L::c/^¦co¦o¦ l:·tcr·:on· íor \a¦¦ la:n':nq· Con·crva':on. L::c/^¦co¦o¦ l:·tcr·:on· íor \a¦¦ la:n':nq· Con·crva':on.

L::c/^¦co¦o¦ l:·tcr·:on· íor \a¦¦ la:n':nq· Con·crva':on. L::c/^¦co¦o¦ l:·tcr·:on· íor \a¦¦ la:n':nq· Con·crva':on.
í:·'or,, La¦ora'or, Lxtcr::cn'· í:·'or,, La¦ora'or, Lxtcr::cn'· í:·'or,, La¦ora'or, Lxtcr::cn'· í:·'or,, La¦ora'or, Lxtcr::cn'·
and Ca·c ´'ud:c· and Ca·c ´'ud:c· and Ca·c ´'ud:c· and Ca·c ´'ud:c·
Luigi Dei Luigi Dei
Department of Chemistry & CSGI Consortium
University of Florence
via della Lastruccia, 3 I-50019 Sesto Fiorentino - Firenze - Italy
colden colden colden colden iule iule iule iule: :: : plysicoclemical compatibility plysicoclemical compatibility plysicoclemical compatibility plysicoclemical compatibility oí tle oí tle oí tle oí tle iestoiation iestoiation iestoiation iestoiation
mateiials witl mateiials witl mateiials witl mateiials witl tle woik oí ait tle woik oí ait tle woik oí ait tle woik oí ait substiate substiate substiate substiate
“Le restaurateur doit rémedier dans la mesure du
possible au divorce fatal que le temps - et plus
souvent les hommes - ont provoqué entre la
matière vieillisante et la forme qu’elle incarne”
Paul Philippot
“Restorers should make up everything possible
for the fatal divorce that the time - and more often
the men - have brought on between the aging
matter and the form it embodies”
Wall Paintings: original binder Ca(OH)
2
Best consolidating agent
according to the golden rule

Slaked lime (grassello),
that is Ca(OH)
2
plus water paste
Saturated soIutions too weak as
consoIidant due to the Iow Ca(OH)
2
soIubiIity (1.6 g.L
-1
)
Water dispersions or suspensions too
kineticaIIy unstabIe (gIazing on the
painted surface due to fast
sedimentation of the binder particIes)
Problems associated with applying Ca(OH)
2
Research strategy
Ca Ca Ca Ca(OH) (OH) (OH) (OH)
2 22 2
dispersions dispersions dispersions dispersions instead instead instead instead of of of of
saturated soIution to increase saturated soIution to increase saturated soIution to increase saturated soIution to increase the the the the
binder concentration binder concentration binder concentration binder concentration, short , short , short , short chain chain chain chain
aIiphatic aIcohoIs as disperdent aIiphatic aIcohoIs as disperdent aIiphatic aIcohoIs as disperdent aIiphatic aIcohoIs as disperdent
media media media media instead instead instead instead of water of water of water of water to enhance to enhance to enhance to enhance
the the the the kinetic stabiIity kinetic stabiIity kinetic stabiIity kinetic stabiIity. .. .
Topics
Plysicoclemical claiacteiisation Plysicoclemical claiacteiisation Plysicoclemical claiacteiisation Plysicoclemical claiacteiisation oí oí oí oí ca ca ca ca(OH) (OH) (OH) (OH)
2 22 2
dispeisions dispeisions dispeisions dispeisions
in sloit in sloit in sloit in sloit clain aliplatic alcolols clain aliplatic alcolols clain aliplatic alcolols clain aliplatic alcolols (c (c (c (c
2 22 2
- -- -. c . c . c . c
? ?? ?
- -- -. c . c . c . c
1 11 1
- -- -. c . c . c . c
0 00 0
- -- -) )) )
Ivaluation Ivaluation Ivaluation Ivaluation oí tle oí tle oí tle oí tle consolidating consolidating consolidating consolidating powei oí powei oí powei oí powei oí tlese tlese tlese tlese
dispeisions dispeisions dispeisions dispeisions on on on on aeiial moitai specimens simulating aeiial moitai specimens simulating aeiial moitai specimens simulating aeiial moitai specimens simulating
diííeient degiee diííeient degiee diííeient degiee diííeient degiee oí oí oí oí decolesion decolesion decolesion decolesion
Ixpeiimentation Ixpeiimentation Ixpeiimentation Ixpeiimentation oí tle oí tle oí tle oí tle piopanol dispeisions piopanol dispeisions piopanol dispeisions piopanol dispeisions in in in in ieal cases ieal cases ieal cases ieal cases
botl botl botl botl in in in in wall paintings wall paintings wall paintings wall paintings and and and and stones conseivation stones conseivation stones conseivation stones conseivation
Physicochemical characterisation of the dispersions
Kinetic stabiIity determined by Kinetic stabiIity determined by Kinetic stabiIity determined by Kinetic stabiIity determined by
foIIowing foIIowing foIIowing foIIowing the the the the behaviour behaviour behaviour behaviour of the of the of the of the
absorbance absorbance absorbance absorbance at 600 at 600 at 600 at 600 nm as nm as nm as nm as a aa a
function function function function of time of time of time of time
Absorbance Absorbance Absorbance Absorbance proportionaI to proportionaI to proportionaI to proportionaI to Turbidity Turbidity Turbidity Turbidity
proportionaI to proportionaI to proportionaI to proportionaI to Kinetic StabiIity Kinetic StabiIity Kinetic StabiIity Kinetic StabiIity
Materials used
· Dispersed phase Dispersed phase Dispersed phase Dispersed phase: :: : Ca Ca Ca Ca(OH) (OH) (OH) (OH)
2 22 2
particIes particIes particIes particIes
from from from from commerciaI commerciaI commerciaI commerciaI sIaked sIaked sIaked sIaked Iime and Iime and Iime and Iime and
commerciaI commerciaI commerciaI commerciaI powder powder powder powder
· Disperdent Disperdent Disperdent Disperdent medium: water, medium: water, medium: water, medium: water, EthanoI EthanoI EthanoI EthanoI, ,, ,
PropanoI PropanoI PropanoI PropanoI, ,, , IsopropanoI IsopropanoI IsopropanoI IsopropanoI, ,, , ButanoI ButanoI ButanoI ButanoI, ,, ,
IsobutanoI IsobutanoI IsobutanoI IsobutanoI, ,, , OctanoI OctanoI OctanoI OctanoI
P PP P a aa a i ii i a aa a m mm m e ee e t tt t e ee e i ii i p pp p o oo o w ww w d dd d e ee e i ii i
s ss s l ll l a aa a k kk k e ee e d dd d l ll l i ii i m mm m e ee e
I II I I II I 1 1 1 1 8 88 8 u uu u i ii i í íí í a aa a c cc c e e e e A AA A i ii i e ee e a aa a
(m (m (m (m
2 22 2
.g .g .g .g
-! -! -! -!
) )) )
! - ! ! - ! ! - ! ! - ! 1 11 1 2 22 2 5 5 5 5 - - - - ? ?? ? u uu u
A AA A v vv v e ee e i ii i a aa a g gg g e e e e p pp p a aa a i ii i t tt t i ii i c cc c l ll l e ee e s ss s
d dd d i ii i a aa a m mm m e ee e t tt t e ee e i i i i ( (( (µ µµ µ m) m) m) m)
0 - S 0 - S 0 - S 0 - S ? - 1 ? - 1 ? - 1 ? - 1
Time (hours)
0 2 4 6 8 10 12 14 16 18
ξ
-
p
a
r
a
m
e
t
e
r
0
20
40
60
80
100
120
slaked lime/water
powder/1-propanol
slaked lime/1-propanol
ξ = {1 - [(A
t=0
- A
t
)/A
t=0
}x100
water
ethanol
1-propanol
2-propanol
1-butanol
2-butanol
1-octanol
ξ-parameter
0
2
0
4
0
6
0
8
0
1
0
0
C
a
(
O
H
)
2

P
o
w
d
e
r
C
a
(
O
H
)
2

S
l
a
k
e
d

l
i
m
e
Evaluation of the consolidating power
AeriaI mortar specimens AeriaI mortar specimens AeriaI mortar specimens AeriaI mortar specimens
(50x50x10 mm) (50x50x10 mm) (50x50x10 mm) (50x50x10 mm) simuIating simuIating simuIating simuIating
different degree different degree different degree different degree of of of of decohesion decohesion decohesion decohesion
obtained by decreasing obtained by decreasing obtained by decreasing obtained by decreasing the the the the
Iime/ Iime/ Iime/ Iime/sand sand sand sand ratio ratio ratio ratio
8ample 8ample 8ample 8ample Iime/sand iatio (v/v) Iime/sand iatio (v/v) Iime/sand iatio (v/v) Iime/sand iatio (v/v)
A AA A !.uuu !.uuu !.uuu !.uuu
I II I u.5uu u.5uu u.5uu u.5uu
c cc c u.??? u.??? u.??? u.???
D DD D u.2uu u.2uu u.2uu u.2uu
I II I u.!25 u.!25 u.!25 u.!25
f ff f u.!uu u.!uu u.!uu u.!uu
Properties tested to evaluate consolidation
· CapiIIary CapiIIary CapiIIary CapiIIary rise rise rise rise profiIes profiIes profiIes profiIes
· Water Water Water Water vapour permabiIity vapour permabiIity vapour permabiIity vapour permabiIity
· TotaI TotaI TotaI TotaI porosity porosity porosity porosity
· X XX X- -- -Rays diffractometry Rays diffractometry Rays diffractometry Rays diffractometry
· Dietrich Dietrich Dietrich Dietrich- -- -Fr Fr Fr Frü üü ühIing caIcimetry hIing caIcimetry hIing caIcimetry hIing caIcimetry
· Resistance to surface abrasion by Resistance to surface abrasion by Resistance to surface abrasion by Resistance to surface abrasion by
microdurometer microdurometer microdurometer microdurometer
· Scotch tape test (STT) Scotch tape test (STT) Scotch tape test (STT) Scotch tape test (STT)
Resistance to surface abrasion by microdurometer
Microdurometer for metaI hardness
Durimet Leitz with a weight of 300
g on the punch and making 30 mm
Iong scratches: k/m k/m k/m k/m
- -- -1 11 1
surface surface surface surface
cohesion parameter defined as cohesion parameter defined as cohesion parameter defined as cohesion parameter defined as the the the the
reciprocaI reciprocaI reciprocaI reciprocaI of the of the of the of the average average average average scratch scratch scratch scratch
width width width width
Loss of surface material due to decohesion
Scotch Tape Test parameter in mg.cm
-2
is
the average mass of surface specimen
taken away by a strip of scotch tape
normalized to the area (method
developed by Prof. Giorgio Torraca,
Rome, Italy)
Dispersion selected for experimental tests
ca ca ca ca(OH) (OH) (OH) (OH)
2 22 2
slaked slaked slaked slaked lime lime lime lime
(? (? (? (?- -- -1 1 1 1 µ µµ µm mm m diametei diametei diametei diametei) )) )
dispeisions dispeisions dispeisions dispeisions in in in in
! !! !- -- -piopanol piopanol piopanol piopanol
u.5 g/!uu u.5 g/!uu u.5 g/!uu u.5 g/!uu cc cc cc cc
Application procedures
Iy biusl onto Iy biusl onto Iy biusl onto Iy biusl onto tle tle tle tle suiíace suiíace suiíace suiíace oí tle oí tle oí tle oí tle moitai specimens moitai specimens moitai specimens moitai specimens
piotecting piotecting piotecting piotecting tle tle tle tle suiíaces by means suiíaces by means suiíaces by means suiíaces by means oí oí oí oí Iapanese papei Iapanese papei Iapanese papei Iapanese papei
sleets sleets sleets sleets
Application Application Application Application oí tle oí tle oí tle oí tle coiiect amount coiiect amount coiiect amount coiiect amount up up up up to to to to tle tle tle tle íoimation íoimation íoimation íoimation oí a oí a oí a oí a
iemnant iemnant iemnant iemnant íilm oí íilm oí íilm oí íilm oí dispeision onto dispeision onto dispeision onto dispeision onto tle tle tle tle Iapanese papei sleet Iapanese papei sleet Iapanese papei sleet Iapanese papei sleet
Waiting Waiting Waiting Waiting ?u ?u ?u ?u days to days to days to days to allow allow allow allow complete complete complete complete setting by caibonatation setting by caibonatation setting by caibonatation setting by caibonatation
Lvaluation of the performance as consolidant
Carrying Carrying Carrying Carrying out some out some out some out some
measurements measurements measurements measurements on the on the on the on the
mortar specimens before mortar specimens before mortar specimens before mortar specimens before
the treatment and after the the treatment and after the the treatment and after the the treatment and after the
treatment (30 treatment (30 treatment (30 treatment (30 days days days days after) after) after) after)
[Time(s)]
1/2
0 2 4 6 8
W
e
i
g
h
t

c
h
a
n
g
e

(
%
)
0
4
8
12
16
Lime/sand 0.125 not treated
Lime/sand 0.125 treated
Time (hours)
0 50 100 150 200 250
W
e
i
g
h
t

c
h
a
n
g
e

(
%
)
-6
-5
-4
-3
-2
-1
0
Lime/sand 0.125 not treated
Lime/sand 0.125 treated
capillaiy absoiption coeííicients capillaiy absoiption coeííicients capillaiy absoiption coeííicients capillaiy absoiption coeííicients cA. cA. cA. cA. suiíace colesion paiametei suiíace colesion paiametei suiíace colesion paiametei suiíace colesion paiametei κ κκ κ. and . and . and . and loss loss loss loss oí mateiial oí mateiial oí mateiial oí mateiial by by by by
scotcl tape test (811) scotcl tape test (811) scotcl tape test (811) scotcl tape test (811) íoi vaiious moitai samples witl diííeient íoi vaiious moitai samples witl diííeient íoi vaiious moitai samples witl diííeient íoi vaiious moitai samples witl diííeient lime/ lime/ lime/ lime/sand sand sand sand volume volume volume volume iatios iatios iatios iatios
beíoie beíoie beíoie beíoie and aítei tle tieatment and aítei tle tieatment and aítei tle tieatment and aítei tle tieatment witl witl witl witl lime/! lime/! lime/! lime/!- -- -piopanol dispeisions piopanol dispeisions piopanol dispeisions piopanol dispeisions
Lime/sand volume ratio CA/g.cm
-2
.s
-1/2
κ κκ κ/m
-1
loss of material by STT/mg.cm
-2
0.500 0.056 1,111 0
0.333 0.048 625 0
0.125 0.064 312 5.19
0.125 treated 0.035 556 1.37
0.100 0.072 227 7.12
0.100 treated 0.042 417 4.12
IXPIkIMIN1A1ION Of 1HI IXPIkIMIN1A1ION Of 1HI IXPIkIMIN1A1ION Of 1HI IXPIkIMIN1A1ION Of 1HI ca ca ca ca(OH) (OH) (OH) (OH)
2 22 2
/! /! /! /!- -- -PkOPANOI PkOPANOI PkOPANOI PkOPANOI
DI8PIk8ION8 IN kIAI cA8I8 IO1H IN WAII PAIN1INc8 DI8PIk8ION8 IN kIAI cA8I8 IO1H IN WAII PAIN1INc8 DI8PIk8ION8 IN kIAI cA8I8 IO1H IN WAII PAIN1INc8 DI8PIk8ION8 IN kIAI cA8I8 IO1H IN WAII PAIN1INc8
AND 81ONI8 cON8IkVA1ION AND 81ONI8 cON8IkVA1ION AND 81ONI8 cON8IkVA1ION AND 81ONI8 cON8IkVA1ION
Wall paintings by Andrea da Iirenze (XIV century), Spanish
Big Chapel, Ilorence
Wall paintings by Santi di 1ito (XVI century), Counterfacade
Ilorence Cathedral
Wall paintings XVIII century ·Il Iuligno' Cenacolo Ilorence
Mural paintings in the Avnso church near Copenhaghen
Medioeval frescoes in the San Irancesco church, Siena
Wall paintings by Conrad Albrizio (J938), State Lxhibit
Building Museum, Shreveport, Louisiana, USA
Carbonatic stones of the external walls, Santa Margherita
Monastry, near Padua
Avnso Church, Copenhaghen
USA6.jpg
Problem of the white glazing
Sometimes Sometimes Sometimes Sometimes, after the , after the , after the , after the evaporation evaporation evaporation evaporation
of the of the of the of the aIcohoI aIcohoI aIcohoI aIcohoI, some , some , some , some Ca Ca Ca Ca(OH) (OH) (OH) (OH)
2 22 2
particIes particIes particIes particIes can can can can remain onto remain onto remain onto remain onto the the the the
fresco fresco fresco fresco surface veiIing surface veiIing surface veiIing surface veiIing the the the the
pictoriaI Iayers pictoriaI Iayers pictoriaI Iayers pictoriaI Iayers. .. .
Remedy Remedy Remedy Remedy: :: : deionized deionized deionized deionized water water water water
compress immediateIy compress immediateIy compress immediateIy compress immediateIy after after after after
drying drying drying drying the the the the surface surface surface surface
New horizons for the research
Reducing Reducing Reducing Reducing the the the the size size size size of of of of Ca Ca Ca Ca(OH) (OH) (OH) (OH)
2 22 2
to to to to the the the the
nanometer nanometer nanometer nanometer regime ( regime ( regime ( regime (fraction fraction fraction fraction of of of of
microns microns microns microns) )) ) to to to to: (i) : (i) : (i) : (i) improve penetration improve penetration improve penetration improve penetration, , , ,
( (( (ii ii ii ii) )) ) minmizing white gIazing minmizing white gIazing minmizing white gIazing minmizing white gIazing, ( , ( , ( , (iii iii iii iii) )) )
aIIow to reach smaIIer pores aIIow to reach smaIIer pores aIIow to reach smaIIer pores aIIow to reach smaIIer pores. In . In . In . In
concIusion concIusion concIusion concIusion, ,, , improving improving improving improving the the the the
consoIidation perfomance consoIidation perfomance consoIidation perfomance consoIidation perfomance. .. .
Ixteinal walls by Ixteinal walls by Ixteinal walls by Ixteinal walls by caibonatic caibonatic caibonatic caibonatic stone stone stone stone Nanto stone Nanto stone Nanto stone Nanto stone` `` `
ex ex ex ex- -- -Monasteio 8anta Maigleiita. Monasteio 8anta Maigleiita. Monasteio 8anta Maigleiita. Monasteio 8anta Maigleiita. Vigonza Vigonza Vigonza Vigonza. . . . Padua Padua Padua Padua
Ixteinal walls by Ixteinal walls by Ixteinal walls by Ixteinal walls by caibonatic stone caibonatic stone caibonatic stone caibonatic stone Pietia Pietia Pietia Pietia di di di di Nanto` Nanto` Nanto` Nanto`
ex- ex- ex- ex-Monasteio 8anta Monasteio 8anta Monasteio 8anta Monasteio 8anta Maigleiita. Maigleiita. Maigleiita. Maigleiita. Vigonza. Vigonza. Vigonza. Vigonza. Padova Padova Padova Padova
1ieatment witl ca(OH) 1ieatment witl ca(OH) 1ieatment witl ca(OH) 1ieatment witl ca(OH)
2 22 2
/!-piopanol dispeisions u.5 g/!uu cc /!-piopanol dispeisions u.5 g/!uu cc /!-piopanol dispeisions u.5 g/!uu cc /!-piopanol dispeisions u.5 g/!uu cc
8ample 8ample 8ample 8ample 811/mgcm 811/mgcm 811/mgcm 811/mgcm
-2 -2 -2 -2
Watei absoiption/° Watei absoiption/° Watei absoiption/° Watei absoiption/°
Iast pait beíoie tle tieatment Iast pait beíoie tle tieatment Iast pait beíoie tle tieatment Iast pait beíoie tle tieatment !u.? !u.? !u.? !u.? ¯.0 ¯.0 ¯.0 ¯.0
Iast pait aítei !st tieatment Iast pait aítei !st tieatment Iast pait aítei !st tieatment Iast pait aítei !st tieatment ?.! ?.! ?.! ?.! not measuied not measuied not measuied not measuied
Iast pait aítei 2nd tieatment Iast pait aítei 2nd tieatment Iast pait aítei 2nd tieatment Iast pait aítei 2nd tieatment 2.S 2.S 2.S 2.S 1.¯ 1.¯ 1.¯ 1.¯
West pait beíoie tle tieatment West pait beíoie tle tieatment West pait beíoie tle tieatment West pait beíoie tle tieatment ?.5 ?.5 ?.5 ?.5 !u.? !u.? !u.? !u.?
West pait aítei 2nd West pait aítei 2nd West pait aítei 2nd West pait aítei 2nd tietament tietament tietament tietament !.1 !.1 !.1 !.1 u.2 u.2 u.2 u.2
Conclusions
ExperimentaI resuIts ExperimentaI resuIts ExperimentaI resuIts ExperimentaI resuIts positive, positive, positive, positive, promising promising promising promising, and , and , and , and
encouraging encouraging encouraging encouraging, ,, , but necessity to widen but necessity to widen but necessity to widen but necessity to widen the the the the ' '' 'case case case case
stud stud stud studies ies ies ies' '' ' and and and and to optimize to optimize to optimize to optimize the the the the methodoIogy methodoIogy methodoIogy methodoIogy
Tests Tests Tests Tests are in progress are in progress are in progress are in progress to verify to verify to verify to verify: :: :
· pre pre pre pre- -- -consoIidation consoIidation consoIidation consoIidation power in power in power in power in waII paintings waII paintings waII paintings waII paintings
conservation for paint Iayer powdering conservation for paint Iayer powdering conservation for paint Iayer powdering conservation for paint Iayer powdering and Iifting in and Iifting in and Iifting in and Iifting in
aIternative aIternative aIternative aIternative to casein to casein to casein to casein or or or or acryIic resins acryIic resins acryIic resins acryIic resins
· consoIidation consoIidation consoIidation consoIidation in in in in waII paintings conservation waII paintings conservation waII paintings conservation waII paintings conservation in in in in
aIternative aIternative aIternative aIternative to Ba to Ba to Ba to Ba(OH) (OH) (OH) (OH)
2 22 2
or or or or poIymeric resins poIymeric resins poIymeric resins poIymeric resins
· consoIidation consoIidation consoIidation consoIidation and and and and protection protection protection protection of of of of carbonatic stones carbonatic stones carbonatic stones carbonatic stones
surfaces surfaces surfaces surfaces in aIternative in aIternative in aIternative in aIternative to poIymeric resins to poIymeric resins to poIymeric resins to poIymeric resins
Acknowledgments
Dr. Arch. M. Lolli Ghetti, Dr. L. M. Medri, Soprintendenza per i Beni
Ambientali ed Architettonici per le Province di Iirenze, Pistoia e Prato
Dr. B. Santi, Dr. C. Alessi, Soprintendenza ai Beni Artistici e Storici di
Siena-Grosseto
Dr. Arch. G. Monti, Dr. L. Norbiato, Soprintendenza per i Beni
Ambientali ed Architettonici per il Veneto Orientale
Restorers: P. Lrrera, M. Piacenti, I. Iacopini, L. Grenier, G.
Schonhaut
Colleagues: Profs. L. Ierroni, P. Baglioni
and best of the gratitude to undergraduate, PhD, and postgraduate students
Rodorico Giorgi, Moira Ambrosi, Barbara Salvadori, Alessio Nanni

Related Interests