Silicon Chemistry 1: 397402, 2002.

2004 Kluwer Academic Publishers. Printed in the Netherlands.

397

Solvent effect on TEOS film formation in the sandstone consolidation

process
Ramon Zarraga 1 , Dolores E. Alvarez-Gasca 2 & Jorge Cervantes 1,
1 Facultad de

Qumica, Universidad de Guanajuato, Guanajuato, Gto., 36050, Mexico,

Arquitectura, Universidad de Guanajuato, Guanajuato, Gto., 36000, Mexico,
Author for correspondence (e-mail: jauregi@quijote.ugto.mx)
2 Facultad de

(Received 11 February 2003; accepted 7 August 2003)

Key words: consolidants, film formation, sandstone, solvent effect, TEOS

Abstract
Alkoxysilanes, low-viscosity monomers capable of polymerizing into the porous network of stone by a sol-gel
process, are widely used as consolidants in the restoration of stone monuments. However, since consolidation is a
non-reversible application capable of causing serious harmful side effects to the original material, stone consolidation is almost always considered a very risky intervention. Alkoxysilanes are insoluble in water, so co-solvented
systems are very often used, but even knowing that the solvent is a determinant parameter for sol-gel reactions,
there is still a lack of information regarding how it can influence the stone-alkoxysilane affinity. For two different
tetraethoxysilane-acidic co-solvented systems we are reporting both the morphological characteristics showed by
gels formed in situ and the affinity reached with the stone in the sandstone consolidation process. Aqueous solutions
of ethanol and methyl-ethyl-ketone (MEK) were the solvents compared. SEM and 29 Si Solid State NMR were used
to determine the alkoxysilane performance on these silicic-based materials. It was found that using MEK solutions
resulted in appreciable sandstone-alkoxysilane interaction, forming a more homogeneous film. On the other hand,
ethanol does not promote alkoxysilane-sandstone compatibility. A brittle film is obtained when ethanol is used.

Introduction
In recent years, an apparent acceleration in the rate of
stone decay and the growing worldwide interest in preserving historic buildings are promoting a significant
increase in the number of studies on restoration. Using
alkoxysilane-based products as stone consolidants to
preserve decayed quartz-bearing rocks, like sandstone
in historical buildings, has become a common practice in the last decades [13]. The market impact is
indicated by the fact that 50% of non-funcionalized
silicon compounds are directed towards architectural
coatings and mineral consolidation [4]. Alkoxysilanes,
such as tetraethoxysilane (TEOS), are applied as low
viscosity monomers or dimers in solutions that may include water, ethanol, other organic solvents (generally
This paper is dedicated to Professor Kohei Tamao, 2002

Kipping Award winner.

MEK and acetone) and some organometallic catalysts.

In a recent overview of current research on stone
preservation, consolidation is considered as an active conservation process . . . where stone is severely
weakened by decay, some form of consolidation may
be necessary to restore some strength. Ideally, one
might hope to make the stone at least as strong as it
was originally, so it might resist further decay. . . [5].
The drawback is that contradictory reports regarding
the performance of alkoxysilane consolidants proliferate in the literature. For some conservationists they
perform well, for some others they perform poorly
on substrates with equivalent mineral composition [6].
Actually we can say that consolidation processes are
not entirely mastered. And to make things more complex, harmful side effects are very frequent in consolidation interventions, suggesting that there is still
a long road ahead until full mastery of the process is
reached [7, 8].

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Scheme 1.

The main reason behind this lack of consistency

in results seems to be basically related to the level of
chemical affinity achieved by the alkoxysilane-stone,
as well as the characteristics in the resulting film
[912]. Sol-gel chemistry is directly involved in the
consolidation process from the moment the alkoxysilane solution is in contact with the stone substrate
until the polymeric film is deposited and dried. In all
cases it has been established by Brinker and Scherer
that the chemical processes behind gel formation are
greatly influenced by the presence of, among others,
the solvent and/or co-solvent added [13].
The effect of the solvent on the consolidation process has been largely neglected. Diverse formulations
with different kinds of solvents have been added to
TEOS in order to decrease its concentration and viscosity, making the initial solution able to penetrate
deeply into the substrate [5]. In order to start the
polymerization, water is required (both in acid and
organometallic catalyzed reactions), but the process is
considerably more efficient if a co-solvent is added
to achieve immediate miscibility. Popular commercial consolidants (Wacker OH and Tegovakon V) are
water-free. However, considering that the purpose here
is to maximize chemical interactions with the surface
silanols in the stone, water is needed as has been suggested by some authors [14, 15] in order to obtain
reactive pre-hydrolyzed species. On the other hand,
hydrolysis and condensation reactions are complicated
by solvent interactions, particularly in their affect
on the orientation of the silanol molecules. It has
been suggested [16] that intramolecular condensation
(cyclization) is promoted in acidic ethanol solutions,
a prejudicial situation for the homogeneous gelation
necessary to achieve an effective consolidation process. Also, if an alcohol is used, it does not merely
act as a solvent. Alcohol, because it is a reaction
product, when added to the alkoxysilane/water system
may cause the reverse of reactions 2 and 3 shown in
Scheme 1 (esterification and alcoholysis) to occur. The
extent to which this occurs depends upon the amount
of the alcohol added and the pH of the system [13].

Application of IR spectroscopy to study alkoxysilane-silanol reactions is limited by the strong background absorption bands of bulk siloxane structures
[14]. However, we have shown recently that it is possible to determine the sandstone decay degree by Solid
State 29 Si NMR methods. We have also suggested that
the value of consolidation obtained is consistent with
some particular modifications in the Q2 Q3 region in
the 29 Si NMR spectrum, which can be attributed to
the chemical compatibility achieved between the alkoxysilane species and the surface silanols on the rock
[11].
In the present work we use 29 Si NMR methods
and SEM to investigate how the TEOS consolidation
process is influenced by the use of different kinds of
solvents in aqueous-acidic systems, in this particular
case ethanol and methyl-ethyl-ketone.
Experimental
Procedure
Different 5 5 3 cm (35.0 1 g) samples of
sound (BET surface area = 5.3 m2 g1 ) and partially decayed (6.2 m2 g1 ) pink quarry stone, the
most common sandstone employed in Mexicos central region, were collected from Jaral Church during
recent renovations. Mineralogical analysis and XRD
confirmed that both samples belonged to the same
bed, showing also that the composition of the sound
stone is mainly albite and quartz, with a small quantity
of hipersterne and hematite. Partially decayed stones
show a lower level of albite and diverse levels of kaolinite [11, 17]. This is evidence that sodium feldspar
(albite) has been hydrolyzed to clay materials in the
process known as kaolinization [18].
Data for each sample were obtained after its collection, and again after they all were sprayed and
permitted to react for 3 weeks in black plastic bags
with 10 mL of two different TEOS solutions at pH = 3
(hydrochloric acid was used). The consolidant solutions used were (% vol): (1) 65% TEOS, 25% EtOH
and 10% water; (2) 65% TEOS, 25% MEK and 10%
water. We named them TEOS EtOH and TEOS MEK,
respectively.
For the compatibility assessment, blank experiments were carried out mixing powders of the untreated samples with both the different xerogels obtained aside from TEOS MEK and TEOS EtOH solutions, in the same proportion as we used in the
consolidation part.

399
Chemical reagents
Tetraethoxysilane (TEOS), 99+% was obtained from
ethanolysis of SiCl4 in a pilot plant facility [19].
Reagent grade solvents used were hydrochloric acid
(HCl), ethanol (EtOH) and methyl-ethyl-ketone
(MEK) and were purchased from Aldrich. All reagents
were used as received without any further purification.
Scanning Electron Microscopy (SEM)
A palladium-gold alloy was vacuum evaporated onto
the dried samples. They were then investigated using
a LAICA S-420 Scanning Electron Microscope.
Nuclear Magnetic Resonance (NMR)
29 Si

MAS NMR spectra were recorded on a Varian

Unity Plus 300 MHz spectrometer operating at 59.58
MHz. A 7-mm diameter silicon nitride rotor with kelF caps was used. The rotor spin rate was 4 KHz,
with a delay time of 8 s, and 1600 transients were
accumulated.

Figure 1. 29 Si NMR spectra of untreated samples. (a) The partially

decayed sandstone; (b) the sound sandstone.

Results and discussion

Information on chemical affinity and gel morphology
was determined using two experimental methods, 29 Si
MAS NMR spectroscopy and Scanning Electron Microscopy (SEM). The results are discussed below.
29 Si

MAS Nuclear Magnetic Resonance (NMR)

29 Si

MAS NMR spectra from the sound stone and

the partially decayed sandstone are shown in Figure 1. Interpretation of 29 Si NMR spectra is based
on data given in the literature [11, 20, 21]. The big
and narrow quartz signal around 100 ppm persists in
both samples, but the broad feldspar signal between
83 and 94 ppm is lower in the decayed sample,
indicating some kaolinization has occurred. Partially
decayed stone mixed with xerogels proceeding from
TEOS MEK and TEOS EtOH solutions exhibits a
slight increase in the Q3 region (around 93 ppm),
as shown in Figure 2. Evidently this change is due to
the abundance of xerogels in the Q3 species, which is
more intense in TEOS EtOH, as can be seen in Figure 3. Small rings (cyclic trimers), formed appreciably
only in the presence of ethanol, can also be observed
in Figure 3(a) by the narrow peak at 87.7 ppm.

Figure 2. 29 Si NMR spectra of partially decayed sandstone mixed

with powders of xerogels using (a) TEOS with EtOH, and (b) TEOS
with MEK.

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Figure 3. 29 Si NMR spectra of xerogels using (a) TEOS with EtOH,

and (b) TEOS with MEK.

The same stone, consolidated with both (a) TEOS

EtOH and (b) TEOS MEK, respectively, is illustrated
in Figure 4. It can be concluded from the higher signal increase observed in both the Q2 and Q3 regions
(around 87 and 93 ppm) that a superior chemical interaction was achieved with TEOS dissolved
in methyl-ethyl-ketone. The higher polarity of ethanol makes this solvent avid for the available silanol
groups in the stone. That is, the substrate, polymer
and solvent form a competitive acid-base triangle. Besides, the significant tendency of alkoxysilanes to form
rings instead of condensing directly with the stone in
acidic ethanol solutions results in an even higher lack
of chemical affinity.
Scanning Electron Microscopy (SEM)
Figure 5 shows a typical decayed sandstone, with high
porosity, some feldspar crystals and some kaolinitic
material product from the weathering processes. In
Figure 6 a characteristic film obtained in situ from
TEOS EtOH solution can be observed. It looks brittle
and thick. On the other hand, a much more continuous and thin film formed from TEOS MEK solution
is shown in Figure 7. The reason for this remarkable

Figure 4. 29 Si NMR spectra of partially decayed sandstone consolidated using (a) TEOS with MEK, and (b) TEOS with EtOH.

behavior seems to confirm the effect above mentioned

of the higher polarity shown by ethanol. The cyclization rate constants are raised for the oligomers recently
formed in the solution, as has been suggested [16]
and observed by 29 Si NMR techniques in Figure 3(a),
producing a bulky and less homogeneous coating.

Conclusions
The sandstone consolidation process with alkoxysilanes is decidedly influenced by the kind of co-solvent
used, including water, in the solutions.
MEK allows appreciable chemical interactions
between the sandstone and the alkoxysilanes. This
affinity was observed with NMR techniques through
the signal increase observed in both the Q2 and Q3
regions. The way the hydrolyzed species attach to
specific silanols in the stone is still unclear.
Lack of chemical affinity and bad quality coatings
are obtained using ethanol, a very polar solvent. This

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Figure 5. Partially decayed sandstone. Bar = 10 m.

Figure 7. Partially decayed sandstone consolidated using TEOS

with MEK. Bar = 10 m.

References

Figure 6. Partially decayed sandstone consolidated using TEOS

with EtOH. Bar = 10 m.

is probably due to the disablement of the superficial

silanols and the tendency to form rings shown by alkoxysilanes in this kind of chemical environments. We
are currently investigating different ways to increase
the number of available silanols on the stone surface
in order to achieve a better chemical affinity.

Acknowledgements
The authors wish to thank CONACYT and SIGHOCONACYT (Mexico), grant 19990204002, for financial support.

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