1. Meeting of Young Geoscientists
Study of Zsolnay building ceramics in aspect of deterioration by environmental factors
Ágnes Baricza
Lithosphere Fluid Research Lab, Eötvös University, Budapest, Hungary
&
Institute for Geological and Geochemical Research, Research Centre for Astronomy and Earth Sciences, Hungarian Academy of Science
Meeting of Young Geoscientists
April 5-6, 2013, Békéscsaba

2. Introduction Human ↔ Environment
Pollutants deposit on the built environment
from transport, heating and industry
Built environment → Natural and man-made silicate based materials
Zsolnay building ceramics
- These ceramics have not examined in this aspect before
Goals:
reveal the effects of air pollutants on building ceramics
study the ceramic body and the glaze (phase composition, microfabrics, deposited layers)
obtain more information about the Zsolnay ceramics

3. The Zsolnay Factory 1853. Inception of the Zsolnay Factory
The Zsolnay products are the most famous Hungarian ceramics: vessels, fireproof bricks, terracotta, majolica, fajance, pyrogranite, lot of glaze and the famous eosine…
: Boom of industrial and building ceramics
In Budapest, between 1875 and 1918, more than 150 buildings were covered with Zsolnay ceramics and applied by the most famous Hungarian architecs (e.g. Ödön Lechner, Miklós Ybl, Alajos Hauszmann, Béla Lajta)
Postatakarékpénztár
Post Saving Bank
Mátyás templom
BME Könyvtár épülete

4. Buildings and materials
The two sampled buildings are:
The Museum of Applied Arts
The Hungarian Geological and Geophysical Institute

5. Environmental Effects
Artificial effects
Natural effects
The principal gaseous pollutants (e.g. SO2, NOx, CO2) and the contacting water easily form
different acids
building materials corrosion
Aerosol particles, soot, dust
„black deposited layer”
on the surface
Minerals and salts:
sulphates (usually gypsum), carbonates (e.g. calcite), glauberithe, weddellite, thenardite
appearance on the surface and in the pores  increase the pressure
Presence of different kind of water
material dissolution
Living forms (e.g. plants, microorganisms)
formation of cracks, ion dissolution

6. Methods SMZ 800 stereomicroscope and Nikon E600 polarizing microscope
mineralogical composition and texture of the ceramics
X-ray diffraction analysis (XRD) with a Philips PW 1730 diffractometer
phase composition of the ceramic body and the depositions
microstructure of the ceramic body and the glaze, their interface, alterations and depositions
Amray 1830 I/T6 scanning electron microscope (SEM)

7. Results 1. The building ceramics characteristics - XRD
Collected 26 samples
26 samples – 3 groups
quartz, mullite > crystobalite, K-feldspar
quartz, crystobalite, mullite
quartz, mullite > crystobalite, K-feldspar, plagioclase
30 samples – 4 group
quartz ~ crystobalite, mullite
quartz > crystobalite, mullite
quartz >> crystobalite, mullite
quartz > crystobalite, K-feldspar, plagioclase, mullite
Collected 30 samples

8. Cr, Fe, Co, Ni, Zn inclusions
Museum of Applied Arts
Results 2. The building ceramic characteristics - SEM
1. group
2. group
3. group
glaze
Pb-contained
K-feldspar
ceramic body
Pb-rich zone
the glaze soaked the ceramic
pores
melted particles
quartz
Glass particles
glaze
feldspar
inclusion
Pb-rich Ca-Al silicate
Cr, Fe, Co, Ni, Zn inclusions
Feldspar inclusions

9. Results 2. The building ceramic characteristics - SEM
The Hungarian Geological and Geophysical Institute
Results 2. The building ceramic characteristics - SEM
1. group
2. group
glaze
Sn-rich inclusions
pores
pores
pores
ortoclase
Slim, uneven glaze
quartz
Pb-rich Ca-Al silicate line
3. group
4. group

10. Results 3. Effects of air pollution
Black deposition/deposited layer covers the glazed and the unglazed sides.
It contains dust, soot and aerosols in variable quantity, and based on the XRD results, it also can consist of weddellite, thenardite
This layer appears in greater amount of the Museum of Applied Arts
Lots of different types of spherules  comes from industrial cumbostion
Fe-rich, silicate spherules and spherules with complex composition, containing Si, Ca, K, Al and S, can be distinguished
Deposition layer on the ceramics
Different kind of spherules

11. Results 4. Effects of environment
Gypsum accumulates on the surface of tiles, mainly on the samples from Museum of Applied Arts
We have also found traces of biological activity, which are probably residues of former microorganisms (bacteria, lichen and/or fungi)
Other crystals, glauberithe found on the The Hungarian Geological and Geophysical Institute samples
Gypsum crystals on the glazed and unglazed sides of the ceramics
Glauberithe crystals on the glazed side of the ceramics
Residues of living forms

12. Results 5 The begining of deterioration…
On some ceramic tile, signs of deterioration have appeared:
- crack, microcraks across the glaze
- some of the samples from Museum of Applied Arts, the major component of the glaze (Pb) was dissolved
- appear the so called „pitting corrosion” phenomena
- and the glaze, started to weather… Fe Pb Si Al P Ca K Ti Cu Zn
glaze
deposition layer
weathered glaze glaze

13. Summary
The purpose: study the Zsolnay building ceramics and its deterioration mechanisms by environmental factors
Two buildings were examined; the Museum of Applied Arts and The Hungarian Geological and Geophysical Institute
We distinguished three and four ceramic groups, resectively
Black deposition layer and spherules (mainly artificial) were observed  transport, heating, industry.
Gypsum on the ceramics from Museum  close to the Buda hills
Residues of former biological activity (bacteria/lichen/fungi), confirmed also by the presence of calcium oxalate (weddellite)
Deteriorating phenomena observed: cracks, pitting corrosion, dissolution of the glaze
Some tiles from the Museum the glaze had started to weather
Summary: The ceramics of the Museum of Applied Arts are in worse condition, perhaps due to the situation of the building (in the middle of the city).

14. Thank you for your attention
Acknowledgements:
I gratefully thank the support for the Hungarian Geological Society.
I also thank Bernadett Bajnóczi Ph.D, Mária Tóth, research fellow and Csaba Szabó, Ph.D. for supervising my work, and all the members of the LRG for their help. I would like to thank the contribution in the making of this study of Dr. Imre Takács and Dr. Tamás Fancsik.