University of Novi Sad,

Faculty of Technology,
Laboratory for Materials
in Cultural Heritage

Functional mortars for conservation of cultural heritage

structures
S. Vucetic, B. Miljevic, O. Sovljanski, J M van der
Bergh, S. Markov, H.Hirsenberger, M. Tzoutzouli-
Malesevic, J.Ranogajec

14/16 October 2020 – On-line edition

Multidisciplinary research group

EXPERTISE
Prof Dr Jonjaua Ranogajec
Head of Department and Laboratory • Examination of building materials
(historical and modern)
• Design and processing of new
functional materials for cleaning ,
healing and protection historical
Prof Dr Siniša Dr Bojan Dr Snežana objects
Markov Miljević Vučetić
• Development of new methods
for materials characterization,
MSc Helena MSc Ana MSc John Milan functionality, compatibility,
Hirschenberger Vidaković durability (in situ and laboratory)
van der Bergh
 THE BACTERIA-BASED SYSTEM FOR EXTERNAL SELF-
HEALING OF SURFACE CRACKS

• Challenges:
1. Development of new bio-activated self-healing system and its
application in laboratory conditions
2. Design of mortar models with high compatibility between
laboratory prepared models and original historical mortars

3. Application of new self-healing system on to the historical mortar

samples and laboratory prepared and aged mortar models
4. Investigation of the self-healing efficiency
INTRODUCTION: THE BACTERIA-BASED SYSTEM FOR
EXTERNAL SELF-HEALING

- The self-healing phenomenon of cement-based and limestone-based

materials has been extensively studied due to emerging awareness of
its beneficial potentials in both modern and historical architecture.
- The self-healing effect strongly depends on a number of factors:
- pH value of structure matrix,
- dissolved inorganic carbon
- nucleation sites and presence of calcium ions available for
chemical reaction with carbonate ion
– The bacterial-induced precipitation of calcium carbonate has large
potential due to its fast and active crack repair, while also being
environmentally friendly and providing efficient bonding capacity
and compatibility
 INTRODUCTION: THE BACTERIAL-INDUCED
PRECIPITATION OF CALCIUM CARBONATE
- Microorganisms can influence the precipitation of carbonaceous
minerals, specifically calcium carbonate (CaCO3) through metabolic
processes such as organic acid utilization, urea hydrolysis and
denitrification
- Bacterial cell surfaces act as heterogeneous crystal nucleation sites in
supersaturated matrix with Ca2+ and CO32- ions

- The alkali-tolerant bacteria with high ureolityc activity have been

extensively used for application on cementitious
materials(Sporosarcina pasteurii, S. urea, Bacillus sphaericus, B.
megaterium).
 RESEARCH APPROACH
RESEARCH APPROACH
1. Characterization of the original materials
2. Design of compatible laboratory models
3. Aging of laboratory models and original materials in weathering chamber
4. Characterization of aged samples
5. Decision about optimal mixture of compatible restoration mortar
6. Creation of artificial cracks on laboratory models based on the surface crack
properties on original samples ( location, orientation and dimensions)
7. Development of the two-component healing agent: bacteria-based system
for external self-healing
8. Application and investigation of self-healing effect of the developed system -
evaluation of crack closure ratio
 MATERIALS AND METHODS
CHARACTERIZATION OF HISTORICAL
MORTAR SAMPLES – HM AND PREPARED
MODEL MORTARS-MM
• Stereo optic microscopy
• Sieving and chemical analysis
• X-ray Fluorescence Analysis (XRF)
• Fourier transform Infrared spectroscopy
(FTIR)
• Structural analysis (XRD)
• Colorimetry
• Textural properties (Hg porosimetry)
• Scanning electron microscopy with energy
dispersive spectroscopy (SEM/EDS)
• Examination of mutual interaction and
cohesion between old and new material –
compatibility test
DESIGN OF BIO-ACTIVATED SELF-HEALING
SYSTEM/SELF-HEALING EXPERIMENT
• Ureolytic bacteria in the MICP process,
Sporosarcina pasteurii as self-healing agent
– BIO-SAMPLES: mortar samples (HM and MM)
with bio-activating agent and nutrient, and
– BLANK SAMPLES: mortar samples (HM and
MM) with nutrient only.
• SELF-HEALING EFFICIENCY:
– The change of surface cracks was monitored every 7 days
during the first 28 day-incubation, and every 30 days
until 150-day period. Portable Digital Microscope )
– The surface morphology of the formed calcium-
carbonate precipitate inside the surface cracks was
examined by SEM and XRD after 28 and 150 days of
incubation period.
– In order to study morphology and structure properties of
the CaCO3 precipitate obtained by the bacterial activity
their activity was also monitored in a test tube and
examined by SEM and XRD.
 COMPATIBILITY CRITERIA
Scale of
Criteria Compatibility indicators Incompatibility risks incompatibility risk
assessment
ΔE<3 0
Total colour change ΔE 3<ΔE<5 5
AESTHETIC ΔE>5 10
COMPATIBILITY
No cracks 0
Appearance of cracks Visible cracks 10

Contact zone is formed 0

Macroscopic and microscopic
CONTACT ZONE testing: before and after aging Contact zone is partially formed 7
Visible cracks in contact zone 10

Similar 0
NATURE OF Aggregate nature Different 5
AGGREGATES AND
BINDERS Binder nature Similar 0
Different 10
0
Lower value of new mortar 0-3
MECHANICAL Bending and compressive strength Similar values (depends on function)
CHARACTERISTICS 5-10
Higher values of new mortar
(depends on function)

J. Delgado Rodrigues, A. Grossi, Indicators and ratings for compatibility assessment of conservation actions. Journal of Cultural Heritage, 8(2007), pp. 32-43
 LABORATORY SAMPLES DESIGN

New mortar
with a small pieces
of ancient mortar
imbedded

Model mortars laboratory preparation

 LABORATORY MODELS
WITH ANCIENT MORTAR SAMPLE

ANCIENT
MORTAR
 LABORATORY AGING - ARTIFICIAL WEATHERING

Aging conditions
• Room conditions
(T = 20˚C i RH = 60%); 7 days

• Extreme conditions:
– (T = 10˚C i RH = 80%); 3 h
– (T = 35˚C i RH = 35%); 3 h
– (T = 45˚C i RH = 35%); 2 h
 5 cycles repeated

Laboratory aging chamber

Binder Climate chamber KBWF 240
 Mortar compatibility assessment (MM and HM
samples)
Table 1. Mechanical properties and spectrophotometry results
Drilling resistance Spectrophotometry
Method/ measurements colour coordinates and ΔE
Average value Max. value
Properties
of drilling of drilling L* a* b* ΔE
force [N] force [N]
Historical mortar
0.5 0.6 79.08 1.45 10.77
(HM)
Model mortar after 0.94
0.3 0.5 79.32 2.36 10.77
artificial aging (MM)

• It is confirmed that the designed model mortars (MM) are suitable for conservation
purposes since they show lower values of average drilling force compared to the original
historical mortar samples (HM).
• The total colour difference (ΔE = 0.94) is lower than 3 which mean MM are visually highly
compatible with the HM (the difference could not be detected with naked eye)
• Colour coordinates for MM samples are approximately the same as in the case of HM
CONTACT ZONE EXAMINATION - MICROSCOPY

good results
of contact
zone
formation
 Bio-activated crack repair
Growth profiles of S. pasteurii DSM 33 on bio-samples
The number of bacterial cells [log/mL]
8
MM bio-sample
7.5
HM bio-sample
7

6.5

5.5
0 20 40 60 80 100 120 140
Incubation time [days]

• Within the first two months of incubation, concentration of vegetative cells was increased for at least 1 log
unit.
• The decreasing trends for both bio-samples were observed to the end of incubation period.
• At the end of the experiment, the concentration of vegetative cells of S. pasteurii DSM 33 was above 6 log
unit.
• It can be suggested that the observed concentration of vegetative cells can sustain the MICP
process and induce precipitation of crystal form in crack zones
 Bio-activated crack repair
Digital optical microscopy
Table 2. Microscopic images of HM and MM bio- and blank samples
Incubation period (days)
0 days 7 days 28 days 150 days 150 days
HM BIO-SAMPLES HM BLANK

x10 x10

x40 x40
MM BIO-SAMPLES MM BLANK

x10 x10

x40 x40

• The process of surface cracks sealing was clearly visible on both HM and MM samples
treated with the bio-activated self-healing agent (bio-samples), in comparison to the blank
samples
• Higher efficiency of the bio-stimulating crack repair was obtained in the case of
conservation mortar models (lack of free calcium ions in historical samples)
 Bio-activated crack repair
SEM analysis of mortar models
Table 3. SEM analysis of MM blank and bio-samples, 28 days of incubation
BLANK BIO-SAMPLES

x200 x200

x1000 x1000

The SEM images of MM bio-samples after 28 days of incubation, Table 3, reveal the effects of
advanced bacteria stimulated formation of calcium-carbonate in the cracks.
 CONCLUSIONS (I)
• Sixteen systems of model mortars were designed and aged under
laboratory conditions in artificial weathering chamber. The most promising
systems (ratio of aggregates and binders 2:1, hydraulic lime, crushed brick
as pozzolanic material, river sand, and milled limestone as aggregates, and
water).

• Designed system stood out and fully complied with the set compatibility
criteria: aesthetic compatibility, mineralogical nature of aggregates and
binders, targeted weaker mechanical characteristics and contact zone
formation.
 CONCLUSIONS (II)
• The present study of the bio-stimulated crack-healing in historical and
conservation mortar samples, showed a promising path to further
investigation of bacteria-based systems for self-healing effect on lime
mortar surfaces.
• The monitored viability of S. pasteurii DSM 33 cells during the 150-day
experiment confirmed potentials of the chosen bacterial culture for self-
healing of the selected substrates.
• Higher efficiency of the bio-stimulating crack repair was obtained in the
case of conservation mortar models, compared to the original historical
mortar samples.
• The presence of CaCO3 crystals in the precipitate obtained in conservation
mortar models (MM) confirmed the activity of the developed bio-system.
• The absence of any crack sealing effect in the blank samples of both
conservation mortar models (MM) and historical samples (HM) stands to
confirm that the selected bacterial culture, under the designed
conditions, precipitated CaCO3 in/on the treated samples and stimulated
surface crack-sealing
 Thank you for attention
Laboratory for the Materials in Cultural Heritage
Faculty of Technology, University of Novi Sad Novi Sad, Serbia

Contact us:
heritagelab@tf.uns.ac.rs