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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 consoli-
dation 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.
Chemical reagents
The same stone, consolidated with both (a) TEOS Figure 4. 29 Si NMR spectra of partially decayed sandstone consol-
EtOH and (b) TEOS MEK, respectively, is illustrated idated using (a) TEOS with MEK, and (b) TEOS with EtOH.
in Figure 4. It can be concluded from the higher sig-
nal increase observed in both the Q2 and Q3 regions
behavior seems to confirm the effect above mentioned
(around –87 and –93 ppm) that a superior chem-
of the higher polarity shown by ethanol. The cycliza-
ical interaction was achieved with TEOS dissolved
tion rate constants are raised for the oligomers recently
in methyl-ethyl-ketone. The higher polarity of eth-
formed in the solution, as has been suggested [16]
anol makes this solvent avid for the available silanol
and observed by 29 Si NMR techniques in Figure 3(a),
groups in the stone. That is, the substrate, polymer
producing a bulky and less homogeneous coating.
and solvent form a competitive acid-base triangle. Be-
sides, 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 Conclusions
of chemical affinity.
The sandstone consolidation process with alkoxysil-
Scanning Electron Microscopy (SEM) anes is decidedly influenced by the kind of co-solvent
used, including water, in the solutions.
Figure 5 shows a typical decayed sandstone, with high MEK allows appreciable chemical interactions
porosity, some feldspar crystals and some kaolinitic between the sandstone and the alkoxysilanes. This
material product from the weathering processes. In affinity was observed with NMR techniques through
Figure 6 a characteristic film obtained in situ from the signal increase observed in both the Q2 and Q3
TEOS EtOH solution can be observed. It looks brittle regions. The way the hydrolyzed species attach to
and thick. On the other hand, a much more continu- specific silanols in the stone is still unclear.
ous and thin film formed from TEOS MEK solution Lack of chemical affinity and bad quality coatings
is shown in Figure 7. The reason for this remarkable are obtained using ethanol, a very polar solvent. This
401
Figure 5. Partially decayed sandstone. Bar = 10 µm. Figure 7. Partially decayed sandstone consolidated using TEOS
with MEK. Bar = 10 µm.
References
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