1265

THE HARDENING PROCESS IN SILICATE PAINTS

OSSWALD, JURGEN
Mineralogisch-petrographisches lnstitut der LMU, Theresienstr. 41c, 80333 Miinchen
SNETHLAGE, ROLF
Bayerisches Landesamt fiir Denkmalpflege, Hofgraben 4, 80539 Miinchen

SUMMARY
Despite the fact, that silicate paints exist for more than 100 years the hardening process is not entirely
known. Especially the formation of hydrated calcium silicates due to the reactions between the water
glass and the calcite of the substrate is often claimed. In the present work the oldest still preserved
silicate painting from 1878 on the east wall of the church in Eichelberg/Bavaria is investigated. The
hardening process of Keim-A-, Keim-B- and Two-Component-Technique is studied in the laboratory
under different conditions
The formation of C-S-H phases could not be observed neither on the object nor in the laboratory
experiment. The formation of such a phase is very unlikely because in the case of potassium water
glass the particle size of the silicate complexes is too great so that the amount of dissolved silica is
too low. Also the concentration of ca2+ ions in the alkaline solution is very low due to the minor
solubility of calcite in alkaline environment. So for both reasons the conditions for a C-S-H phase
formation are not fullfilled. Calcium ions which are present in the silica gel are absorbed on the silica-
surface and can be exchanged easily with weak-acidic water.
The general formula which is commonly used for the water glass reaction conveys a wrong picture
because the reaction is not released and determined by the access of C02 from the air. The
precipitation of the silica gel is much faster and can be finished after some minutes. Only later on the
formation of K2C03 will take place.
By FT-IR Technique it was found that the kind of the fillers and pigments used have great influence
on the kinetics of the reaction and the network of the silica gel formed. The asymmetric Si-0-Si
stretching vibration at 1086 cm-1 is significantly shifted towards lower wave numbers indicating a
higher energy level of the bonds. More than other pigments ZnO enhances the reactivity of the water
glass as well as it causes the greatest peak shift.

1. INTRODUCTION

The first silicate paints were developed by Johann Nepomuk von Fuchs, who rediscoverd the water
glass, and Josef Schlotthauer in 1842. They called this Technique .stereochromie". The binder of
these paints were water glass and should increase the durability of the paintings against
environmental impacts. However this technique was not able to fulfill these expectations. On the
basis of the work of Schlotthauer and Fuchs, Adolf Wilhelm. Keim has created a two-component-
technique still used today. This technique is called Keim-A-Technique.
For the painting a special ground is needed. A. W . Keim used a lime mortar with pumice admixture
which was treated with phosphoric acid to remove the lime sinter on the surface of the mortar and
then impregnated with water glass. On this ground the painting was done with pigments and water.
Only specific, alcaline resistant pigments were allowed. After the painting was ready it was
impregnated several times with a mixture of potassium water glass and liquid ammonia.
This development was patented in 1878. In the same year the painting on the east wall of the church
in Eichelberg/Bavaria was executed under the care of A. W. Keim. This painting is the oldest still
preserved outwallpainting known.
The next development, the Keim-B-Technique, introduced in 1881 has the advantage that the
pigments are mixed with water glass bevor painting is done. The following impregnating of the ready
painting is not necessary any more. The next significant development was introduced to the market in
1967 with the one-component silicate paint with synthetic additions.
 1266

2. THE KNOWN HARDENING PROCESS IN SILICATE PAINTS

Since the development of the ,,Stereochromie" the reaction of water glass with the C02 from the air
and with polyvalent kations were known. The products of these reactions are potassium carbonate
and hydrated silicates.
Usualy these reaction are described with the following equations:
1. Reaction of potassium water glass with C02 from the air
K203Si02·xH20 + H20 +C02 -> 3 Si02·xH20 + K2C03
2. Reaction of potassium water glass with pigments, fillers and substrate, e. g. the reaction with
Ca(OH)2 with formation of C-S-H phases
Ca(OH) 2 + K2o 3Si02 ·xH20 + mC02 -> CaSin02n-1(x+1)H20 + mK2C03
3. By desorption of water the formed silica gel is compressed.

2.1 the question of K2C03 formation

The formation of silica gel in silicate paints is completed after a few hours. The reaction speed of the
gelling-process depends on the reactivity of the pigments. Suppose reaction 1, a acid-base reaction,
takes place in the gelling process, the pH is lowered. The pH of the water glass solution used here is
12. These solution is stable if the pH is higher than 10.6 (WELDES 1969). However this decrease
cannot be observed. Under laboratory conditions the pH decreases from 12 to 10.6 within 10 hours. In
silicate paints the water content is decresed by 75% within three hours under the same conditions.
After three hours the gelling process is completed. The formation of K2C03 takes place within few
days at the surface of the gel. Therefore the absorption of C02 has no influence on the gelling
process of the binder in silicate paints.

2.2 The question of C-S-H phase formation

It is known that C-S-H phases can be formend under ordinary temperatures (TAYLOR 1964). These
phases appear amorphouse, but X-ray pattern show a certain degree of crystallinity. The degree of
crystallinity rises with the time. Since the painting in Eichelberg is more than 115 years old there is a
legitimate hope to find these phases with X-ray techniques. For this, tiny needles can be found at the
surface of dolomite under the polarized light microscope.
X-ray powder diffraction on grinded painting ground shows first of all dolomite (mortar filler) and
calcite (mortar binder). The reflections of these two phases overlay the detraction patterns of other
phases. For this it is necessary to remove dolomite and calcite from the sample without destroying
the C-S-H phase. This is made by dissolving the carbonates in a 4% monochloric acetic acid solution.
The determinable phases are goethite, baryte and quartz from the historic silica paint and rutile and
kaolin from a paint the wall painting was overpainted within the late fifties. A X-ray diffraction analysis
made with the tiny needles prepared out of the microscopic preparation shows that these needles are
gypsum.
If a C-S-H phase is formed it is amorphouse. There is a possibility to proof a amorphouse C-S-H
phase by FT-IR spectroscopy. The C-S-H phases is similar to sheet silicates (TAYLOR 1964). The
position of the OH stretching vibration is determind by the cation in the octahedral gap of the layer
formed by the OH groups on the silica sheets and the adsorbed water (McMILLAN 1988).The amount
of the shift depends on the electronegativity of the kation. The more electronegative the more the
band moves to lower wavenumbers (STRENS 1974). If there is a C-S-H phase a shift to lower
wavenumbers must be detected.
To proof this a sample was prepared in the same way like the x-ray sample. Also three samples were
made in the laboratory,
- a silica gel made of air dried water glass
- a gel precipitated with ca2+ ions
- a gel precipitated with Mg2+ ions.
 1267
0.10 0.200

--gemessen
0.09 geme"90 berechnet:
berechrwit : 0 . 17 5 Loge FWHM Int.
Bonde 1 .35.31 18.3 0 .05
Looe FWHM Int. Bonde 2 .34 26 19.3 0 .1.3
o.oe
Bonde 1 =1 237 0 .02 Bonde .3 .32.34 18.3 0.01
Bonde 2 ~428 zoe 0 .06
0. 150
Band< 3 32 31 160 0.01
0.07

O. IZO
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c
.2
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0.05 c
0 0.100
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0 .075

0. 0~

0.050

0.02

0.025
0.01

0.00 0 .000
.l800 '700 .l800 3500 :;<00 3.300 3200 3100 .lOOO 3800 3700 3600 3500 3400 3300 3200 3100 3000
Wellenzohl [c m - 1] Wellenzohl [cm-1 J

fig. I a: OH vibration of air dried water glass fig 1b: OH vibration of historic sample from Eichelberg

0.60
0.15
- - gemessen
- - gemessen
O. B 0.55 berechnet
berechnet:
FWHM Int. Lage FWHM lint.
Lage
0. 13 3545 196 0 .06 Bonde 1 3560 192 0. 1
Bonde 1 0.50
Bonde 2 341 7 195 0.
Bonde 2 3 422 210 0.1
0.12 3239 255 0.0 323.3 182 0. 1
0.45
0. 11

0. 40
0. 10

0.09 0 .35
c
0

c
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0.03
0.1 0

0.02
0.05
0. 01

0.00
0.00 3800 3700 .)600 3500 3400 3.300 3200 .;100 3000
3700 3600 3500 3400 3.300 3200 3100 3000
3800 Wellenzohl [ cm-1)
\lle llenzohl [cm -1 )
2
2
fig. I c OH vibration of Ca + precipitated gel fig. Id: OH vibration of Mg + precipitated gel
 1268

The measurements were performend on a BRUKER IFS 48 FT-IR spectrometer. KBr discs were used
and 64 scans with a resolution of 1 cm-1 were recorded . Lorenz functions were fitted to the recorded
spectrum with a least square method on the computer. The fitted spectra are given in figure 1.
Band position of the gel without kations and the sample from the painting in Eichelberg at 3428 :t: 1
cm-1 lies within the fitting accuracy. The band of the ca2+ precipitated gel is moved downwards to
2422 cm-1 and that of the Mg2+ precipitated gel to 2417 cm-1 as expected.
The formation of C-S-H phases can not be measured.

2.3 Some considerations about C-S-H phase formation in silicate paints

C-S-H phases produced at ordinary temperatures were made with sodium water glass. The degree
of polymerisation in sodium water glass is of about 15 Si02 groups {ILER 1979 S.133), in
potassium water glass of about 90. Because small primary paticles are more soluble, in sodium
water glass the amount of monosilicic acid which can react with calcium under forming a C-S-H
phase is bigger than in potassium water glass.
On the other hand the solubility of calcite which is a phase in the painting ground, is very low in
alkaline solutions. In a potassium hydroxide solution with pH 12 grinded calcite with an particle size
smaller than 0.125 mm shows solubility of 6 ppm during 24 hours. On the basis of these figures and
assuming that
- the complete water content of the potassium water glass is at disposal to dissolute the lime mortar
- the formation of C-S-H phase starts at the border lime - water glass
- the calcium ions in the solution are equally distributed
a rough appraisal of the probability of C-S-H phase formation can be done.
For a silicate painting of 1 m2 about 500 ml water glass is needed. This amount penetrates the lime
mortar to a deep of about 5 mm, though 10 kg lime mortar are weted, which corresponds to a
mortar surface of 30000 m2 . 500 ml water glass contains 479 ml water, in which 4.4*1019 ca2+ ions
can be dissolved.
With these assumptions the average distance of the calcium ions at the internal surface is 263 ionic
radii. Regarding, that in reality, less water is at disposal for dissolution of ca2+ ions, because of the
very porous structure of the gel formed, a formation of C-S-H phase is very unlikely because the
distance between the calcium ions is too far to form crystal seeds and crystal growth would need a
very high ion-mobility. At least, therefore, smalest amounts of C-S-H phases could be formend
which, however, are not relevant for the hardening prozess and stability of silicate paints.

3. THE REACTION OF WATER GLASS IN SILICATE PAINTS

3.1 Structure of water glass solutions

The potassium water glass used in the present work has a molar ratio Si02:Me o of 4:1 . If the
2
molar ratio is bigger than 1:1 the silicic acid is not monomeric anymore, it condenses to polymeric
particles. The degree of condensation, measured with silicomolybdic acid reaction , is 90 Sio
2
groups per particle which corresponds to a diameter of 2.3 nm. The interior of these particles is
hydroxy-free and shows a b-cristobalite structure {ILER 1979 S.320). The surface is covered with
OH groups connected with Si atoms on the surface of the body. 40 % of the surface hydroxy groups
are ionized {ILER 1979 S.134).

3.2 The gelling processes in water glass solutions

There are three possible gelling processes: on the one hand the lowering of pH below 10.6, on the
other hand the addition of coagulating agents and last the loss of water. In silica paints a lowering of
pH can not be observed, though only two mechanism must be discussed.
Gelling with coagulating agents can be released with polyvalent kations. These kations absorbed on
a negativ charged Si-0- group on the surface of a silica particle are not fully compensated. There is
 1269

a positiv charge left, which for his part can compensate a negativly charged surface group of an
other silica particle. The polyvalent kation builds up a bridge between silica particles, which causes
gelling (fig. 2).
In silica paints the polyvalent kations must be dissolved out of pigments or painting ground. In
usually used pigments only ZnO and in mortars only Ca(OH)2 are soluble enough in alkaline
conditions. The addition of these two substances to water glass causes rapid gelling.
The silica particles in water glass solutions are stabilized by their negativly charged surface, they
repell each other. If water is lost by evaporation, the silica concentration in the solution rises. The
particles collide more often and gain more kinetic energy until they are fast enough to overcome the
repulsiv barrier of the other particles. In this case the surface hydroxyl groups can condensate and
build up a Si-0-Si bridge between these particles, so that gelling starts (fig. 3).

- -". --
- - .
--.1 -::
-._

i; - -
Oberfl!lchenspannung
' CH
1::1- ----
ti - II
- .:.,----...:- - ---:--.];·- -
( H

·, ( tj
" -·
1r -
n -
_.-"..:-
.. , '- H
ff -

fig. 2: coagulation with polyvalent kations fig 3: coagulation by evaporation of water

For most pigments and mortar fillers the increasing concentration due to evaporation is the
predominant gelling mechanism.

3.3 The gel structure in silica paints

Rapid gelling causes a different gel structure than slow gelling in the case of water loss. The gelling
process in colloid systems like silica solutions follows the cluster-cluster-aggregation model
(WIJNEN 1991). Rapid gelling leads to a branched, fragile, porous gel while slow built aggregates
are more compact (JULIEN 1987). The gels are fractal aggregates. During ageing of the fresh made
gel, more water evaporates. The water in the capillaries of the gel is under a reduced vapor
pressure. If water evaporates, the capillaries being under tension transmit this tension to the
capillary walls. If the tension is big enough the gel structure collaps. On the other hand, as silica is
dissolved at parts of the gel with small radii of curvature and deposited at parts with a bigger
curvature, the structure becomes less branched and fragile (fig. 4).

fig. 4: left: freshly precipitated gel; right: aged gel

 1270

The different stuctures lead to different specific surfaces. For both the gel is microporous like
expected for primary particle size of 2.3 nm. The specific surface was measured by nitrogen
adsorption (BET) and by alkali titration method of Meffert (MEFFERT 1970). The specific surface of
2
rapid gelled gels showes BET surface of 579 m2 /g and surfaces between 874-940 m /g by alkali
2
titration. The data for slow gelled gels are about 70 m2 /g BET and 396-568 m /g by alkali titration.
The differences between BET and alkali titration value is caused by the microporosity of the gels,
because N2 molecules only penetrate pores with a diameter bigger than 1.2 nm, hydronium ions
even smaller ones. The difference of the specific surface of the fast and slow gelled gels shows
their different structure.

4. REACTION BETWEEN WATER GLASS AND PIGMENTS AND FILLERS

For the reaction of pigments and fillers with water glass in silica paints three reactions are
conceivable.
- reaction with formation of a new phase
- the hydroxylated surface of the pigments condenses with the hydroxylated surface of the silica
particles
- there is no reaction between silica and pigment, the adhesion is a physical one
The formation of a new phase on the border pigment-silica is not very likely (cf. 2.2 and 2.3)
because therefore a certain solubility of pigments and fillers is necessary.This is only given by ZnO
and Ca(OH) 2. But these polyvalent kations lead to rapid gelling. They become bridging kations
between silica particles in the gel. The concentration of kations in the gel decreases with distance to
the border pigment-gel, because gelling starts on the pigment surface and increasingly hinders the
further dissolution of polyvalent kations. No phase boundary exists.
In alkaline solutions all pigments and fillers have a negativ zeta-potential, thus their surface is
covered with hydroxyl groups (PARFITT 1976). These hydroxyl groups are able to condense with
the hydroxyl groups on the surface of the silica particle in the water glass solution. A \Si-0-Me-
bridge is formed .
If there is no reaction between water glass and pigments the adhesion force is caused by van der
Waal forces and shared hydrate films.
Because the first case does not take place, a distinction between the second and third must be
made. This is possible with FT-IR spectroskopic techniques. If there is no reaction , the spectrum of
the paint below 1500 cm-1 must be the same as an addition of the spectrum of pure silica gel and
the spectrum of pure pigment, because the weak van der Waals forces have no influence on the
strong bonding forces in pigment and gel.
Building up oxygen bridging bonds between silica gel and pigment, these bonds influence the
neighbour bonds. Neighbouring bonds are deformated, so that a change in band position must be
observerd in the FT-IR spectrum.

4.1 Experimental background

position (cm-1] assignment

1200 longitudinal lattice vibration

1087 asymmetric Si-0-Si stretching vibration
950 Si-OH stretching vibration
796 symmetric Si-0-Si streching vibration
570 Si-OH bending vibration
467 asymmetric Si-0-Si bending vibration

tab. 1: FT-IR band assignment of silica gel

 1271

Pigments, Ca(OH)2 and Caco3 were mixed with potassium water glass to obtain a paintable mixture.
ZnO and Ca(OH)2 immediately formed a gel. To obtain an ease of brushing, more water glass was
added to the mixture. These paints were dried for one week under laboratory conditions, then grinded
and washed three times with water. The powder was dried over five days at 140°C, then 0.2 to 0.5 mg
of this powder were mixed with 300 mg KBr and dried again at 150 °C. Subsequently the samples
were pressed to 13mm KBr discs and investigated with a BRUKER IFS 48 from 4000 cm-1 to 400
cm-1 with 64 scans registrated.

4.2 FT-IR spectrum of silica gel

The spectrum of silica gel consists mainly of the three Si-0 vibrations, the asymmetric and symmetric
Si-0-Si stretching vibration and the asymmetric bending vibration. A summary is given in table 1. The
position of the vibrational bands depends on density, porosity and manufactering process (GUITON
probe band positions

potassium water glass 1086 793

KEIM Fixativ 1085 803
historic binder 1087 799
Ca2+ precipitated gel 1089 790

tab. 2: band position of silica gels made in different

ways

1993). The FT-IR measurement of four silica gels (tab. 2) made with different procedures shows 'no
drift of the asymmetric Si-0-Si stretching vibration within the confidence interval!. For this the
influence of reaction with pigment surface hydroxyl groups can be measured with this vibration.

4.3 FT-IR spectra of silica paints

To decide whether there is a reaction between pigments and water glass or not, a calculated
spectrum of the paint is needed. This spectrum is an addition of the pure silica gel spectrum and the
pure pigment spectrum multiplied by a scaling factor. The scaling factor was determined by a least
square method fitting the calculated spectrum to the measured. The spectra of four pigments is
considered, ZnO and Ca(OH)2 for pigments causes rapid gelling and chromium green and iron oxid
yellow for the others.

4.3.1 FT-IR spectrum of ZnO

The pigment ZnO can be identified as zincite by X-ray technique. The spectrum of the pure pigment
(fig Sa) shows also a little content of quartz. The bands at 539 cm-1 , 509 cm-1 and 430 cm-1 can be
assigned to zincite (FARMER 1974 S.187). The spectrum of the paint shows clear differences (fig.
Sb). The position of the Si-0-Si stretching vibration is shifted significantly to lower wavenumbers. The
amount of this shift depends on the rate pigment water glass.

4.3.2 FT-IR spectrum of Ca(OH)2

The binder CaOH is identified by X-ray as portlandite and a certain content of calcite. The band at
1417 cm-1 875 cm-1 and at 713 cm-1 are carbonate vibrations, the broad band at 414 cm- 1 is
assigned to portlandite (fig Sa). Again a significant shift of the stretching vibration to lower
wavenumbers can be observed (fig. 6b). Also a shift of the carbonate vibration at 1416 cm- 1 to higher
wavenumbers is measured. This behavior is typical, if the crystal field built up by nearest neighbours
of the carbonate anion, is disturbed. This can be caused by nearest neighbour calcium atoms which
build a oxygen bridge with silica particles.
 1272
z.o

0. 14.
1.11
- - ge"'1essen
ber~chn~

0.12
1.e

0. 10 1.4

1.2
0.08 c
a
c
E
e. 0 1.0
a. "'
0
~
0.06 -11.
.c
<
~
0.11

0.0-1

0.6

om
0.4

0.00 0.2

~'-1µ-l--1-+--1-+-'--t-'--t-'-+-'----t----'-·-j-'- ..,_ -Tl~:-'-+--'-'

1
-0.02 i-.L.-l--L-1--...L-+._j_--+_L-J.---'-l_JL_f-1-+-.L+-...L.+..L+-'--'I 0 .0

1000 1soo 1400 1300 1200 11 00 1000 900 eoo 100 600 soo •oo 1600 1500 1400 1300 1ZOO 1100 1000 900 600 700 600 500 400

Wellenzohl (cm-1] Wellenzohl [cm-1]

fig. Sa: FT-IR spectrum ofZnO fig Sb: FT-IR spectrum ofZnO with water glass

0-"<J

0.4.0 --,..-- 9emesssen

· · · · - berechnet
.,
+
0.40
;
1.5 m

O.J5
+
"'8
: ~

O..JO

c c
0 \ 0 0
0.20
:;:;
~ c.
0 0
<"'
D "'
-11. 0.2<1

0.1~

00

0 . 10

0.05

0 .0
0.00

1600 1500 1400 1.lOO 1200 1100 1000 900 600 700 600 500 WO 1600 1500 1400 1.lOO 1200 1100 1000 900 600 700 600 500 400
Wellenzohl (cm- 1) Wellenzohl [ cm -1]

fig. 6a: FT-IR spectrum ofCa(OH\ fig. 6b: FT-IR spectrum ofCa(OH)2 with water glass
 ~
1273

0.55

~
~
0 .50 - gemesssen ~
1.2 · · · · · - tierec hnet
0.45

1.0 MO

·~ O.J.5

o.a
O.JO

c c
0 .Q
~0 ~
0
0.25
0 .6
,,"' _,,"'
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0 .20

0 .4
0 .1 5

.,, 0.10
:;

0.0!5

1600 1500 1400 1300 1200 I 100 1000 900 BOO 700 600 500 400 1 600 1500 1400 I 300 1200 1100 I 000 900 800 700 600 500 400

Wellenzohl [ c m-1] We llenzohl [ cm-1]

fig. 7a: FT-IR spectrum of chromium green fig. 7b: FT-IR spectrum of chromium green with water
glass

20 1.0
"~
~ g_emesss en

0.9 · · · · · • berec hnet

1.8

1.6 0.8

1.4 0.7 ~
~
~
1.Z "'"'+ c
0.6 ~ N
~

c: 0
~ g
.0
c
.... :g_ 8 N
N
e-0 1.0
0 0 .5
~

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08
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0.2

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0 .0 1-~µ-f-1-J.-1.-+-'-+...L+-'-+-.L.t-"-t-'-lr-'-t-'--1
1600 l !'lOO 1400 ! JOO 1200 1100 1000 900 600 700 600 ~ 400
1roo 1.500 1400 1.soo 1200 1100 1000 900 aoo 100 eoo ~ 400

Wellenzohl (c m- 1] Wellenzohl [ cm - 1]

fig. 8a: FT-IR spectrum of iron oxide yellow fig. 8b: FT-IR spectrum of iron oxid yellow with water
glass
 1274

4.3.3 FT-IR spectrum of chromium green

Chromium green consists of escolaite. The spectrum (fig. 7a) shows bands at 645 cm- 1 , 582 cm-1,
443 cm-1 and 415 cm-1. There is also a little quartz visible. In the spectrum of the paint (fig 7b) a
shift from 1086 cm-1 to 1080 cm-1 can be observed.

4.3.4 FT-IR spectrum of iron oxid yellow

Iron oxid yellow is being identified as goethite. The spectrum (fig. 8a) shows bands at 900 cm- 1 and
798 cm-1 caused by hydroxy groups of gothite and at 667 cm-1, 621 cm-1, 456 cm- 1 and about 400
cm-1 vibration bands of oxygen rocking . A shift from 1089 cm- 1 to 1083 cm- 1 is being observed (fig.
Sb). Additionally a carbonate band at 1438 cm-1 occures which is probably caused by less accurate
preparation and shoulders at 1183 cm-1 and 1120 cm-1 .

4.4 Discussion of the results

The shift of the asymmetric Si-0-Si stretching vibration to lower wavenumers indicates a deformation
of this bond. This deformation is caused by the condensation of a surface hydroxyl group of the silica
with a surface hydroxyl group of the pigment. The deformation is given by a change in the electric
field in the neighbourhood of the deformated Si-0-Si bond. The energy level of the bond rises, so less
energy is nesessary to cause vibration, the band position drifts to lower wavenumbers. The measured
band position is an superposition of these deformed vibrations and the normal ones. The value of the
shift depends on the amount of oxygen bridging bonds created and the electronegativity of the
participateing metal kations. The lower the electronegativity in comparison to the silicium atom (1.90)
is the greater is the shift. Calcium with an electronegativity of 1.0 causes the biggest shift, followed by
zinc with 1.65. The significant smaller shift in the case of chromium with an electronegativity of 1.66
o
must be explained by the very small solubility of Cr2 3 in alkaline solutions, therefore less bridges
were build as in the case of ZnO where zn2+ ions penetrate the water glass. The smallest shift is
observed on iron with an electronegativity of 1.83
The results confirm the formation of a \Si-0-Me- bridge between pigment and silica gel.

5. CONSEQUENCES FOR THE PRACTICE

The different gelling caused by pigments leads to different gel structures. There is also an effect on
the macroscopic appearance of the paints. Pigments that cause rapid gelling hinder the water glass to
penetrate deeply in the painting ground. The result is a hard and compact layer on the surface (fig.
11). On the other hand it is explainable why silica paints should not be applied on fresh lime mortar.
The carbonatisation process on lime mortar is a slow process. After a few weeks after application only
the outer layer of the mortar is converted in calcite which is on his part treated with acid befor paint is
applied. Though the mortar consists mainly of Ca(OH)2 which also causes rapid gelling. Only little
penetration depth can be obtained. The result is a hard layer of paint on a mortar with low resistance
against shear forces caused by shrinking of the drying paint. The result is the loss of adhesion.

ACKNOWLEDGMENT
The investigations were kinedly granted by KEIM FARBEN GmbH & Co KG.

REFERENCES
FARMER, V. C.: The i. r. spektra of minerals. Mineralogical Society Monograph 4, London, 1974
GUITION, T . A. , PANTANO, C. G .: Infrared reflectance spectroscopy of porous silica. Colloids and
Surfaces, 74, 33-46, 1993
ILER R. K. : The chemistry of silica. John W iley & Sons, New York, 1979
 _/
1275

JULIEN R., BOTET, R. : Aggregation and fractal aggregates. World Scientific Publishing Co Pte ltd,
Singapore, 1987
MEFFERT, A ., LANGENFELD, A. : Bestimmung der Oberflache von hochdisperser Kieselsaure durch
automatische potentiometrische Titration mit Natronlauge. Z . anal. Chem. , 249, 231-233,
1970
OSSWALD J .: Die Struktur und Reaktionen des Kieselsauregels in den Silikatfarben der Keim'schen
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