Romain Bordes

Silica Nanoparticles:

A building block in Art Conservation

NanoInnovation 2020

Acknowledgements

Chalmers 2

Chalmers

Krister Holmberg

Oleksandr Nechyporchuk

Krzysztof Kolman

Kinga Grenda

Elyse Canosa

NanoRestArt:

This project has received funding from the European Union’s

Horizon 2020 research and innovation programme under grant

agreement No 646063.

APACHE: This project has received funding from the European

Union’s Horizon 2020 research and innovation programme

under grant agreement No 814496

Michael PerssonPiero Baglioni’s group

NanoInnovation 2020

Work of Art, Conservation Science and Nanosilica?

Chalmers 3

o Readily available

o Environmentally friendly

o Can be surface modified

Applied Surface Science, 2011, (257), 4250-4256

NanoInnovation 2020 Chalmers 4

Two applications:

Strengthening of textiles Development of adsorbent for pollutants

NanoInnovation 2020 Chalmers 5

Cotton degrades: damaged fibers

Reasons: oxidation and acidification

10 µm

Nechyporchuk et al., Journal of Cultural Heritage 2017, 28, 183-187.

NanoInnovation 2020

Traditional lining

Chalmers 6

Gainsborough Products, LLC

o Natural protein-based glue (e.g.

rabbit glue)

o Synthetic adhesive (e.g Plextol

B500, D360 or BEVA 371)

o Thermoplastic…

NanoInnovation 2020 Chalmers 7

Nanosilica is not working as such

+ silica2 µm

Iler, The chemistry of silica, Wiley-Blackwell, New York, 1979.

NanoInnovation 2020 Chalmers 8

Neat cationic particles

- strong attachment

Neat anionic particles

last layer = cellulose

Carboxymethylcellulose (CMC)

Bare silica:

• 4 – 200 nm

• Negatively charged

• Alkaline

Silica + polyelectrolytesPolyethyleneimine

PEI

Surface modification

Key aspects:

- Inspired from paper industry

- High concentrations

NanoInnovation 2020 Chalmers 9

+ silica

+ silica + PEI + CMC

Mechanical reinforcement

+ silica + PEI

10 µm

2 µm

2 µm

Kolman et al. Colloids Surf., A 2017, 532, 420-427.

Kolman et al. ACS Appl. Nano Mater. 2018, 1, 2036-2040

Palladino et al. Nanomaterials 2020, 10(5), 900.

NanoInnovation 2020

Adsorbent development

J.Mater.Chem., 2011, 21, 15100–15120

Physical impregnation

• Easy to prepare

• Easy to up-scale

• The most practical for use on large scales

• Amine-containing polymers as polyethylenimine

(PEI) are often use due to low volatility and high

amine content

• The silica-PEI composites are more robust to a

variety of treatment conditions

Porous silica

support

Hollow structures provide

space for accommodation of

PEI, leading to high adsorption

capacities

Silica

NP

Silica-based

adsorbentWet Impregnation

with polyethylenimine (PEI)

NanoInnovation 2020 Chalmers 11

One-pot wet impregnation

Polyethylenimine

(PEI)Solven

tMeOH

H2O

Polyethylenimine (PEI) Solvent

Silica-PEI

Final product

• FTIR• BET• SEM (selected

samples)• TGA

Characterization

BET – Brunauer-Emmett-Teller

SEM – Scanning Electron Microscope

TGA – Thermogravimetric Analysis

FTIR – Fourier Transform Infrared Spectroscopy

MeOH

H2O

Mw =800; Mn=600

Mw =25 000; Mn=10 000

Mw =1 300; Mn=1 200

Mw =60 000; Mn=750 000

▪ PEI loading: 5-65 wt%

Linear (L)

Branched (B)

SilicaLevasil CS30-236

Quartzene Z1

Silica byproduct

Levasil CS20-730

Levasil CS4-4110

NanoInnovation 2020 Chalmers 12

Laboratory tests Field tests

Swedish National

Archives:

Nitrate/acetate negative

storage

Vasa Museum:

Display case copper corrosion

✓ Acetaldehyde

Pollutants:

✓ Acetic acid

✓ Formaldehyde

✓ Formic acid

✓ NO2

Analytical approach✓ Flow-bed reactor

• DRIFT-MS

• DSC-MS

✓ ODDY test

✓ Accelerated ageing

NanoInnovation 2020 Chalmers 13

Conclusionso Nanosilica

o Can be adapted to various purposes

o Find inspiration in industrial application to tackle conservation

science problems

o Textile reinforcement

o CMC or PEI terminated – control surface distribution

o Provide a stiffer reinforcement

o Adsorbent development

o Versatile

o Surface modification