Silica and Silanes-II

Muhammad Farooq
 DBP Number
• The assessment of the liquid-absorbing capacity of synthetic silicas
and silicates may involve the absorption of dibutylphthalate (DBP) .
This largely automated measurement technique provides an
indication of the total volume of liquid that can be absorbed by a
silica sample. The magnitude of the DBP number (24M4-DBP) gives an
initial indication of the inter-aggregate structure and the processing
and dispersion properties of a silica.
• Owing to the toxicity of DBP oil, attempts are being made to replace it
with paraffin oil. Considering the polarity of the silica, polar
substances such as triethanolamine (TEA) can also be used to
determine the inter-aggregate structure (24M4-TEA), analogous to
the DBP measurement.
 Void Volume
• The void volume, i.e., the silica structure as a function of the pressure, is
considerably more reliable than the DBP number. In the void volume
method, the sample is subjected to a defined coarse crushing and then
a specified quantity of the sample is transferred to a cylindrical glass
chamber with a volume scale.
• The chamber is sealed by means of a moving piston. For the
measurement, a constant pressure is applied to the piston until the
volume of the sample in the chamber remains constant.
• Then the measured value is read off. Subsequently, the pressure exerted
on the sample is increased again. Figure shows the decrease in structure
(or the void volume) as the pressure increases. This involves comparison
of a new silica, prepared using a modified manufacturing method, with
the reference silicas Zeosil 1165 MP, Ultrasil 7000 GR, and the
conventional silica Ultrasil VN 3 GR with the same CTAB surface area.
2. Characterization of Surface Chemistry
Chemical Reactions of Silanol Groups
• In the literature, a variety of methods are described that are suitable
for determining silanol groups and their chemical reactivity on the
surfaces of silicas.
• In the determination of silanol groups with lithium aluminum hydride
(LiAlH4), a silica sample is first degassed in a vacuum and then allowed
to react with LiAlH4 at room temperature, and the resultant hydrogen
is determined volumetrically . A further method is the reaction of a
sample with an alkyl lithium or alkyl magnesium reagent followed by
volumetric determination of the resulting alkane. Further reactions
may be performed with alcohols , chlorosilanes ,
hexamethylendisilazane; BCl3, AlCl3 , or boroethane
 NMR Spectroscopy
• With Si NMR examinations of solids, it is possible to detect different
surroundings of the silicon atom on the basis of the oxygen atoms and
hydroxy groups in the silica sample. The ratios of the detected signal
intensities correspond to the proportions of the various Si surroundings in
the sample
• With the solid NMR method, it is possible to distinguish between three
main groups around the silicon atom in silica:
1. Siloxane bridges (bulk)
2. Isolated, terminal SiOH
3. geminal-SiOH
The relative content of isolated or geminal silanol groups and siloxane
bridges is quantifiable, and the different silanol groups are assigned
different reactivities. For example, with respect to organosilanes as coupling
agents , geminal groups are considered to be the most reactive.
 Thermoanalytical Methods
• Thermal analysis is the term given to a group of methods that measure a
physical property of a substance (and/or its reaction products) as a function
of temperature or time while subjecting the substance to a controlled
temperature program. With differential thermal analysis (DTA) it is possible
to monitor the changes in enthalpy of a sample during the course of a
temperature program. The precondition here is that the corresponding
processes (e.g., chemical reactions, phase changes) are sufficiently short to
allow a thermal effect to be observed. DTA is often combined with thermo
gravimetry (TG), which records the weight loss of the sample as a function
of the temperature. From the mass loss, information can be obtained on
resulting products and on the possible course of degradation reactions . In
the case of silica, rational information can be obtained only by means of a
combined DTA–TG measurement, because the thermal effects observed in
DTA are generally negligible on their own
 Small-Angle Scattering
• The method of small-angle scattering (SAS) is a well-known tool to
characterize the structure of fine particles and has been used to
investigate fillers for about 60 years.
• Because precipitated silicas behave in most cases as fractal scatterers,
the scattering of these materials can be described with fractal
structural concepts . In a typical scattering experiment it is possible to
estimate primary particle size and distribution, mass fractal
dimension, and aggregate size; all these parameters depend on the
type of silica investigated. For precipitated silica samples, typical mass
fractal dimensions of dm=1.9 ± 0.2 can be found.
• A huge advantage of the small-angle scattering method is the
examination of silica structure when the material is dispersed in
various media, for example, in rubber
 3. Chemical Bulk Analyses
X-Ray Diffraction
• Synthetic silicas and silicates are amorphous solids. That is, unlike
crystalline solids, they do not possess an infinite three-dimensional
long-range order.
• Consequently, use of the classic X-ray diffraction method is not
possible. Silicas, however, like glass, do have areas of short-range
order that can be determined by appropriate evaluation of the diffuse
X-ray diffraction bands.
• Silicas from a variety of manufacturing processes differ from one
another in terms of their X-ray diffraction bands. When the sample is
tempered, changes in the short-range order can be detected at
temperatures as low as 200C using X-ray diffraction .
D. Process and Technology
1. Production Process
• The various steps of manufacturing silica are displayed schematically
in Scheme 2. In the first step (precipitation), the raw materials
consisting of water glass (sodium silicate solution) and a mineral acid
(normally sulfuric acid is used) are dosed into a stirred vessel
containing water. In many cases, once a defined pH value has been
set, the components are fed continuously to the reactor, this process
taking place simultaneously over a certain time interval. Another
possibility is to first supply a particular quantity of water glass and
initially dose just the sulfuric acid. Normally, this is followed by a
second stage in which water glass and sulfuric acid are added
simultaneously under defined reaction conditions.
2. Influence of Process Parameters on
Product Properties
• During the reaction time, primary particles are first formed in the reactor;
later these particles react with each other, accompanied by dehydration, to
form aggregates. Within the aggregates, the primary particles are linked
together via siloxane bonds. During this process, the aggregates are deposited
to form larger units, or agglomerates. In these agglomerates the aggregates
are held together by hydrogen bonding or van der Waals interactions that are
considerably weaker than siloxane bonds. A state of equilibrium, which is
dependent on the process conditions and can be easily influenced, is reached
between the aggregates and agglomerates. After that, the obtained
suspension is filtered and the filter cake washed. It can then be resuspended
and spray-dried or fed directly to a short-term drying process. Depending on
the drying technology, the product can be optionally first milled and then
granulated or granulated directly to convert it into a low-dust form.
3. Dispersibility and Surface Activity
• An easy incorporation of the silica into the rubber mixture and its
good dispersion are crucial because they have a considerable effect
on the processing costs and on the rubber product’s performance. By
selecting appropriate process parameters, it is possible to influence
the surface properties and therefore the reactivity of the silicas
toward the organosilane. The silanol groups on the silica surface
should be present in a sufficient amount and be accessible for
reaction with organosilanes to ensure a quantitative coupling.
Furthermore, the silane should not be adsorbed in silica pores, not
accessible for the rubber.
4. Typical Process for Rubber Silica
• At present, a variety of manufacturers supply products that can be
divided into three groups:
1. Products that can be described as first-generation, standard, or
conventional silica.
2. Products belonging to the second generation of silica. Today, such
products are frequently termed easily dispersible silica or semi-
highly dispersible (semi-HD) silica.
3. The third and latest generation of silica comprises a product group
characterized by excellent dispersion. These products are described
as highly dispersible (HD) silica.
Modified Production Processes
• Another possibility of yielding products with new technical properties is to
modify the manufacturing process for silicas. For example, reports have
been made on a group of silicas (highly dispersible reactive silicas, HDR)
that allow the reaction with organosilanes to proceed faster and more
effectively owing to the greater reactivity of the silanol groups on the silica
surface.
• A major objective of today’s developments at Degussa is to extend the use
of silica to other tire components and applications such as truck tires and
tire body compounds. For such applications high dispersible silicas with
CTAB surface areas of approximately 190 and 110m2/g have been
introduced to the market.
• They possess a new type of structure that also allows hitherto seemingly
impossible improvements in rubber characteristics. For example, it is
possible to significantly enhance the reinforcing properties of the products
without raising the viscosity of the mixture.
 III. SILANES
Basic Considerations
• Inorganic materials based on silicon or metals and the world of
organic substances founded on carbon chemistry are as incompatible
as oil and vinegar.
• To link these antipoles the main task consists obviously in joining the
two, with the silicon and the carbon in a single molecule. Silanes fulfill
this requirement and are therefore predestined as adhesion
promoters in composite materials.
• The most commonly used bifunctional silane coupling agents are
based on the two structures I and II.
 Definitions: Primer, Adhesive, Modifier
• For the bonding of a polymer to an inorganic substrate, several kinds of
adhesion promoters have to be used. Depending on the thickness and
composition of the bonding layer (interface), the adhesion promoter
may be defined as 1) a primer, 2) an adhesive, or 3) a finish or modifier.
• A primer mainly consists of a lubricant, a binder, and a coupling agent
capable of bonding to the substrate.
• The primer is applied from solution and forms a film with a thickness of
0.1–10 µm and a certain mechanical strength. The primer may be used
for the direct adhesion of the matrix or as a preparation for a following
top coating able to provide the coupling to polymer.
• Hydrolyzable silanes are commonly used as coupling agents that
condense to a polysiloxane structure on the surface
• An adhesive is a gap-filling composite consisting of, e.g., polymers or
resins, fillers, and an adhesion promoter, in some cases a silane.
• In contrast to these adhesion formulations that provide a uniform and
rather thick coverage of the surface, a finish or surface modifier
forms a very thin layer, theoretically a monolayer thick. However,
most of the hydrolyzable silanes result in a several-monolayer-thick
modification of the surface. In this regard the coupling agents used for
the silanization of a siliceous filler in rubber applications should be
defined as surface modifiers.
Function of Silanes as Adhesion Promoters and
Fields of Application
• Bifunctional silanes can be used to chemically link an organic material to
an inorganic substrate. Historically one of the first main applications was
the bonding of glass fibers to thermosetting and thermoplastic resins to
increase the reinforcement, especially at high humidity.
• Depending on the type of polymer system, the functional group X can
consist of an amino, glycidoxy, methacryloxy, or chloro group. The
reinforcement of thermoplastics and rubbers by silane-modified siliceous
fillers is another ‘‘big-volume’’ application.
• For this application sulfur-functional silanes or vinylsilanes are often used.
Silanes with an amino, epoxy, or mercapto group promote the
improvement of the adhesion of sealants to an inorganic surface
Overview of Reactions of Silane Coupling
Agents
• In general a silane adhesion promoter consists of a hydrolyzable group
such as trimethoxy- or triethoxysilyl that provides the coupling of the
silane to the inorganic substrate. In the case of siliceous materials
bearing silanol groups on the surface, Si-O-Si bonds are formed and
alcohol is released. In the presence of moisture an intermolecular
condensation reaction between neighboring silanes is also possible. This
condensation reaction can lead to the formation of multilayers and
stabilization of the silane layer on the surface.
• Aminosilanes may be used as adhesion promoters in several composites
such as phenolic, melamine, or furane resin; epoxy composites; and
polyurethanes as well as coupling agents for polyesters and polyamides.
 B. Essentials of Rubber Silanes
General Structure of Rubber Silanes
• As mentioned above, for the coupling of siliceous fillers to unsaturated elastomers,
silanes with one hydrolyzable moiety to couple with the filler and one functional group
to react with the rubber are optimal (structures I and II).
• The silica coupling is most often achieved by a trialkoxysilyl group, preferably a
trimethoxy- or triethoxysilyl moiety, reacting with the silanol groups on the filler surface
during mixing.
• In the case of sulfur-cured compounds, sulfur-functional silanes are recommended,
because they react with the rubber in the allyl position to the double bond during the
vulcanization process.
• In peroxide-cured compounds, unsaturated silanes such as vinylsilanes perform best.
With exception of the vinylsilane, the two functional groups in the silane are linked by a
propylene group, which also contributes to the hydrophobation of the polar silica
surface.
Types of Rubber Silanes and General
Applications
• For sulfur-cured rubber compounds, the three following types of sulfur functional
silanes are commonly used:

• Whereas the mercapto- and thiocyanatosilanes are used mainly for industrial rubber
goods and for shoe soles, the main application of the di- and polysulfide silanes is in
the tire industry.
continued
• Compared to the high amounts of silane needed in tire tread
applications, the consumption of silanes for industrial rubber goods is
rather low.
• As mentioned above, vinylsilane I is best suited for the reinforcement
in peroxide-cured compounds such as sealants, cables, and profiles.
But owing to the low flash points of the trimethoxy- and
triethoxysilanes, the trimethoxyethoxysilane (I, with R=CH3-O-CH2-
CH2-), with its higher flash point, or fillers premodified with a
vinylsilane are also often used.
D. Characterization of Silanes and
Reactions
Methods of Analysis
• For the characterization and quality control of silanes, several analytical
methods based on the identification of the functional groups are well
established. The different methods can be classified as 1) those
analyzing a characteristic element or a functional group and 2) those
identifying the silane component itself. The most important methods
used to analyze a characteristic functional group are
1. Gravimetric measurement of residue on ignition, which determines
the amount of SiO2 resulting from the content of silicon in the silane .
2. Elemental analysis to determine, e.g., the amount of sulfur, carbon,
chlorine, and nitrogen.
3. Infrared spectroscopy (IR) to identify the functional group by its
characteristic vibration modes
Silica–Silane Coupling
• For the performance of a silane, the reactions are of major importance. The alkoxysilyl group of the
silane can react with silanol groups of the surface of glass fibers or siliceous fillers. This hydrophobation
reaction has been studied intensively for a number of substrates and silanes under various conditions.
• For the rubber industry it is of crucial importance to understand the coupling behavior of
trialkoxysilanes with silica and silicates during the mixing process (in situ modification) and the
presilanization of fillers (ex situ modification).
• The kinetics of the coupling reaction can be determined by using a model system of silica and an inert
solvent to imitate the rubber matrix.
• Taking the results of the above-cited studies into account, it is reasonable to assume that prior to the
silica–silane coupling at least one alkoxy group is hydrolyzed to the more reactive silanol, which then
reacts with a silanol group of the silica, releasing water (primary reaction).
• The hydrolysis reaction is the rate-determining step, and up to a certain point, an increase in water as
well as an increase in temperature increase the reaction speed. Furthermore, the hydrolysis and
condensation reactions are catalyzed by acids and alkalines. The reactivity of the silane decreases with
more alkyl substituents bound to silicon and with increasing steric hindrance of the alkyl and alkoxy
groups
• Due to the fact that trialkoxysilanes can also undergo an intermolecular condensation reaction, oligo-
and polysiloxanes can be formed on the silica surface (secondary reaction) and, as a side reaction, in the
rubber matrix. This condensation reaction needs water and is slower than the primary reaction
Silane–Rubber Coupling
• The reaction of the organofunctional group with the rubber takes place
during the vulcanization process. Therefore it is reasonable to
investigate the silane coupling reaction in commonly used model
systems imitating the vulcanization mechanism. Suitable model olefins
such as 2-methyl-2-pentene, 2,3-dimethyl-2-butene, and squalene,
which imitate the diene rubber, and methods used to follow the
vulcanization reaction were reviewed by Nieuwenhuizen et al.
• Investigations regarding the mechanism and kinetics of coupling
reactions of TESPD and TESPT with sulfur and an accelerator system
have been performed using squalene as the model olefin. It has been
demonstrated that the sulfides Sx with x>2 can react with the rubber at
high temperatures, but the addition of sulfur and accelerators speeds
up the reaction strongly and increases coupling efficiency.
continued
• Furthermore, it has been shown that the reactivity of the polysulfide
increases with increasing sulfur chain length.
• According to the results, it is evident that the disulfide silane needs to
incorporate sulfur for the succeeding coupling reaction, which is possible
only in the presence of an accelerator system.Without sulfur and
accelerator a coupling reaction is not possible . In conventional and
semiefficient cure systems, the tetrasulfide silane TESPT also acts as a sulfur
acceptor, because the formation of di- and polysulfidic bridges requires
more sulfur than the silane already contains. This sulfur incorporation for
an effective coupling reaction is pictured in Scheme on name slide. The
existence of the chemical silica–silane–rubber coupling in the rubber is
demonstrated clearly by the significant increase in reinforcement, as
demonstrated by works of Wagner, Wolff , and Thurn and Wolff