching, rocking, wagging, and bending. The vibrational
transitions of inorganic and organic molecules take place in the
infrared (IR) region of light. The typical excitation energy, ∆E, is
between 10–12 J and 10–19 J, and the corresponding frequency (f) is
about the magnitude of 1013–1014 Hz (1 Hz = 1 s–1):
∆E = hf (11.5)
where h is p (Planck’s constant) = 6.626 × 10–34 Js.
In IR spectroscopy transitions are usually expressed in terms
of their wavenumbers, v, which are reciprocals of the wavelength, λ.
The wavenumber region is typically in the scale of 3000–300 cm–1
for the majority of organic molecules. Given this, the principle of
IR spectroscopy is based upon the absorption of particles in the
IR region. Absorption occurs when the energy of IR is equal to the
molecular vibration. The absorption frequency is specific for various
functional groups of the molecule as the amount of energy absorbed
is different. The relationship between absorbance and the sample
concentration is given by Beer’s law:
A = εbc (11.6)
where A is absorbance, ε is the extinction coefficient, b is the sample
thickness, and c is the sample concentration (in a selected solvent).
Silane coupling agents are important hybrid inorganic-organic
molecules that are applied to some dental materials. They absorb IR
light in the mid-IR region, namely, between 4000 cm–1 and 600 cm–1
[12, 13].
Surface Characterization Techniques 367
For analysis of the sample surface, the attenuated total internal

reflectance (ATIR) IR technique is used. In this technique, the sample
is in close contact with both surfaces of a high refractive index
crystal. A multiple internal reflectance of the IR beam on the sample
surface is achieved. The IR spectrum gives information regarding the
chemical structure of the sample surface.
Another very widely used technique that is based on interference
is Fourier transform infrared (FTIR) spectroscopy. An IR beam is
split by a beam splitter, which is positioned 45° to the incident beam.
The two beams are reflected by a fixed and a movable mirror to
recombine the resultant beam. The interference pattern is analyzed

by a mathematical model called Fourier transform. It may be used
effectively since the siloxane groups (…–Si–O–Si–…) yield very
strong (and complex) absorbance signals [13].
The FTIR method produces fingerprint spectra for every
compound that is prone to the method. The modern computational
spectral subtraction capability of FTIR spectrometers enables
selective monitoring of the structure of the coupling agent. The FTIR
method is convenient, fast, and widely applied, for example, in silane
research. The spectra can be mathematically processed to minimize
noise and also to make the spectra comparable. The hydrolysis and
condensation reactions usually can be followed with FTIR analysis
[12–14].
11.4.2 Scanning Electron Microscopy

Scanning electron microscopy (SEM) is an important technique
to analyze the material surface topography. The material surface
is sputtered with a thin layer of gold metal so that the surface is
conductive before SEM analysis. A beam of electrons is focused
onto the sample surface. The interaction of the electron beam and
the sample surface produces excited secondary electrons, back-
scattered electrons, and X-ray photon energy. A detector collects the
emitted particles to produce the image of the sample surface.
11.4.3 Energy Dispersive X-Ray Spectroscopy

Energy dispersive X-ray spectroscopy (EDX or EDS) is a very useful
technique to identify and quantify the chemical composition of
the material surface structure. When electrons of the atoms on

the sample surface are excited by a high-energy electron beam, an
emission of photon energy with wavelengths of X-rays is detected.
An energy-dispersive detector analyzes the corresponding elements.
This gives the chemical composition of the sample surface.
11.4.4 Transmission Electron Microscopy

The basic principle of transmission electron microscopy (TEM) is the
scattering or diffraction of electrons. This occurs upon interaction
with the crystalline planes of the sample when a high voltage of

focused electron beams is passed through a thin solid sample. A TEM
system comprises three sections:
1. An illumination system
2. A sample stage
3. An imaging system
The illumination system has an electron gun and condenser
lenses to focus the electrons onto the sample. The sample stage is
used to position the sample in the TEM system. The imaging system
has three or more lenses to produce a magnified image of the sample
on the screen.
11.4.5 Atomic Force Microscopy

The first commercially available atomic force microscope (AFM)
was introduced in 1989. The instrument is very useful as it can be
applicable to both conductive and nonconductive material surfaces.
The basic principle of atomic force microscopy is the measurement of
intermolecular forces between the AFM tip and the sample surface.
An AFM can be used to image and manipulate atoms and structures
on a variety of material surfaces.
There are three AFM operational modes for surface topographic
imaging, depending on the application: 1. noncontact mode, 2. contact
mode, and 3. tapping mode. In noncontact mode, the cantilever tip
is above the sample surface to detect the intermolecular forces
between the tip and the sample. Surface topographic images are
acquired by scanning the tip across the sample surface. In contact
mode, the cantilever tip is in close contact with the sample surface.
Surface Pretreatment Methods Used in Dental Laboratories 369
However, the tip may damage the sample surface due to the lateral
movement of the tip and the image is distorted. Thus, this mode is
not suitable for biological and polymer surfaces. In tapping mode,
the cantilever tip is oscillated at the resonant frequency. Then, the
vibrating tip is moved close to the sample surface until it taps lightly
the surface. There is energy loss of the tip due to contact with the
surface. The change in the amplitude of vibration is measured to plot
the surface topography of the sample [10, 13].
11.5 Surface Pretreatment Methods Used in

Dental Laboratories
Some of the common surface pretreatment methods used in dental
laboratories for indirect restorations are:
• hydrofluoric acid (HF) etching;
• grit blasting;
• pyrochemical silica coating;
• tribochemical silica coating.
These treatment methods can alter the surface properties of
dental restorations, physically, chemically, or both ways, such that
strong and durable bonding may be established between resin
composites and these surface-treated materials. These surface
treatment methods have been demonstrated to improve bonding
and are well documented in the literature [7, 15–17].
11.5.1 Hydrofluoric Acid Etching

HF has wide applications in many areas such as glass etching and
oxide removal from metals [18]. As a matter of fact, hydrogen
fluoride is a colorless gas, and it fumes in humid air. It is very
soluble in ethanol and water, and its solution with water is called
hydrofluoric acid. It is strongly corrosive, and it is an excellent ionizing
solvent and dissolves many inorganic and organic compounds
[7, 19].
In dental laboratories, HF is used to etch porcelain veneers/
crowns/onlays and, in principle, in intraoral repair the fractured
porcelain restoration surface. However, intraoral use should be
avoided [17, 19]. When the porcelain veneer surface is treated with
HF etching gel, the HF dissolves the glass matrix of the porcelain
(no other mineral acids dissolve that effectively). After rinsing
the acid-etched surface with water and air-drying, a microporous
structure on the porcelain veneer surface is obtained. These porosities
enhance micromechanical interlocking retention for durable bonding
[7, 17, 20, 21].
Although HF is a weak acid, it is highly corrosive and toxic to
humans. It penetrates skin tissues much more quickly than other
inorganic acids due to its low ionization constant. This results in
causing extensive internal tissue damage [18]. In a typical dental

HF gel the actual HF content is around 4% to 10% and so can be
used safely. Definitely the best advice is to follow the manufacturer’s
recommendation, or if no specific instruction is given, a good rule
of thumb is to etch for between one and two minutes to obtain
adequate roughness [17, 19].
11.5.2 Grit Blasting

In this methodology, the surface of materials is blasted usually with
alumina powder of an average particle size of, for example, 50 µm
under compressed air, for example, at a pressure of 380 kPa. Usually
the blasting time is around 10–15 seconds at a perpendicular
distance of about 10 mm from the nozzle to a surface area of
ca. 1 cm2 [15, 16]. Grit blasting increases the surface roughness of the
materials that would thereby enhance the mechanical interlocking
for bonding [7, 21–23]. Inevitably, a layer of alumina, Al2O3, particles
may be embedded onto the substrate surfaces after grit blasting. The
amount of alumina embedded and the degree of surface roughness
depend on the grit size, nozzle distance to the surface, blasting time,
and applied pressure [15, 24–26]. The presence of alumina particles,
however, may deteriorate the ceramic–metal and resin–metal
bonding [27, 28].
11.5.3 Pyrochemical Silica Coating

In this method, a silica (SiO2) layer is deposited onto the substrate
surface by means of pyrochemical processes. From the historical
point of view, there are several pyrochemical silica-coating sys-
tems (aka thermal silica-coating systems) that have been utilized in

dental laboratories: Silicoater™ Classical, Silicoater MD and Siloc™
(Heraeus-Kulzer, Wehrheim, Germany), and PyrosilPen™ device
(SurA Instruments, Jena, Germany) [15–17, 29]. Tetraethoxysilane
(TEOS) (aka tetraethylsilicate) solution is injected into a flame and
burned with oxygen in the presence of fuel gas butane. The inter-
mediates (–SiOx–C) formed reach the substrate surface and de-
posit onto the surface. When the silica-coated substrate surface is
cooled to room temperature, a silane coupling agent is applied onto
the coated surface and is followed by cementation [30]. This per se
chemically interesting surface-conditioning method is not anymore

used in dental technology [16].
11.5.4 Tribochemical Silica Coating

A tribochemical Rocatec™ System (3M ESPE, Seefeld, Germany) was
introduced in 1989, and it is continuously used for surface treatment
of various dental materials such as metals, metal alloys, and
ceramics in dental laboratories [15, 28, 31–34]. The silica-coating
of the substrate surface can be carried out using Rocatec™ Soft
(30 µm silica-coated alumina powder) or Rocatec™ Plus
(110 µm silica-coated alumina powder) with defined operational
parameters, such as under a compressed air pressure of 280 kPa for
30 s/cm2 at a perpendicular distance of around 10 mm [31]. Thus,
a silica-coated layer is formed on the surface and further treated
by silanization. A durable siloxane linkage is formed after drying.
The silica-coated and silanized substrate is cemented with a resin
composite to complete the restoration [13]. The Cojet™ system
(3M ESPE, Seefeld, Germany) is an in-office silica-coating system
that employs 30 µm silica-coated alumina powder for sandblasting
the substrate surface. It may be used for intraoral repair of fractured
metal ceramic (porcelain fused to metal [PFM]), all-ceramic, resin
composites, and even amalgam restorations [15, 17, 35].
11.5.5 Silanization
When silanes promote adhesion between dissimilar materials,
silanes react to form a siloxane film (sometimes called a silane film)
between these materials. It is usually expected that at least one
of the surfaces should be siliceous for its chemistry, that is, silica,
silicates, or glass should be available on the substrate surface.
The silane solutions must be optimized (e.g., silane concentration,
solvent consistency, pH, hydrolysis/activation time, etc.) to avoid
silane polymerization before the deposition [15, 36].
Silanization (silanation) means application of a silane
coupling agent. When deposited on an inorganic surface, silanol
oligomers react with each other, forming branched hydrophobic
siloxane bonds, –Si–O–Si–. With a surface of an inorganic matrix
(e.g., silica and metal oxides containing hydroxyl, –OH, groups), they
form metallosiloxane bonds of the type –Si–O–M– (where M = metal).

In dentistry and dental technology, silane coupling agents are used
to promote adhesion between a luting resin composite cement and
a silica-coated base metal and noble metal alloys, Ti, etc. [15, 17]. As
a coupling agent, silanes have two different functional groups that
react to link them together.
There is a plethora of commercially available dental silane
products, and they differ from each other for their formulations and
properties [37]. Silane coupling agents for dental use are usually
supplied as ca. 1–2 vol% in their prehydrolyzed form in a 90–95%
ethanol/water solvent. Ethanol (or some other alcohols) is necessary
to use to dissolve hydrophobic silane monomers. Silanes have to be
activated by hydrolysis before application. When activated silane is
deposited onto the inorganic substrate surface, a chemical reaction
occurs, which allows bonds to be formed between activated silane
and the substrate (see also Chapter 3).
In general, various silane coupling agents find numerous
applications in coatings and adhesion promoters in steel, aluminum,
and brass pretreatments (see Fig. 11.3).
Also in these applications, silanes are not supposed to react
with the metal substrate in depth but to wet it and deposit as thin
films. Stable condensation products of silanization, silane coatings
(also called polysiloxane coatings), may alter the wetting and
adhesion characteristics of a silanized substrate surface [36].
There are also some silanes, such as methyltrichlorosilane and
trimethylchlorosilane (including their alkoxy derivatives), that are
employed to render materials (e.g., masonry, laboratory glassware)
water repellent. In these cases, silanes change the wettability
characteristics of a substrate surface. In general, it can be stated that
low surface energy results in low adhesion and high surface energy
in high adhesion [7, 38].
Figure 11.3 Some silane coupling agents. BTSE is a so-called cross-linking

silane. Abbreviation: BTSE, bis-1,2-(triethoxysilyl) ethane.
Silanes are characterized by direct silicon–carbon (Si–C)

bonds, which are calculated to be as strong as, and in some cases
even stronger than, the analogous C–C bonds. Chemically, silanes
are hybrid inorganic-organic compounds that are synthesized
by reduction of silica (SiO2). Silica is abundant on the earth.
Silica reacts with carbon at high temperatures to produce silicon
(Eq. 11.7). In the case of a trialkoxysilane (Fig 11.3.), those with
methoxy groups, –OCH3, may be effective without catalysis. The
degree of silane polymerization is determined by the amount of
water that is available and also by the organofunctional moiety [36].
The silicon (Si) produced from silica reacts with hydrogen

chloride (HCl) in the presence of a Cu catalyst to produce trichlo-
rosilane. Coupling of trichlorosilane with haloalkene followed by
alcoholysis gives the alkoxysilane [36], as presented below:
SiO2 + C Æ Si + CO2 (11.7)
Si + 3 HCl Æ HSiCl3 + H2 (11.8)
ClH2RCH=CH2 + HSiCl3 Æ ClH2RCH2CH2SiCl3 (11.9)
ClH2RCH2CH2SiCl3 + 3 R’OH Æ ClH2RCH2CH2Si(OR’)3 + 3 HCl(11.10)
When talking about stability it is noteworthy that elements
other than C or Si bonded directly to Si generally undergo somewhat
rapid hydrolysis. Water necessary for hydrolysis can originate from
various sources: it may be present originally on the surface, it may be
added, or it may come from the atmosphere. However, most bonds
to Si oxidize slowly, and protecting silanes from moisture is more
important than protecting them from O2.
3-Methacryloxypropyltrimethoxysilane (MPS) is commonly
used in clinical commercial silane products. This silane monomer
is prehydrolyzed in an acidified solvent mixture of ethanol and
water before its use on a restoration surface [15, 36]. Several factors
determine the silane reactivity, for example, the drying time on a
substrate surface prior to cementation, in this case [39].
In dental laboratories, the standard procedure of the surface
treatment of some indirect dental restorative materials such as metal
alloys and, for example, Ti [12–15], zirconia [40, 41], or porcelain [17,
26, 42], is first sandblasting or HF etching, rinsing, and drying. Then,
a solution of the silane coupling agent is applied onto the treated
surface with one thin coating using a clean fine bush. The silane is
Current Studies on Other Surface Pretreatment Methods 375
then allowed to dry and react: in chair-side clinical applications the

curing is expected to happen at room temperature in a few minutes.
On the other hand, when dental restorations are made in the dental
laboratory, prolonged curing times and higher temperatures can be
used [16]. The step of applying a silane coating is called silanization
(or silanation). Cementation should then follow immediately after
silanization.
Silane coupling agents should be activated because the condensation

between hydrolyzed silane, that is, silanols (–SiOH), and surface
hydroxyl groups on the substrate surface is fast at room temperature

through hydrogen bond formation.
The condensation between unhydrolyzed silane monomers and
surface hydroxyl groups is slow at a reduced temperature.
11.6 Current Studies on Other Surface

Pretreatment Methods
Many laboratory studies show bond degradation over time under
artificial aging with the conventional surface treatments discussed
above [41, 43]. Moreover, surface treatment by grit blasting and
tribochemical silica-coating may introduce surface flaws that will
affect long-term performance of, for example, ceramics [44]. As
a result, other surface pretreatment methods are developed to
increase bond durability under artificial aging. In these methods,
substrate surfaces are modified physically or chemically. All methods
have different mechanisms of treatment to activate surfaces, and
these will be discussed in section 11.7.
11.6.1 Chemical Treatment

At room temperature, the surfaces of metal oxides, metals, and
metal alloys are partially hydroxylated. For some metals, such as Cr,
Al, and Ti, and some metal alloys, a passive oxide layer is formed.
The presence of hydroxyl groups (–OH) will favor the interaction
with silane coupling agents by forming hydrogen bonds first.
This is followed by condensation to form a linkage and finally
covalent bonds. The extent of condensation depends on the surface
hydroxyl group density and the nature of substrates. The degree of

hydroxylation is different between ceramic and metal surfaces. The
density of hydroxyl groups can be increased by treatment with acids.
In this method, the substrate surface is first sandblasted, rinsed,
and dried. Then, the substrate surface is immersed in a strong acid
solution such as hydrochloric acid. After the hydroxylation process,
the number of hydroxyl groups is increased, which depends on the
types of acids and the processing temperature [45, 46].
11.6.2 Selective Infiltration Etching

The selective infiltration etching (SIE) method is a specifically

developed novel pretreatment method for zirconia-based surface
treatment to enhance resin zirconia bonding. A special glass powder
conditioning agent containing SiO2, Al2O3, Na2O, TiO2, and K2O is
mixed with water to form a paste. The zirconia surface is coated
with a thin layer of this paste and cured at high temperature. Next,
the coated zirconia is cooled to room temperature. This glass-
conditioning agent is etched away with dilute HCl and then rinsed
with deionized water. This creates a highly reactive and retentive
surface. After silanization (or without it) a resin cement is used
for bonding the zirconia surface [47–49]. The SIE method is also
covered in Chapter 14.
11.6.3 Laser Treatments

Three types of lasers are used for surface treatment of different
dental materials:
(1) Erbium: yttrium-aluminum-garnet (Er:YAG)
(2) Neodymium: yttrium-aluminum-garnet (Nd:YAG)
(3) Carbon dioxide (CO2)
Different types of lasers are used for different dental materials and
dental tissues as the emission wavelength of absorption varies with
different materials. During laser treatment, the substrate surface is
irradiated with a laser beam. This produces surface irregularities
that increase the mechanical interlocking, retention [50]. The main
drawback of this method is that too high a power setting of laser
irradiation would create surface cracks [51]. Therefore, it is very
Current Studies on Other Surface Pretreatment Methods 377
important that appropriate laser operating parameters be used for

different materials to minimize crack formation.
11.6.4 Nanostructured Alumina Coating

In this specific coating method, a dilute suspension of aluminum
nitride (AlN) in deionized water is prepared and heated to 75°C.
Then, zirconia specimens are immersed in the suspension.
Aluminum nitride undergoes hydrolysis to form boehmite (g-AlOOH),
which deposits onto the zirconia surface. A nanostructured alumina
coating is thereby formed on the zirconia surface. The coated

zirconia surfaces are air-dried in an oven and thermally treated in
a furnace in air at 900°C. During the heat treatment, the boehmite
undergoes phase transformation through two stages to d-alumina
[52]. A large microretentive area is created on the zirconia surface,
which increases the micromechanical interlocking (retention) for
resin bonding.
11.6.5 Internal Porcelain Coating

In this technique, zirconia surfaces are coated with silica-based
ceramics by fusion. The surfaces are first polished and then air-
abraded with alumina powder to increase surface roughness. Then,
the treated zirconia surface is coated with fusing porcelain, which
is prepared by stirring the porcelain powder with distilled water.
The porcelain powder is mainly composed of SiO2 and with a small
amount of Al2O3, Na2O, and K2O. The thickness of the porcelain layer
is about a hundred micrometers. The coated porcelain layer is fired
at temperatures higher than 800°C in vacuum for one minute. After
the firing, the surface is cleaned, air-abraded, and then followed by
silanization. Thus, a highly retentive and silica-based coated zirconia
surface is obtained for resin bonding [53].
11.6.6 Chemical Vapor Deposition

The zirconia surface can be pretreated with oxygen plasma to
remove organic contaminants and increase the degree of surface
hydroxylation. In the molecular vapor deposition system, a pretreated
zirconia specimen is fixed in position in a vacuum chamber. A mixture

of tetrachlorosilane (SiCl4) and water is heated. The vapor mixture is
passed onto the zirconia surface. The silane undergoes hydrolysis to
form silanols (–SiOH), which react with the surface hydroxyl groups
of zirconia. A silica seed layer (SixOy) is deposited on the zirconia
surface and a by-product HCl gas produced. The layer thickness is
controlled by the deposition time [54]. The presence of the SixOy
seed layer is reported to form durable siloxane bonds with a silane
coupling agent, and this improves adhesion to zirconia.
11.6.7 Plasma Fluorination

This is another advanced technique in which the zirconia surface
is chemically modified to be more reactive by means of plasma
treatment. In an inductively coupled plasma reactor, zirconia samples
are exposed to a continuous flow of sulfur hexafluoride (SF6) gas at
a constant pressure for a certain period of time. Plasma is generated
when an electric current is applied. The sulfur hexafluoride forms
a highly reactive species and reacts with zirconia. After plasma
fluorination, an oxyfluoride surface layer is formed. When a silane
coupling agent is applied onto this active layer, a reaction occurs
such that surface silanation is achieved. However, the mechanism of
bond formation between silane and the oxyfluoride layer remains
still unknown [55].
11.7 Mechanisms of Surface Pretreatment

Methods
In this section, the mechanisms of each surface pretreatment method
introduced above are discussed to help the readers to understand
the underlying principles. Each method has a different mechanism
to achieve surface modification such that strong adhesion is
attained. In principle, a surface is more reactive after treatment by
(a) increasing the surface roughness for mechanical interlocking or
(b) increasing the surface chemical reactivity for chemical bonding
formation or both [7].
Mechanisms of Surface Pretreatment Methods 379
11.7.1 Hydrofluoric Acid Etching

There is a general agreement that HF etching followed by silanization
generates higher bond strengths than either treatment alone
[17]. Application of a silane coupling agent is a procedure called
silanization. It is understood to create hydrogen and covalent bonds
between the luting resin cement and the ceramic substrate, while
etching per se provides micromechanical interlocking [15–17, 26].
When HF is applied on the surface of a porcelain veneer, a series of
reactions (Eqs. 11.11–11.13) occur:
SiO2 (s) + HF (aq) Æ SiF4 (ad) + H2O (l) (11.11)

SiF4 (ad) + 2F¯ (aq) Æ SiF62¯ (aq) (11.12)
SiF4 (ad) + 2HF2¯ (aq) Æ HSiF6¯ (aq) (11.13)
where HF2¯ is formed from HF and dissociated F– [56]. The SiF4 formed
is adsorbed (= ad) on the surface and then further reacts with F–.
The etching rate depends on the surface structure, HF concentration,
and which types of dental porcelain are used [57]. The etching of
the amorphous state is faster than the crystalline state as the former
is in a higher energy state than the latter. In clinical practice, the
HF etching of a porcelain veneer is to remove the amorphous silica
structure in order to increase the surface roughness and thus the
micromechanical interlocking retention [42, 58].
Some other reagents, such as ammonium hydrogen difluoride
(NH4HF2), may also etch porcelain [17]. It was suggested that HF
etching might be substituted by grit blasting using alumina powder,
followed by so-called modified silanization, that is, an idea to utilize
hot air to cure the siloxane film [59].
11.7.2 Pyrochemical Silica Coating

A pyrochemical reaction is defined as the process of chemical
reactions at high temperatures. For pyrochemical silica coating,
the silane, in this case tetraethoxysilane (i.e., tetraethylsilicate),
Si(OCH2CH3)4, is injected into the flame. The fuel gas is butane and
is burned in atmospheric oxygen, that is, a combustion reaction. The
reaction mechanism is a series of free-radical reactions. The initial

step is hydrogen abstraction of tetraethoxysilane by oxygen to form
reactive free radicals [60]. Then, a series of free-radical reactions
proceed, and e.g., SiOx-C species are formed. These reactive species
deposit and condense onto the substrate surface to form a glass-like
layer [29].
11.7.3 Grit Blasting and Tribochemical Silica-Coating

The principles of grit blasting and sandblasting are basically the
same [15, 34]. Sand (actually, we should use the word powder)
particles are projected under compressed air from a nozzle onto
the substrate surface. The impact of the particles on the substrate
surface causes kinetic energy transfer. The energy is transformed into
heat energy. The energy absorbed by the substrate surface results
in melting. The powder particles are partially incorporated into the
substrate surface [61]. A suggested mechanism for grit blasting and
tribochemical silica coating is shown in Fig. 11.4.
Figure 11.4 A schematic diagram of sandblasting on a substrate surface.

11.7.4 Silanization
A silane coupling agent (silane) contains two functional groups, with
the general formula of Z-(CH2)k-Si-(OR’)3: Z is an organofunctional
group, –(CH2)k– is a linker (connector) segment, and –OR’ is a
hydrolyzable group. Silanes can react with the resin composite and
inorganic dental restorative materials to join together. Silanes have
to be activated such that free silanol groups are produced that react
with the hydroxyl groups on inorganic substrate surfaces [15, 36].
When the silanes undergo hydrolysis, the alkoxyl group is
protonated at pH 3–5. A bimolecular nucleophilic substitution takes

place at the central silicon atom. A backside attack of a nucleophile,
water, to the silicon atom, an electrophile, gives a pentavalent
transition state. A new covalent bond is formed, and a covalent bond
is cleaved between the silicon and the leaving group [36]. The silane
hydrolysis mechanism is shown in Fig. 11.5.
Figure 11.5 A reaction mechanism of silane hydrolysis.
The rate of silane hydrolysis is affected by steric and inductive

effects of alkoxy groups. The steric effect is the major factor that
affects the reaction rate [62]. If the alkoxy group (–OR’) is large in
size, it is more difficult for the nucleophile (water) to approach the
silicon central atom. The activation energy of the transition state
formation is increased, and the hydrolysis rate is thus decreased
[7, 36].
In use, silane monomers are usually strongly diluted in a
solvent that is usually ethanol (plus some water). The final silane
concentration may be somewhere in the range of 0.1–5 vol% for
coupling purposes. When the silane coupling agent is applied
onto a silica-coated substrate surface, the silanol groups (–SiOH)

interact with the surface hydroxyl groups of the substrate by
forming hydrogen bonds. This is followed by condensation to form
a siloxane (…–Si–O–Si–…) linkage. The silane monomers react
with other silane monomers through the silanol groups to form a
3D polysiloxane network. The degree of polymerization of silane
monomers is controlled e.g., by the amount of water available and
also the organofunctional moiety [15, 36]. After the process of
silanization of the restoration, a resin composite cement is applied
onto the silanized substrate surface, fitted on the prepared tooth,
and finally light-cured.

The actual thickness of a silane coating (polysiloxane layer)
is determined by several factors, such as silane concentration,
drying (reaction) time, solvent used, pH, deposition technique, and
temperature [36]. In practice, silane coatings are extremely thin 3D
multilayer systems.
Figure 11.6 demonstrates how initially hydrophobic silanes first
turn hydrophilic during hydrolysis—and they condense to form
dimers, oligomers, etc. Next, silanes deposit onto the surface, and
after curing (setting), they form a hydrophobic siloxane layer [36].
Figure 11.6 The processes of silane hydrolysis, silanization, and setting

reaction with a resin composite luting cement.
Interestingly, silane blends, that is, combinations of functional

silanes and cross-linker silanes (e.g., BTSE) in a solvent (see Fig. 11.3)
may have a significant impact on bonding to a substrate, increasing
mechanical strength and hydrolytic stability in many coatings and
composite systems. Some silane blends containing BTSE can provide
excellent protection for corrosion in applications where steel
sheets are silanized and then finally painted. It is noteworthy that
cross-linker silanes are strongly diluted and blended at the ratio of
1:10–1:5 to an organofunctional silane [38].
A so-called novel silane system concept for resin-bonding
promotion in dental applications was introduced by Matinlinna et

al. [63]. Laboratory studies suggest a significant growth in shear
bond strength for resin Ti bonding [63–67], resin porcelain bonding
[68], and resin zirconia bonding [69, 70] when the control has been
a commercially available dental silane [37]. To demonstrate a novel
silane system in dentistry, we may have a look at silica-coated and
silanized zirconia substrates (Fig. 11.7).
Figure 11.7 An illustration of a novel silane system applied in resin zirconia

bonding.
A functional silane, in this case MPS, is blended with BTSE,

and they form a durable, hydrolytically stable 3D siloxane film to
connect the silica-coated zirconia surface to a resin composite luting
cement. This novel silane system approach in resin bonding might
have clinical success (durable cementation) when meticulously
optimized.
In addition to a novel silane system, the use of some other
functional silane monomers on bonding resin to silica-coated
substrates may be a key for durable bonding [71–75].
When speaking about silane-aided bonding in conjunction
with resin composites, we may notice the role and importance of

chemistry. The resin composites used in dentistry are predominantly
methacrylate monomers such as 2,2-bis[4(2-hydroxy-3-
methacryloxypropyloxy)-phenyl] propane (bis-GMA) and urethane
dimethacrylate (UDMA or UEDMA) that contain the polymerizable
>C=C< functional groups.
The initiators in the resin composite decompose by blue visible
light to form energetic free-radical species. These reactive species
react with the >C=C< groups in resin monomers. This process
generates other reactive free radicals. These free radicals react
with resin monomers to form new C–C single bonds. After the light-
curing process, the resin composite and the inorganic substrate
are connected by the silane coupling agents [36, 75]. A suggested
mechanism of the whole process is shown above in Fig. 11.6. More
about resin composites in dentistry is found in Chapter 6.
11.7.5 Chemical Treatments

On a metal oxide surface, the outermost surface layer is composed of
oxide ions. These are very reactive sites for surface chemical reactions.
When the oxide surface is treated with an acid, the dangling oxygen
atoms form intermolecular hydrogen bonds with the acid. After
rinsing with deionized water, surface hydroxyl groups are formed
after hydroxylation [45]. A suggested mechanism of hydroxylation of
metal oxide by acid treatment is shown in Fig. 11.8.
The degree of hydroxylation depends on the acid concentration
and what type of acid is used and on the time and temperature of
the treatment [76]. For metals/metal alloys, a layer of passive oxide
layer is formed at ambient temperature. The presence of this oxide
layer favors the formation of hydroxyl groups after acid treatment.
Figure 11.8 The process of hydroxylation on a metal oxide surface by acid

treatment. Modified from Ref. [45].
11.7.6 Selective Infiltration Etching

One of the most interesting new openings in zirconia surface
pretreatments is SIE (see also Chapter 14). The basics for this
treatment are heat-induced structural maturation and grain
boundary diffusion to transform the relatively smooth nonretentive
surface of yttria-stabilized zirconia into a highly retentive surface
[47, 77]. As described above, when a zirconia surface is coated
with a special glass-conditioning agent and heated above its glass
transition temperature, the molten glass particles infiltrate into the
surface grain boundaries and induce surface tension, which results
in movements of the surface grains. This creates an intergrain
porosity. Finally, the glass infiltration agent is removed by acid-
etching treatment with HF and rinsing with water. The zirconia
surface is thereby transformed into a highly reactive and retentive
surface [49].
11.7.7 Laser Treatments

The acronym “laser” stands for light amplification by stimulated
emission of radiation. It is a process of optical amplification from
stimulated emission of photons absorbed by atoms or molecules
[78]. When a laser beam hits a substrate surface, there are four ways
of interaction.
The first one is reflection: the beam bends back from the surface
and causes no effect. The second one is scattering, in which the beam
is deflected in different directions. The third one is transmission,
during which the beam passes through the surface without any
interaction. The fourth one is absorption: the laser energy is absorbed
when the laser beam interacts with the material [79]. Absorption of
the laser energy leads to conversion into heat energy. This causes
melting of the material and change of surface morphology. However,
when the laser intensity increases, more heat is generated, and
thus microcracks are formed (Fig. 11.9). One approach to minimize
microcrack formation is to use a lower laser power setting [80].
11.7.8 Nanostructured Alumina Coating

Aluminum nitride can undergo hydrolysis to form boehmite and
ammonia (Eqs. 11.14 and 11.15). At the initial stage of hydrolysis
of aluminum nitride, there is an increase in the concentration of
aqueous aluminum (poly)cations in the suspension. This leads to
supersaturation that allows the heterogeneous nucleation of lamellar
boehmite on the substrate surface immersed in the suspension. After
the coating process, the coated surface is heat-treated. The boehmite-
coated layer then undergoes a series of phase transformations
accordingly [81]:
AIN + H2O g-AlOOH + NH3 (11.14)
300-500°C 700-800°C 900-1100°C
g-AlOOH g-Al2O3 d-Al2O3
1000-1100°C
q-Al2O3 a-Al2O3 (11.15)
The alumina-coated layer is heat-treated up to 900°C. The

reason for this heat treatment is that during phase transformation
from g-AlOOH to a-Al2O3, the surface area of the alumina particles
increases from g-AlOOH to a maximum at d-Al2O3 and then decreases
to a minimum at a-Al2O3 [82]. A large surface area is obtained

after heat treatment to 900°C. This increases the micromechanical
interlocking (retention) for resin bonding.
Figure 11.9 A schematic diagram of the effect of laser treatment. Modified

from Ref. [79].
11.7.9 Internal Porcelain Coating

The mechanism of internal coating is similar to SIE: a zirconia
surface is coated with a fusing porcelain powder, a ceramic veneering
material that is suspended in distilled water. During the firing of the
porcelain coating on zirconia at high temperature, the porcelain
particles infiltrate into the grain boundaries of the zirconia surface
layer. A thin layer of porcelain is finally fused on the zirconia surface.
The composition of the ceramic veneering material is similar to
the glass-conditioning agent used in the SIE technique [47, 49]

(see above).
The main difference between these two techniques is that a
silica-based coating is formed for the internal porcelain coating,
whereas a highly retentive surface is created after removal (etching)
of the glass infiltration agent by HF [83].
11.7.10 Chemical Vapor Deposition

Chemical vapor deposition (CVD) is defined as a process in which a
thin film is deposited on a substrate by means of chemical reactions

of the gaseous reactants at a high temperature near or on a heated
substrate [84]. CVD is a chemical process used to produce high-
performance and high-purity solid materials. The process often
finds applications in the semiconductor industry to produce specific
thin films.
The process of CVD involves several steps [85]:
1. Flow of gaseous reactants into the system
2. Diffusion of gaseous reactants through the boundary layer to
the substrate
3. Adsorption of gases onto the substrate surface
4. Chemical reactions of the adsorbed species with the substrate
at the surface layer
5. Desorption of by-products from the substrate surface
6. Diffusion of gaseous by-products through the boundary layer
to the bulk gas
7. Exit of gases from the system
The actual process is shown below in Fig. 11.10.
11.7.11 Plasma Fluorination

The main advantage of this method over CVD is that the reaction
activated by plasma could be processed at a lower deposition
temperature. Plasma is an active species, which is composed of
highly excited ionic and free-radical species. It is produced when
reactant gases are excited into energetic states by microwave, radio
frequency, or electrons from a hot filament discharge [86]. When
atoms or molecules gain enough energy, ionization occurs.
Figure 11.10 A schematic diagram of the CVD process. Modified from Ref.
[85].
A mechanism suggested by Hodak et al. [87] for the plasma

fluorination of silk fabrics, using sulfur hexafluoride (SF6) as the
source gas, is:
SF6 Æ SF5· + F (11.16)
SF5· Æ SF4 + F (11.17)
SF5· + SF6 Æ S2F10 + F (11.18)
S2F10 Æ 2 SF5· (11.19)
The fluorine atoms generated react with the fabric surface to
form a fluorinated layer. The SF5· radicals generated would either
decompose into SF4 and F or combine with SF6 to form S2F10 and F,
since no sulfur is detected on the modified silk fabric surface from
X-ray photoelectron spectroscopy (XPS) analysis [87]. This reaction
mechanism can be used to explain the fluorination of zirconia
surfaces in resin zirconia bonding reported by Piascik et al. [55].
These surface treatment methods, with different approaches,
modify the surface properties of some dental materials (e.g., zirconia)
in order to enhance adhesion. However, some of them employ toxic
precursors such as sulfur hexafluoride and other use expensive
instruments such as a molecular vapor deposition system. Further
laboratory studies of these treatment methods are necessary. These
are important factors to consider before these methods are fully
implemented in dental practice.
11.8 Conclusions
The surface pretreatment methods of dental indirect restorative
materials are discussed thoroughly in this chapter. These methods
are currently in use, either at dental laboratories or under intensive
development in research laboratories. This research takes place
in vitro, in vivo, and in silico. In the future, validation of these new
methods in clinical practice will be carried out. On the other hand,
other new surface treatment methods will obviously emerge and be
investigated globally [88].
We may conclude that an ideal surface treatment method should:

1. be nondestructive to substrate surfaces;
2. provide strong and durable bonding;
3. be sustainable in the oral environment for long-term
performance; and
4. be convenient to use for dental technicians and/or dentists.
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Chapter 11

Surface Pretreatment Methods and

Christie Ying Kei Lung and Jukka P. Matinlinna

The clinical success of dental restorations depends on the adhesive

Handbook of Oral Biomaterials

treatment methods, (4) some other new surface treatment methods

and the restoration (resin composite materials are discussed

11.2 Surface Science

11.2.1 Interface and Surface Tension

change in the system properties with distance. Properties that show

surface tension [3]:

11.2.2 Contact Angle

The ability of a liquid to keep in contact with a solid surface is

11.2.3 Critical Surface Tension

11.3 Theories of Adhesion

substrate surface is a combination of different mechanisms.

Currently, there are six dominating theories of adhesion to

11.3.1 Mechanical Interlocking Theory

presence of voids at the interface lowers the adhesion. In general,

11.3.2 Wetting Theory

11.3.3 Diffusion Theory

11.3.4 Weak Boundary Layer Theory

Therefore, surface pretreatments before bonding are necessary to

11.3.5 Electrostatic Theory

11.3.6 Chemical Bonding Theory

11.4 Surface Characterization Techniques

11.4.1 Infrared Spectroscopy

All molecules are capable of vibrating above 0 K, that is, –273.15°C,

For analysis of the sample surface, the attenuated total internal

recombine the resultant beam. The interference pattern is analyzed

11.4.2 Scanning Electron Microscopy

11.4.3 Energy Dispersive X-Ray Spectroscopy

the material surface structure. When electrons of the atoms on

11.4.4 Transmission Electron Microscopy

with the crystalline planes of the sample when a high voltage of

11.4.5 Atomic Force Microscopy

11.5 Surface Pretreatment Methods Used in

11.5.1 Hydrofluoric Acid Etching

causing extensive internal tissue damage [18]. In a typical dental

11.5.2 Grit Blasting

11.5.3 Pyrochemical Silica Coating

tems (aka thermal silica-coating systems) that have been utilized in

chemically interesting surface-conditioning method is not anymore

11.5.4 Tribochemical Silica Coating

form metallosiloxane bonds of the type –Si–O–M– (where M = metal).

Figure 11.3 Some silane coupling agents. BTSE is a so-called cross-linking

Silanes are characterized by direct silicon–carbon (Si–C)

The silicon (Si) produced from silica reacts with hydrogen

then allowed to dry and react: in chair-side clinical applications the

Silane coupling agents should be activated because the condensation

hydroxyl groups on the substrate surface is fast at room temperature

11.6 Current Studies on Other Surface

11.6.1 Chemical Treatment

hydroxyl group density and the nature of substrates. The degree of

11.6.2 Selective Infiltration Etching

The selective infiltration etching (SIE) method is a specifically

11.6.3 Laser Treatments

important that appropriate laser operating parameters be used for

11.6.4 Nanostructured Alumina Coating