The Use of Nano-Materials For The Conservation of Historic Architecture

20/01/2017
The use of nano-structured

materials for building and
stone conservation
Outline:
Introduction
Nanotechnology in building materials
Nanotechnology and Cultural Heritage
Nano-consolidants for stone materials
Surface nanocoatings for stone materials
Other nanomaterials (paper, wood, painting)
Prof. Lucia Toniolo lucia.toniolo@polimi.it
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20/01/2017
What is Nanotechnology?
Nanotechnology deals with nanomaterials
Nanomaterial:
Any form of a material that is composed of discrete functional

parts, many of which have one or more dimensions of the order
of 100 nm or less.
structures sized between 1 to 100 nanometer and involves the

use and the development or modification of materials or
devices within that size
Nanomaterials present new properties or improved properties
How much is a nanometer?
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20/01/2017
Cement and concrete:
Nano-SiO2 and clinker used to increase

densification, mechanical properties
and durability of cementitious materials
Addition of photocatalytic nano-TiO2

to reduce carbon monoxide and NOx
emissions on roadways
Carbon nanotubes have the potential

to enhance the strength, to effectively
hinder crack propagation in cement
composites, and to act as nucleating
agents

Glass:
Addition of nano-TiO2 to coat glazing
since it is able to lead to the
degradation of organic and inorganic
pollutants that can aggregate on the
surface
nano-TiO2 is hydrophilic and water

create sheets instead of water drop,
removing dirt particles
traditional self-cleaning
glass glass
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Coatings:
Addition of different
nanoparticles (Ag, ZnO,TiO2 ) in
the formulations of paints in
order to obtain antimicrobial
and self-cleaning surfaces
Self-disinfecting and depolluting

surfaces
Photovoltaics:
Most used photovoltaic material is
silicon but there is an increasing
use of dye-sensitized nano-TiO2
Large surface area of nano-TiO2

greatly increases photovoltaic
efficiency
it has potential for lower material

and processing costs compared to
conventional solar cells
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Application in architecture
Music and art city hall in

Chambery (France)
Church Dives in Misericordia in Rome

Italy Pavilion at EXPO 2015
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Snail shell-inspired
self-cleaning tiles
SEM image of snail shell

Early Cultural Heritage Nanomaterials
Lycurgus cup: example of late

Roman glass industry, which
presents unusual dichroism due
to the addition of silver-gold
alloy nanoparticles in the glass
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Cu and Au
nanoparticles were
also found in Roman
mosaic glass tesserae
and red stained-glass
windows
Luster pottery represents

the first high-density
nanocluster thin film
containing silver and
copper ever made

Blue pigment Maya Blue,
first produced in the 8th
century AD, contains
indigo adsorbed on the
surface on clay
nanopores
Damascus steel blades

(17th-18th century) present
carbon nanotubes and
cementite nanowires, able
to enhance the strength
and resistance of the swords
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What we can do?
Preventive Active
conservation conservation
Cleaning
Consolidation
Surface coating
Nanotechnology:
novel and effective strategies for
conservation of Cultural Heritage
Nanotechnology for Cultural Heritage

Some European research projects:
- Nano-materials for the conservation and preservation of movable and

immovable artworks - NANOforART
http://www.nanoforart.eu/
- Nano-systems for the conservation of immoveable and moveable

polymaterial Cultural Heritage in a changing environment - NANOMATCH
http://www.nanomatch-project.eu/
- Protection of Cultural Heritage objects with multifunctional advanced

materials HEROMAT
http://www.heromat.com/
- Stone Conservation for the Refurbishment of Buildings STONECORE

http://www.stonecore-europe.eu/index.php
- Plasma and nano for new age soft conservation - PANNA

http://www.panna-project.eu/
New call Horizon 2020: Bando NMP-21-2014Materials-

based solutions for protection or preservation of
European cultural heritage Prof. Lucia Toniolo lucia.toniolo@polimi.it
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20/01/2017
Nanotechnology for the conservation Cultural Heritage
The synthesis and application of nanoparticles and nanocomposites lead

to significant improvements in the field of conservation and restoration of
Cultural Heritage.
Surface Coatings
Dispersions of
nanoparticles (TiO2, SiO2)
Consolidants
Nanocomposites:
Ca hydroxide polymer + nanoparticles
nanoparticles
Silica nanoparticles
Particle-modified Deacidifying Materials
consolidants
Ca or Mg hydroxide
nanoparticles
Consolidants
Definition from Lazzarini and Tabasso, Il

restauro della pietra:
treatment with the aim to improve the

characteristics of cohesion and
adhesion between the constituents of a
material
as a result of a consolidation, the

mechanical strength of the material
should therefore be improved
treatment will increase the resistance to

weathering processes, especially those
that occur with change in volume
within the network of capillaries...
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20/01/2017
Consolidants
Requirements:
1. Strengthen the materials
2. Good penetration depth
3. Chemical bonding to the stone
4. Suitable viscosity to move beyond the areas to be
consolidated
5. Proper surface tension to be distributed homogeneously on
the surface
6. Physicochemical and mechanical compatibility between
the healthy and the consolidated stone
7. No cracks during shrinkage
8. No esthetical change of the surface
Nano-Consolidants
1. Ca hydroxide
nanoparticles
2. Silica nanoparticles
3. Particle-modified
consolidants
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Ca hydroxide nanoparticles: introduction
Advantages of inorganic conservation treatments:

- chemically and structurally similar with the substrate they are applied on
- better aging compared to polymer-based conservation treatments
Degradation of a wall painting. (A) Paint layer detachments (white spots). (B) Salt efflorescence. (C) Paint layer flaking and detachment
due to the presence of organic coatings. The polymer coating acts as a barrier preventing the natural breathing of the surface and
consistently increasing the mechanical stresses due to salt crystallization at the paintingpolymer interface.
Long tradition on the use of inorganic compounds for the protection and
consolidation of building materials such as stone: limewater (calcium
hydroxide saturated solution)
Ca(OH)2 + CO2 CaCO3 + H2O
The limewater method does not seem to be very effective:
1. the limited solubility of Ca(OH)2 in water (1.7 g L1 at 20 C)

precludes the introduction of sufficient amounts of
consolidant into the porous system of the treated material
2. the use of large quantities of water is also an important risk
(potential substrate dissolution, clay-swelling, mobilization
of salts or freezethaw damage, growth of microorganisms)
3. poor penetration in the substrate
4. surface white glazing
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20/01/2017
Why is nanolime better than limewater?
1. higher reactivity
2. particles have enhanced physico-chemical properties
3. higher penetration efficiency in the stone substrates
4. reduction of carbonation time
5. stability even in presence of acrylic copolymers as
residues in the porous matrix
6. reactivity and properties can be controlled and
modulated controlling the particle size
Ca hydroxide nanoparticles: synthesis
What is a nanolime?
Water or alcoholic dispersions of calcium hydroxide nanoparticles
A wide range of different synthesis pathways for the preparation of calcium
hydroxide nanoparticles dispersed in short-chain alcohols (e.g. 1-propanol)
Critical point: the control of the size and shape of the particles
Some products are available on the market: NANORESTORE PLUS (distributed

by CTS) is a family of different nanolimes produced by CSGI of University of
Florence (Italy) and CALOSIL (IBZ-SALZCHEMIE)
400 nm
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Ca hydroxide nanoparticles: application

APPLICATION:
a. Consolidants for stone, lime mortars and wall painting
b. Deacidification of paper, canvas, and wood
Ca hydroxide nanoparticles: case-studies

Wall painting
(A) Wall painting belonging to a

Mesoamerican archeological site.
(B) Details of a flaking surface exhibiting
sulfate efflorescence.
(C) The same surface after the
desulfation treatment with
ammonium carbonate and the
application of a mixed calcium and
barium hydroxide nanoparticle
dispersion.
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Wall painting
Wall paintings by Santi di Tito

(XVI century) Gli Angeli
Musicanti on the Counter
faade of the Santa Maria
del Fiore Cathedral in
Florence.

Wall painting
Wall paintings of Chiesa

della Missione in Mondov:
Frescoes by Andrea Pozzo:
problems of salts
cristallization
Test areas
White glaze
after the
application of
nanolime
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Stones
Ca Granda, Milan, Italy. On the left, the untreated and powdering portion of
Pietra DAngera
To obtain good consolidation effect,

the treatment must be repeated Alberese and
Gallina stone:
many times A and C untreated
Consolidation of the first layers of the stones
B and D treated
stone stones
Silica nanoparticles
The goal is the use of SiO2 nanoparticles

as inorganic nanostructured
consolidant with an higher long term
stability with respect to synthetic
polymers actually used
Some products are available on the

market:(NANOESTEL (CTS), SIOXAL (IBZ-
SALZCHEMIE), LUDOX PX30 and PW30
(GRACE) and PARNASOS ZG000012 and
ZG000014 (COLOROBBIA)
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Silica nanoparticles: application
Application of dispersions of
nanosilica during the last
restoration of the Leaning Tower
in Pisa for the consolidation of
capitals
1) Laser cleaning to remove black

residues
2) Filling of the holes
3) Consolidation with nano SiO2,
applied by dip coating (2-
6litres/each application on capital )
Particle-modified consolidants
Preparation of the particle-modified consolidants:

loading silicate consolidant with colloidal oxide particles
nano SiO2 , Al2O3, TiO2 + pre-polymerised tetraethoxysilane (TEOS)
TEOS as a consolidant: sol-gel process

Si(OC2H5)4 + 2 H2O SiO2 + 4 C2H5OH
TEOS (monomer)
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Particle-modified consolidants
Application on Ohio sandstone: better performance of

PMCs
Improved properties compared with the unfilled TEOS:

1. protection from salt crystallization damage
2. strong reduction of silicate network shrinkage
3. Increase of the elastic modulus
4. Decrease of thermal expansion
Nanocomposites
Calcium-oxalatesilica
nanocomposite
Nanocomposite composed of silica and calcium oxalate

Nano-calcium oxalate monohydrate colloidal solution was
synthesised (CaOx):
Ca(OH)2 + H2C2O4.2H2O CaC2O4.H2O + 3H2O
Incorporation of CaOx in TEOS yields a crack-free, stable

nanocomposite (SilOxal)
The approach followed for the synthesis can be considered
biomimetic to natural ones occurring on monuments and in
biominerallization
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Calcium-oxalatesilica Nanocomposites
nanocomposite
Mesoporous microstructure of SilOxal has physico-

chemical compatibility with stone
SilOxal does not alter the microstructure of the

treated stone
SilOxal improves the hygric properties and the

tensile strength of stone
The physico-chemical stability and compatibility of

the nanocomposite with stone created a potential
strengthening agent with a partial protective effect
for inorganic porous building materials.
Deposition of the product in the walls

of the pores (red cycles) (figures a, b).
The deposited product exhibits an
easily recognized microstructure that is
characterized by well distorted spheres
(red arrow) (figures b, c).
Surface Coatings
Protective coatings:
Materials with specific optical characteristics that are
applied, in form of thin films, on the surface of an artifact in
order to protect it towards decay agents, such as water,
pollutants, vandalism etc.
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Surface Coatings
They need specific requirements to be applied in the field of

conservation and restoration of Cultural Heritage:
chemical inertness
stability
protective efficacy
no harmful by-products
maximum water vapor permeability
maintaining the original aesthetic characteristics
retreatability
Surface Coatings
Main classes:
a. Dispersions of nanoparticles
b. Nanocomposites: polymer +
nanoparticles
Additional properties compared to the

traditional protective treatments:
- self-cleaning
- biocidal and antifouling action
- increase of the hydrophobicity
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20/01/2017
Self-cleaning coatings: a big dilemma
Hydrophilic Hydrophobic
Introduction Task 1 Task 2 Task 3 Conclusion
Surface Coatings
Self-cleaning coatings
Idrophilic Idrophobic
- Photocatalytic - Lotus-effect
- Semiconductors: ZrO2, ZnO, CdS, TiO2 - nano SiO2, Al2O3
- Multiporous structures
Superficial nano-
roughness
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Surface Coatings: self-cleaning TiO2 coating
Nano-TiO2 is able to
degrade organic and
inorganic pollutants
It is able to make the

surface superhydrophilic,
easily removing dust by
rainfall
Reduction of cleaning and

maintenace costs
90s: first application on building materials
a. Air depollution (outdoor and indoor): plaster, external coatings

DRAWBACK: lower catalytic activity because of the reduction of
active surface
b. Self-cleaning: cement, mortars, glass, tiles

DRAWBACK S: durability, degradation of organic binders
c. Self-disinfecting: contrasting results in literature

- TiO2 slows down biofilm growth
- Biocidal activity against planktonic bacterial cells but not on biofilm
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Dispersions of nanoparticles
Water or alcoholic dispersions of nano TiO2 (40-
50 nm,1%)
Different synthesis routes of NPs
Anatase is more photocatalythic than rutile and
brookite
Application on stone, mortars, plasters, bricks by
spray or brush
No change of esthetic, wettability, water
absorption properties after the application
Problems of aggregation of nanoparticles and
cracks
Lack: durability tests, outdoor application,
application on real case-studies
Extension of the range of absorption toward the
visible: Au and Ag nanoparticles

Ca Ti
Nanocomposites:
APPLICATION WITH TEOS
Mesoporous coating: SiO2(from TEOS), nano

TiO2 (P25 Evonik AEROXIDE, 21 nm, untill 2%),
non-ionic surfactant (n-octylamine)
Increasing nanoparticle cocentration:
improvement of photocatalythic properties
untill 4%
No cracks
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Nanocomposites:
Loading of TiO2 and Ag nanoparticles
The integration of higher Ag loadings in a TiO2SiO2 network (10% w/w) significantly

increase the photoactivity of the coating containing 1% (w/v)TiO2 due to the improved
absorption of visible light and higher surface area of the photocatalyst.
For higher TiO2 contents (4%) there is an increase in photoactivity for 1% (w/v) Ag
loading.
Higher amounts of Ag loadings (5% w/w) generate an undesired color change on stone
or inhibit the solgel transition of the coatings (10% w/w).
Nanocomposites:
APPLICATION WITH OTHER POLYMERS:
- Polydimethylsiloxane
- Polialchilsiloxane
- Acrilic polimers
- Poly(2-ethyl-2-oxazoline)-Aquazol: application on paintings
- Cellulosic polymer: Klucel G
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Nanocomposites:
nano TiO2 dispersions in

ethanol and spray
application on Klucel G
Application on paper of
single dispersions and
nancomposite
Klucel G - TiO2: less
oxidation of paper, good
mechanical properties, no
biofilm
Good reversibility of the
treatment
Surface Coatings: antibacterial and antifouling
Bactericidal and antifouling coatings:

the inhibition of microbial colonization
of stone artworks.
Use of different nanoparticles (Ag, Cu,

ZnO) as dispersions or mixed with
consolidant and protective
treatments
They can also prevent the

biocolonization
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Conclusions
Nanomaterials exhibit enhanced properties compared to traditional
methods: high physico-chemical compatibility with the original
materials of works of art, avoiding relevant changes of the original
aesthetic properties of the substrates
Different classes of nanomaterials show less toxicity and have less

impact on both the workers and the environment
The innovative nanomaterials show enhanced effectiveness in their

main properties as their higher surface area make them more
reactive
Some products are available on the market
They need to be tested on selected areas, before their application

on site because they are not appropriate for every substrate
Lack of information about the durability of these nanomaterials
Nanoscale 3D printed model of St. Stephen's Cathedral, Vienna
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The Use of Nano-Materials For The Conservation of Historic Architecture

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20/01/2017

The use of nano-structured

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology deals with nanomaterials

Any form of a material that is composed of discrete functional

structures sized between 1 to 100 nanometer and involves the

Nanomaterials present new properties or improved properties

Prof. Lucia Toniolo lucia.toniolo@polimi.it

How much is a nanometer?

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

Cement and concrete:

Nano-SiO2 and clinker used to increase

Addition of photocatalytic nano-TiO2

Carbon nanotubes have the potential

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

nano-TiO2 is hydrophilic and water

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

Self-disinfecting and depolluting

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

Large surface area of nano-TiO2

it has potential for lower material

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

Music and art city hall in

Church Dives in Misericordia in Rome

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology in building materials

SEM image of snail shell

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology and Cultural Heritage

Lycurgus cup: example of late

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology and Cultural Heritage

Luster pottery represents

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Nanotechnology and Cultural Heritage

Damascus steel blades

Prof. Lucia Toniolo lucia.toniolo@polimi.it

What we can do?

Nanotechnology for Cultural Heritage

- Nano-materials for the conservation and preservation of movable and

- Nano-systems for the conservation of immoveable and moveable

- Protection of Cultural Heritage objects with multifunctional advanced

- Stone Conservation for the Refurbishment of Buildings STONECORE

- Plasma and nano for new age soft conservation - PANNA

New call Horizon 2020: Bando NMP-21-2014Materials-

Nanotechnology for the conservation Cultural Heritage

The synthesis and application of nanoparticles and nanocomposites lead

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Definition from Lazzarini and Tabasso, Il

treatment with the aim to improve the

as a result of a consolidation, the

treatment will increase the resistance to

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Prof. Lucia Toniolo lucia.toniolo@polimi.it

Ca hydroxide nanoparticles: introduction