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MODIFICATION OF ALKOXYSILANE GELS BY SIO2


NANOPARTICLES

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Barbora Benetkov , Monika Slavkov , Adla Peterov ,


Petr Kotlka,b

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ICT Prague, Technick 5, Prague, Czech Republic

ICT Prague, Technick 5, Prague, Czech Republic

corresponding author: benetkob@vscht.cz

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Abstract.

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Alkoxysilanes are the most frequently used consolidants for building materials. Bonding role of
previously deteriorated binder provides SiO2 gel, forming in the porous system. However the cracking of
this gel occures over the time, causing the decrease of bonding properties of the gel. In this article, the
cracking was tried to be supressed by the addition of SiO2 nanoparticles into alkoxysilane consolidant.
To evaluate the degree of cracking of the formed gels, the image analysis process was examined.

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Keywords: alkoxysilanes, image analysis, consolidant, building materials, nanoparticles.

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1. Introduction

2. Methods and materials

Alkoxysilanes or silicic acid esters are usually used


as consolidants of building materials. The binding
gel of silicon dioxide from alkoxysilanes is made by
the hydrolysis and condensation reactions and forms
inside the porous system of building material. This gel
replaces the original deteriorated binder [1][2]. However, the cracking occurs during the time, that causes
the decrease of binding abilities of the silicon dioxide
gel. The purpose of this work was to decrease the
degree of cracking by the modification of the original
consolidant by the SiO2 nanoparticles. Nanoparticles should act in the system as mechanical barrier of
spreading cracks and they should also change the properties of the porous system to be less predisposed to
crack. It is assumed that the modified porous system
should better resist the cracking [3][4][5] . The porous
system (porosity and average pore diameter) of the
formed gel should be influenced by added nanoparticles. When small amount is added, the porous system
of the gel is modified only slightly and is affected by
the gel itself. As the quantity of nanoparticles in the
system rises, the porous system is more and more
affected by them. In the end, the main part of the
porous system should be determined by the intergranular space of nanoparticles [6][7][8]. The pore radius
should grow with increasing amount of nanoparticles.
According to this hypothesis, it was observed, how
the degree of cracking depends on amount of added
nanoparticles. The degree of cracking was evaluated
in previous experiments only subjectively. That made
it immpossible to compare the results from different
experiments. In this work, the new evaluation method
- the image analysis in the graphical program ImageJ
- was used to characterize the behaviour of the gels.
That should help to compare more objectively the
results of experiments.

The basic consolidant, modified during the experiment, was Dynasylan 40 (oligomer of tetraethoxysilane, Evonik Industries) catalysed by the neutral
catalyst dibuthyltindilaurate (Sigma-Aldrich). This
mixture is the basis of many commercially provided
alkoxysilane consolidants. This basic mixture was
modified by the silicon dioxide nanoparticles of different grain size Fig 1. Each mixture was prepared with
and without the addition of the methylen blue dye.
The dyed samples were used for image analysis. The
surface area of differently behaved mixtures was than
tested by the BET method.

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2.1. The preparation of mixtures and


samples

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The basic unmodified undyed consolidant mixture


was formed by the Dynasylan 40 and 0,03 mol. % of
dibuthyltindilaurate (D-L). This mixture was shaked
and placed in ultrasonic bath for two hours. To prepare the modified undyed consolidant, the mixture
D-L was after shaking divided into several containers.
The nanoparticles were added to mixtures in containers in amount of 1, 5, 10 and 25 wt %, relative to
the weight of Dynasylan 40. Thus prepared modified mixtures were shaked again and placed in the
ultrasonic bath for two hours. For image analysis all
prepared mixtures were dyed by the addition of 10%
ethanol solution of methylen blue. The dye was added
in the amount of 1 drop (ca 0,018 g) for 7 ml of D-L
mixture. After the ultrasonic bath, 4 ml of mixture
was pipetted on polystyrene petri dishes (diameter
6 cm). Three samples of every mixture were prepared.
The mixture S-V-25 was not prepared because of its
nonnewtonic character, that made the preparation
impossible.

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Figure 1: Designation of prepared modified mixtures

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Figure 2: Procedure of evaluation of shrinkage and


degree of fragmentation by image analysis

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2.2. Image analysis


The samples were kept under the laboratory conditions
for five weeks. They were observed during this time
and photo-documentation was carried out. The pictures of dyed samples were analyzed in image analysis
to find out how shrinked the gels were and what was
their degree of cracking. First, the area was selected
on the photography, that was about to be evaluated.
Than the image was converted into shades of grey and
if needed, the fragments were separated manually at
this stage. The picture was treshold and the ratio
of marked area (gel) and the total selected area was
evaluated to obtain the degree of contraction of the
gel Fig 2. To obtain the value of the cracking degree
the number of fragments was evaluated as the number
of divided marked areas.

2.3. Surface area


The surface area of pores in selected gels was measured
by the BET method. BET method is standard technique of measuring the surface area by the nitrogen
adsorption. According to theory, less fractured gels
should have different surface area in comparison with
unmodified gel, so that low-molecular weight products of hydrolysis and condensation could easily leave
the system. To confirm this claim, less cracked gel
was chosen (S-S-10) to be compared with unmodified
gel (D-L) and modified mixture with lower content of
nanoparticles (S-S-1).

3. Results and discussion


Following figures show the behavior of alkoxysilane
gels 4-5 days and 5 weeks after preparation Fig 3.
The time dependence of shrinkage of gels with different composition shows Fig 4, 5, 6. The experiment

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Figure 4: Time dependence of shrinkage of gels S-M

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had to be terminated earlier for gels disintegrated into


small fragments, or in case that the fragments blew
out into surrounding. Mixtures with higher content
of nanoparticles were less contracted five weeks after
preparation. The standard deviations were enough
small to observe this trend. The only exception was
the mixture S-S-25 that was probably overfilled. It disintegrated quickly into small fragments and remained
of more or less of the same quantity during the five
week experiment. The decrease in shrinkage with
higher content of nanoparticles could be caused by
filling of the free volume in polymeric net, that is responsible for shrinkage. The mixture S-M was chosen
as a representative of the behaviour of modified gels
for the evaluation of time dependence on number of
fragments Fig 7. The magnitude of standard deviations points to the irregularity in fragmentation of gels
of one mixture. The other mixtures acted the same.
This shows that to evaluate the degree of cracking
this way is not appropriate. However, subjectively
was observed that the gels of mixtures S-M-25 and
S-S-10 cracked less than the unmodified consolidant
gel (mixture D-L).
The surface area of pores was measured for three
types of gels D-L, S-S-1, S-S-10 Fig 8. According
to theory, with higher content of nanoparticles, the
surface area grows. The decrease in cracking of gels
filled with higher content of nanoparticles could by
caused by the growth of surface area of pores related
with easier leaving of low-molecular products from the
porous system. The degradation - cracking occured

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Figure 3: A, B Unmodified consolidant mixture (D-L) 5 days (A) and 5 weeks (B) after preparation; C, D
Modified consolidant mixture S-S-10 4 days (C) and 5 weeks (D) after preparation

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Figure 5: Time dependence of shrinkage of gels S-S

Figure 7: Time dependence of fragmentation of gels


S-M

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Figure 8: The surface area of pores of mixtures D-L,


S-S-1, S-S-10 measured by the BET method

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Figure 6: Time dependence of shrinkage of gels S-V

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during the measurement, so the values are probably


not absolutly exact, but are sufficient enough for comparison.

4. Conclusions
Modified alkoxysilane consolidants were prepared that
were less cracked in comparison with the unmodified
consolidant after five week experiment. Those were
mixtures S-S-10 and S-M-25. It was proved, that with
help of image analysis, shrinkage of the gels can be
objectively observed. The degree of fragmentation
can be evaluated by the image analysis as well, but
the comparison of average values is not possible, due
to unequal behaviour of samples of the same mixture.
The surface area of pores of three samples of different

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mixtures was measured and compared with each other.


The surface area rises with the degree of filling of the
basic mixture with nanoparticles. This change of
pore surface area may be the reason why the more
filled mixtures crack less. The research in this field
continous and now it is focused on the method of
image analysis, that could better characterize the
degree of fragmentation.

Acknowledgements

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This
work
was
supported
by
the
project
No. DF11P01OVV012 New materials and technologies
for the conservation of historical materials of monuments
and the preventive conservation care in a program NAKI
of the Ministry of Culture of the Czech Republic. Financial support from specific university research (MSMT
No. 20/2013).

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