Proceedings PKM 2019

TECHNICAL UNIVERSITY OF KOŠICE
FACULTY OF MATERIALS, METALLURGY

AND RECYCLING
PREPARATION OF CERAMIC MATERIALS

PROCEEDINGS OF EDITED CONTRIBUTIONS
Slovak Silicate Society

Slovak Glass Society
th
25th – 27 June 2019 Jahodná, Slovakia
TECHNICAL UNIVERSITY OF KOSICE
FACULTY OF MATERALS, METALLURGY
AND RECYCLING
Institute of Materials Research  Slovak Academy of Sciences, Kosice

Institute of Geotechnics  Slovak Academy of Sciences, Kosice
Slovak Silicate Society
Slovak Glass Society

Proceedings of the XIII t h International Conference
Jahodná
25 t h – 27 t h June, 2019
Internet: Full text available online at http://web.tuke.sk/seminar_PKM/
Proceedings - XIIIth International Conference

Jahodná, 25 t h – 27 t h June, 2019
Copyright  Technical University of Kosice 2019
June 2019,
I. edition
Number of Copies – 75
Number of Pages – 206
The publication of proceedings was supported by

SLOVAK SILICATE SOCIETY- ASSTS
SLOVAK GLASS SOCIETY
TECHNICAL UNIVERSITY OF KOSICE,
FACULTY of MATERIALS, METALLUGY and RECYCLING
Edited by:
Prof. Ing. Beatrice Plešingerová, CSc.
Ing. Dávid Medveď, Ph.D.
Reviewers:
Assoc. Prof. Ing. Miroslav Hnatko, Ph.D.
RNDr. Martin Fabián, Ph.D.
Ing. Diana Horkavcová, Ph.D.
Ing. Dana Ivanová, Ph.D.
ISBN: 978-80-553-3314-4
Acknowledgements:
Members of Organization Committee thank all Companies and Institutions:
PROMAT, s.r.o. Praha Železiarne Podbrezová, a.s.
SLOVMAG, a.s. Lubeník SMZ, a.s. Jelšava
SSi VTS, SSkS RONA, a.s. Lednické Rovne
for support of XIII. International Conference
SCOPES OF THE CONFERENCE:

- Refractories and Fireproof Ceramics
- Construction and Building Ceramics
- Fine Ceramics and Surface Treatments
- Glass, Glass-Ceramic Materials
- Modeling and Simulation of High-Temperature Processes and Corrosion
Information - Correspondence:
TECHNICAL UNIVERSITY
FACULTY OF MATERIALS, METALLURGY AND RECYCLING
P r o f . I n g . B . P l e š i n g e r o vá , C S c .
L e t n á 9 , 0 4 0 0 2 K O Š I C E , S l o va k R e p u b l i c
tel.: +421/ 55/ 602 2900
e-mail: beatrice.plesingerova@tuke.sk
CONTENT
LECTURES
L1 Ľ. Ďurik , J. Švantner, Ľ. Parilák, M. Brenkus 11

DEVELOPMENT OF ULTRALOW-CEMENT SPINEL CASTABLE
FORWORKING LINING OF LADLE IN ZP, a.s.
L2 B. Udvardi, R. Géber, I. Kocserha 17
EXAMINATION OF DIFFERENT WASTE MATERIALS FOR ROAD
CONSTRUCTION
L3 M. Hujová, J. Kloužek, R. Pokorný, J. Kraxner 25
CONVERSION OF BATCH-TO-GLASS ANALYSIS: APPLICATION
TONUCLEAR WASTE
L4 R. Bystrický, M. Hnatko, J. Sedláček 33
PREPARATION OF LIGHTWEIGHT AGGREGATES FROM INDUSTRIAL
WASTE
L5 M. Fabián, B.I. Arias-Serrado, A. A. Yaremchenko, H. Kolev, 39
M.Kaňuchová, J. Briančin
ELECTRICAL CONDUCTIVITY IN Ca DOPED LaAlO3 PEROVSKITES
PREPARED BY BALL MILLING
L6 D. Furka, S. Furka, M. Naftaly, M. Čaplovičová, M. Janek 45
TERAHERTZ TIME-DOMAIN SPECTROSCOPY OF THE BORON DOPED ZnO
MATERIALS
L7 K. Jilkova, M. Mika, P. Kostka, F. Lahodny, R. Bures 51
GLASSES IN THE PbO-Bi2O3-Ga2O3 SYSTEM WITH ADDITION OF Ag2O
ANDSb2O3 FOR ELECTRO-OPTIC LIGHT MODULATORS
L8 F. Lofaj, M. Kabátová, J. Dobrovodský, M. Beňo, D. Vaňa 57
HYDROGENATION OF CARBON MATRIX IN W-C:H COATINGS DURING
HYBRID PVD-PECVD SPUTTERING BY ERDA
L9 L. Kvetková, M. Kabatová, F. Lofaj, A. Kovalčíková 65
HARDNESS AND FRICTION IN HiTUS W – C:H COATINGS DEPOSITED
WITH ACETYLENE AND METHANE
L 10 M. Mánik, F. Obert, J. Ondruška, T. Húlan, I. Štubňa 71
SHORE HARDNESS AND YOUNG’S MODULUS OF ALUMINA PORCELAIN
MIXTURE FIRED AT 300 °C – 1250 °C
L 11 D. Medveď, M. Ivor, T. Chmielewski , D. Golański, K. Pietrzak, 77
M. Chmielevski, A. Srojny-Nedza, D. Kottfer, J. Dusza
MICROSTRUCTURE CHARACTERISTICS, TRIBOLOGY AND NANO-
HARDNESS OF HVOF AND PLASMA SPRAYED NiCrRe COATING
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L 12 H. Bruncková, M. Kaňuchová, H. Kolev, Ľ. Medvecký 83
XPS CHARACTERIZATION OF EuNbO4 THIN FILM PREPARED BY SOL-GEL
METHOD
L 13 M. Kavanová, A. Kloužková 89
IDENTIFICATION OF DEFECTS OF SURFACE CERAMIC FINISHING
L 14 Ž. Dohnalová, M. Šnajdarová 94
PREPARATION OF TRANSITION METALS DOPED SrSnO3
L 15 M. Kavanová, A. Kloužková, P. Dvořáková, R. Šefců 99
CHARACTERIZATION OF PIGMENTS AND DYES OF SURFACE FINISHING
USING RAMAN SPECTROSCOPY
L 16 M. Hnatko, M. Hičák, J. Sedláček, P. Šajgalík 103
SURFACE MODIFICATION OF DENSE SILICON NITRIDE
L 17 M. Tatarková, P. Tatarko, I. Dlouhý, J. Dusza 111
SINTERING BEHAVIOUR AND MICROSTRUCTURAL EVOLUTION
OFSILICON NITRIDE COMPOSITES WITH BORON NITRIDE PLATELETS
L 18 M. Janek, T. Gabošová, R. Fialka, Z. Hajdúchová, P. Veteška, 115
K. Tomanová, J. Feranc, R. Plavec, V. Kovár, P. Peciar Ľ.Bača,
P.Alexy
HYDROXYAPATITE BASED MATERIALS FOR FDC 3D PRINTING FILAMENTS
APPLICABLE IN TISSUE SCAFFOLDS DEVELOPMENT
L 19 K. Švagrová, D. Horkavcová, A. Helebrant 123
MEASUREMENT OF BIOACTIVITY AND ANTIBACTERIAL EFFECT
OFTITANIA BASED COATINGS WITH Ag, Ca, P
L 20 A.Kloužková, P. Dvořáková, M. Kohoutková 128
SYNTHESIS OF CUBIC/TETRAGONAL LEUCITE BY CONTROLLED ION
EXCHANGE
L 21 N. P. Govindan, M. Michálková, D. Galusek 133
Ce3+
DOPED YTTRIA NANOPOWDERS FOR TRANSPARENT YTTRIA
CERAMICS PREPARED BY PRECIPITATION METHOD
L 22 M. Abdelfattah, I. Kocserha, R. Géber 141
THE EFFECT OF CALCIUM FLUORIDE ON MINERAL PHASES AND
PROPERTIES OF LIGHTWEIGHT EXPANDED CLAY AGGREGATES
L 23 J. F. M. Ibrahim, E. Kurovics, L.A. Gömze 147
NEW ZEOLITE-ALUMINA COMPOSITE MATERIALS - DEVELOPMENT AND
INVESTIGATION
th
XIII International Conference
6 PREPARATION OF CERAMIC MATERIALS
CONTENT
L 24 P. Dvořáková, F. Oujiří, A. Kloužková, M. Kavanová, 153

M.Kohoutková
INFLUENCE OF COMPOSITION ON PROPERTIES OF A CALCIUM CERAMIC
BODY
L 25 A. Kloužková, P. Dvořáková, M. Kavanová, M. Kohoutková, 158
V.Pulcová
CHARACTERIZATION OF CERAMIC BODIES AND GLAZES OF FAIENCES
FROM HRADČANY PALACES
L 26 A. Kloužková, M. Kohoutková 163
USE OF HYDROTHERMAL CONDITIONS IN THE FIELD OF SPECIAL
CERAMIC MATERIALS
L 27 B. Plešingerová, P. Vadász, G. Jablonský, D. Medveď, 169
R.Dzurňak, Ľ.Popovič
SEASONAL VARIABILITY IN COMPOSITION AND PROPERTIES OF ASHES
FROM COMBUSTION OF WOODCHIPS
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POSTERS - Abstracts
P1 E. Kurovics, L. A. Gömze 180

THERMO-ANALYTICAL ANALYSIS OF KAOLIN AND BIO-ADDITIVE
MIXTURES USING A DERIVATOGRAPH AND HEATING MICROSCOPE
P2 J. Hroch, Ž. Dohnalová 182
COLOUR PROPERTIES OF PEROVSKITE SrSn1-xMnxO3 PREPARED
BYCERAMIC METHOD
P3 L. Šimková, P. Šulcová 184
THE HYDROXYAPATITE AND ITS ANTI-CORROSION PROPERTIES
P 4 Ľ. Medvecký, R. Stulajterová, M. Giretova, T. Sopčák, 186
M.Hnatko, T.Fenclová
PROPERTIES AND MICROSTRUCTURE OF CALCIUM PHOSPHATE
CEMENT COMPOSITE CONTAINING Si3N4 MICROGRANULES
P5 R. Stulajterova, Ľ. Medvecký, M. Giretová, T. Sopčák, 188
J.Briančin
EFFECT OF ALGINATE HYDROGELS ON MECHANICAL PROPERTIES
OFTETRACALCIUM PHOSPHATE/ NANOMONETITE BIOCEMENT
P6 K. Švagrová, D. Horkavcová, A. Helebrant 190
TITANIA SOL-GEL COATING ENRICHED BY Ag, Ca, P PREPARED BY DIP
COATING TECHNIQUE
P7 I. Czudková, A. Helebrant, H. Hradecká 192
IN VITRO TESTING OF CHEMICAL SOLUBILITY OF THERMAL INSULATION
FIBRES
P8 M. Kyslytsyna, P. Raschman, G. Sučik 194
CRITICAL EVALUATION OF LEACHING KINETICS EXPERIMENTS
P9 P. Vadász, D. Medveď, B. Plešingerová, G. Sučik, Ľ. Ďurík, 196
Ľ.Popovič,, Ľ. Parilák
CORROSION OF SPINEL CONCRETES
P 10 E. Grambálová 198
CORROSION OF REFRACTORY MATERIALS IN ALUMINUM PRODUCTION
P 11 K. Pánová, D. Rohanová, H. Sedláčková 200
CHARACTERIZATION OF DIFFERENT TYPES OF WOOD ASHES USED
INHISTORICAL GLASSMAKING
P 12 D. Hršak, A. Štrkalj, I. Jandrlić, L. Slokar, Z. Glavaš 202
LONG TERM ENVIRONMENTAL THREATS FROM WORLDWIDE
INDUSTRIAL WASTE
th
LECTURES

XIII t h International Conference
Jahodná, Slovakia
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25 -27 June, 2019 9
L 1
DEVELOPMENT OF ULTRALOW-CEMENT SPINEL CASTABLE

FOR WORKING LINING OF LADLE IN ŽELEZIARNE PODBREZOVÁ
a,c b c c
Ľuboš Ďurik , Jozef Švantner , Ľudovít Parilák , Matej Brenkus
a
ŽIAROMAT a.s., Továrenská 1, 985 01 Kalinovo, SR,
b
ŽP a.s., Kolkáreň 35, 976 81 Podbrezová, SR,
c
ŽP VVC s.r.o., Kolkáreň 35, 976 81 Podbrezová, SR
e-mail: ldurik@ziaromat.sk, svantner.jozef@zelpo.sk, brenkus@zelpo.sk
The design of ladle linings in Železiarne Podbrezová has developed through a several stages
resulting in the current complex form. A pouring ladle (primary metallurgy) uses fireclay bricks
in the entire cross-section. Refining ladle (secondary metallurgy) uses a combination of bricks
and castable, i.e. the permanent lining uses fireclay bricks and castable, the working lining of
the walls and bottom is composed of monolithic lining, the slag line is bricked with
magnesium-carbon construction materials and refractory material is used under the ladle
collar. The ladle uses the upper and lower nozzle made of castable and quick-hardening
plastic mastic for refractory materials binding. Currently the bottom and walls are made of low-
cement castable. The current global trend consists in introducing working linings of ladles with
very low-cement content which compared to low-cement castable show low content of low-
melting components and thus higher high-temperature properties what ultimately positively
influences the application-operational properties as well. For 2018 – 2019 ŽP VVC accepted
in the research project no. 8 Research and Development of High Density Ceramics –
REFRACER Topic 1: Ultra-low cement (ULCC) castables based Al2O3 which includes the
ULCC castable with addition of Al2O3.MgO of spinel as well.
Keywords: ultra-low cement castable, ladle bottom and walls, monolithic lining
Introduction
In the production of steels, the linings of casting and refining ladles play a very
important role in the overall consumption of refractory materials. These refractory
linings are one of the elements that affect the quality of the steel because they are a
possible source of impurities and inclusions. Therefore, there is considerable effort
to reduce the specific consumption of refractory materials. Consumption of refractory
material also has economic implications, as the use of new linings making
technologies is one way to reduce costs. The introduction of new technological
processes in the production and processing of steel has created a permanent need
for the development of new superior refractory materials. Consumption of traditional
types of materials is decreasing and the consumption of special but also expensive
products used in ladles metallurgy is increasing.
Over the past 20 years, there has been a noticeable increase in the use of
refractories containing magnesium-aluminate (MA) spinel with low cement content
and low water addition. Currently, however, very low-cement spinel castables,
known as ultralow-cement refractory ULCC, are already emerging on the market.
The basic material is either Tabular Alumina or White Fused Alumina. Spinel is used
in fine fractions.
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DEVELOPMENT OF ULTRALOW-CEMENT SPINEL CASTABLE FOR WORKING LINING OF LADLE IN ZP, a.s.
Ľ. Ďurik, J. Švantner, Ľ. Parilák, M. Brenkus
ULCC with MA-spinel addition

Characteristic
The term "spinel" stands for the class of minerals where the two oxides are arranged
in a cubic crystalline structure. Their formula itself can be expressed as AB 2O4: "A"
represents divalent metal ions such as magnesium, iron, nickel, manganese, or
zirconium, and "B" trivalent such as aluminium, iron, chromium, and manganese.
The most widely used spinels in refractory systems are those containing iron,
magnesium, aluminium and chromium (FeF2O4, FeAl2O4, MgFe2O4, MgAl2O4,
MgCr2O4). Among these, MgAl2O4 (MA) a MgCr2O4 (MCr) spinels provide excellent
chemical and physical properties, including high refractoriness and chemical
influences resistance.
6+
Due to the carcinogenic effect of Cr , MCr spinel is gradually replaced by MA
spinel. MA spinel is a single compound in MgO-Al2O3 binary system (71.67 wt.%
Al2O3 and 28.33 wt.% MgO or in a 1 : 1 molar ratio for stoichiometric composition) as
shown in Figure 1.
Fig.1 Binary diagram of MgO-Al2O3
MA spinel has a high melting point (2135 °C) and due to the different thermal
expansion of its phases (MgO and Al2O3), spinel-containing refractories exhibit high
resistance to sudden temperature changes.
Effective use of MA spinel in refractory materials from the point of view of resistance
to slag corrosion and the depth of its infiltration is conditioned by knowledge of its
optimal addition and grain size itself. In Figures 2 and 3 we can see their influence.
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L 1
Fig. 2 Corrosion resistance index and infiltration depth for different MA contents in spinel
refractory
Fig. 3 Effect of spinel grain size on spinel refractory infiltration depth
It follows from the above diagrams that the optimum MA spinel content of the
refractory should be in the range of 15 to 25 % and in the grain size of 0 to 1 mm.
Top ULCC spinel refractories with a water addition of 3.9 % exhibit the following
typical properties, as shown in Table 1 [1].
Table 1 Typical properties of top ULCC spinel castable

Dried at 110 °C Fired at 1500 °C
Cold Cold Cold Cold Permanent
Bulk Apparent
modulus crushing modulus of crushing linear
density porosity
of rupture strength -3 rupture strength change
[g.cm ] [%)
[MPa] [MPa] [MPa] [MPa] [%]
10 50 3.20 12.1 52 270 – 0.42
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Experimental results
Based on the already mentioned task, in 2018, a specific laboratory-operational
development of ultralow-cement castable with the addition of MA spinel started. This
type of castable under the designation ŽNU 1800 SP is developed for ŽIAROMAT,
a.s., which is to be subsequently applied and used in ŽP a.s. for the working lining of
the bottom and the walls of the ladle.
Currently, the steelworks at ŽP a.s. use low-cement spinel castable under the
designation ŽN 1750 SP (typical properties of Table 2) with the addition of water at
the level of 4.4 % from ŽIAROMAT for the working lining of the bottom and wall of
the ladle.
Table 2 Typical properties of low-cement castable ŽN 1750 SP

Bulk Apparent
modulus crushing modulus of crushing linear
density porosity
of rupture strength -3 rupture strength change
[g.cm ] [%)
13 75 3.00 19 42 133  0.3
Based on a thorough research and analysis of ULCC castable in 2017, a test

prototype formulation was designed based on which input components were
provided. The basic input components were tubular corundum, reactive oxide, MA
spinel and spinelite cement. The weighed input components were dry blended for
5minutes in a 16 kg laboratory mixer. Subsequently, water of 480 ml (2.9 %) was
added and the wet mixing time was 4 minutes. The wet refractory mass was
deposited in the form of 5 testing prisms with dimensions of 55 × 65 × 235 mm.
Testing prisms were disassembled after 24 hours. On these test prisms, cold
properties (ambient temperature), as set forth in Table 3, were determined.
Table 3 Typical properties of developed ULCC spinel castable ŽNU 1800 SP

Bulk Apparent
modulus of crushing modulus of crushing linear
density porosity
rupture strength -3 rupture strength change
[g.cm ] [%)
23 107 3.23 13.25 63 > 142 + 0.09
Tables 1 and 3 show that the prototype ULCC spinel castable test formulation under
the designation ŽNU 1800 SP has achieved even better cold properties than the top
ULCC castable from literature [1] shown in Table 1. In particular, we have achieved:
1. Lower water addition by 1 %, i.e. 25 % reduction.
2. After drying testing prisms at 110 °C:
 higher cold modulus of rupture by 13 MPa, i.e. 130 % increase
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L 1
 higher cold crushing strength by 57 MPa, i.e. 114 % increase

-3
 higher bulk density by 0.03 g.cm , i.e. 1.4 % increase.
3. After firing testing prisms at 1400 °C:
Our testing ULCC prisms were fired at 1400 °C, i,e only 100 °C lower, resulting in
a higher porosity of 1.15 %, i.e. an increase of 9.5 %. However, it can be
assumed that a firing rate of 1500 °C would result in 12 % porosity. As far as cold
modulus of rupture is concerned, it was reported to be 11 MPa higher (21 %
increase), despite firing only at 1400 °C. Cold crushing strength is more difficult
to evaluation as the cold modulus of rupture determination device at ŽIAROMAT,
a.s. determines cold crushing strengths of up to 142 MPa. However, we can also
count in this case with an increase in cold crushing strength based on the
increase in cold modulus of rupture up to 320 MPa with firing at 1500 °C. We will
not compare permanent linear change in this case, as it is two different firing
temperatures of 1500 and 1400 °C.
If we focus on comparing the cold properties of ŽN 1750°C (currently used for
bottom and ladle walls) and ŽNU 1800 SP (developed ULCC castable), we will also
find the following from Tables 2 and 3:
1. Lower water addition by 1.5 %, i.e. 34 % reduction.
2. After drying prisms at 110 °C:
 higher cold crushing strength by 32 MPa, i.e. 43 % increase
-3
 higher bulk density by 0.23 g.cm , i.e. 7.7 % increase.
3. After firing prisms at 1400 °C:
 lower porosity by 5.75 %, i.e. 30 % reduction
 higher cold crushing strength, we cannot determine the exact value because
ŽNU 1800 SP quality prism did not undergo destruction even at the maximum
readability of the device of 142 MPa.
Reduced compactness and increased strength properties of ultralow-cement
castable in the quality of ŽNU 1800 SP have been achieved by:
 Specially modified grain size composition of the input components and the
resulting blended mixture.
 Reducing the addition of water.
 Using a special reactive alumina and a solidification additive.
Conclusion
For 2018-19, it was accepted for ŽP VVC in research task no. 8 Research and
Development of High Density Ceramics - REFRACER Topic 1: Ultralow-cement
(ULCC) Al2O3 based castables, which also include ULCC castable with MA spinel.
The aim of the development is to develop a new type of castable for the working
lining of the bottom and wall of the ladle, which will show better utility and application
properties than the existing type of castable.
The first results of the development of ultralow-cement castable under the
designation ŽNU 1800 SP for the working lining of the bottom and wall indicate that
Jahodná, Slovakia
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the formulation was optimally designed in terms of increased compactness and cold
strength. However, in the following period it is necessary to confirm the positive
results by determining properties at high temperatures and also by corrosion tests
and to compare again with the currently used quality of low-cement castable ŽN
1750 SP at the steelworks at ŽP a.s..
Acknowledgement: This work was supported by the Slovak Research and

Development Agency within the project APVV-17-0483 entitled "Ceramic materials
for refractory lining of boilers with intensified combustion of biomass".
References
[1] Long, B., Buhr, A., Jung, I., Jin, S.: Comparison of cement and hydratable alumina-
bonded alimina-spinel materials for steel ladle, In: Refractories Worldforum, August 2017,
pp. 93-106
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EXAMINATION OF DIFFERENT WASTE MATERIALS FOR ROAD

CONSTRUCTION
Bella Udvardi, Róbert Géber, István Kocserha

Institute of Ceramics and Polymer Engineering, University of Miskolc, Miskolc,
Hungary
e-mail: ubella07@gmail.com, robert.geber@uni-miskolc.hu,istvan.kocserha@uni-miskolc.hu
Primary mineral materials are essential raw materials for asphalt production, but mining of
these minerals will cause the depletion of sources. For this reason, it is necessary to search
for potential materials to substitute these minerals in part or in full. Potential materials are
included secondary materials, which are produced as by-products during industrial processes.
During the research work the usability of different secondary waste materials (aluminum
dross, brick powder and concrete powder) as a filler were investigated for road construction.
During the tests limestone was used as a reference material, because this is the most
frequently filler in asphalt technology.
In this research different tests were made, which are suitable to characterize the samples and
the cohesion between asphalt binder (bitumen) and filler can also reveal. Particle size
distribution, chemical element composition was determined on filler. Scanning
electronmicrographs were taken and oil adsorption test were also made.
The results show that dross is alike to limestone powder. Results of the particle size
distribution are close to each other. According to hydrophilic coefficient two waste materials
(dross and brick) are available for asphalt pavement.
Keywords: aluminum dross, asphalt, brick powder, concrete powder, filler, hydrophilic
coefficient, waste materials
Introduction
Road construction industry continuously uses a high amount of primary mineral
resources for asphalt production. Yielding of mineral materials are finite, therefore it
is necessary to search for alternative substances, which are suitable for road
construction applications. Waste material is produced all over the world in certain
industrial process. Treatment and storage of these materials are not necessarily
solved; therefore these waste materials can also cause environmental damage in
the long term. This is the reason that several industrial sectors and especially the
road construction are trying to use these materials as an alternative.
Researchers are continuously looking for possible materials which can be used for
asphalt production [1-15]. Ali et al. examined the effect of fly ash on the mechanical
properties of asphalt mixtures. On the basis of their results, it has been found that
the use of fly ash is preferable since it improves the strength of asphalt concrete [1].
Likitlersuang et al. made asphalt concrete mixtures using cement and fly ash (C
type), and the performance of mixtures were tested. According to their results
stiffness modulus of mixtures has increased by utilizing cement and fly ash as
asphalt filler [2]. Oluwasola et al. applied electric arc furnace steel slag and copper
Jahodná, Slovakia
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EXAMINATION OF DIFFERENT WASTE MATERIALS FOR ROAD CONSTRUCTION
B. Udvardi, R. Géber, I. Kocserha
mine tailings to replace conventional aggregates used in asphalt pavements. They

found that mine tailings and slag can be used as additives in road construction [9].
The research results of Mailar et al. have shown that recycled aluminium dross is
suitable for the partial replacement of cement required for concrete production [14].
Guo et al [16] dealt with steel slag treatment and recycling in China, where the steel
slag is the main by-product material of the steel production process. They found that
a new political step is needed to increase the utilization of slag as a road
construction material.
According to literature data [2, 3, 18] fly ash has already been used as a road
construction material.
Mistry et al [18] investigated that the fly ash used in the asphalt mixture affects the
replacement of hydrated lime filler. They results show that replacing hydrated lime
with fly ash not only complies with the standard but also strength compared to
conventional filler.
Chen et.al [19] investigation of the recycled brick powder in asphalt mixture: They
used the brick powder as a replacement of mineral filler. According to their results
the mixture with recycled brick powder has better mechanical properties, than the
reference material (limestone).
Aliabdo et al [20] examination of the demolition of brick building material as fine
aggregate for concrete industry: They made X-ray diffraction, thermogravimetric
analysis, and microstructural test were also made. They examined the compressive
strength of samples. The results of compressive strength that use of brick powder as
a cement addition increase mortar compressive strength value.
In this research work different tests were made to characterize the waste materials.
Particle size distribution, chemical elements composition and microstructural tests
were made. Hydrophilic coefficients of fillers were determined, oil adsorption test
were made, as well.
Materials and methods
In this research work two types of construction and demolition (C&D) wastes (brick
(B) and concrete (C) powder) and aluminum dross (D) as industrial by-product, were
investigated. During the work limestone (L) was used as a reference material.
Waste materials were comminuted by planetary ball mill at 20 min and 200 rpm.
Limestone was obtained in the appropriate fraction from the manufacturer. The
standard particle size for asphalt fillers is under 0.063 mm, so using standard sieves
the required proportion of powders were prepared. Raw materials were dried in a
laboratory drying chamber for weight-constancy.
Results and discussion
Particle size distribution
Determining the particle size distribution of fillers is an important assignment in
asphalt technology. It is essential, because the distribution of fillers has an effect on
the viscosity of the binder and thereby the stiffness of the asphalt pavement. Particle
size distribution was determined by Malvern Mastersizer X type particle size
analyzer. Fig. 1 illustrates the gradation of fillers.
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The results indicate that all powders are polydisperse materials. Limestone has the
most modes. It can be concluded that concrete powder has four modes and three of
these are under 100 µm. Average particle size (d 50) of the fillers are the following:
d50L:14µm<d50C:20 µm<d50B:26 µm and d50D:26 µm, as well. According to the
cumulative curves limestone is the finest material. The coarsest fraction is dross and
brick powder. Those fillers, which have finer particles, are required to increase the
stiffness effect of the asphalt mixture.
Fig.1 Particle size distribution of fillers
Chemical element composition and microstructure

It is important to reveal the material structural features and composition of fillers to
know better the behaviour between mineral materials and bitumen. Chemical
element composition tests were made using energy dispersive X-ray spectroscopy.
Table 1 Chemical composition of fillers

Chemical Limestone Aluminum dross Brick powder Concrete powder
element [wt.%] [wt.%] [wt.%] [wt.%]
C 9.20 0.00 25.94 15.76
O 37.34 18.13 34.94 37.4
Mg 0.49 2.90 0.75 0.95
Al 0.87 31.8 8.92 2.39
Si 2.08 1.31 21.3 23.73
Ca 49.59 3.32 0.53 15.9
Na 0.00 10.39 0.35 0.48
Cl 0.00 25.82 0 0
K 0.45 5.79 1.67 0.98
S 0 0 0 0.65
Fe 0 0 5.31 1.74
Ti 0 0 0.29 0
Total 100.2 99.46 100 99.98
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The experimental results show that dross was more complex material, than the
reference and the other two waste materials. Dross contains large quantities of
aluminum, besides Na, Cl and K elements are in significant amounts, which
indicated the presence of slag-forming agents (NaCl, KCl).
During the research work scanning electron micrographs were taken to observe the
surface features of fillers. SEM photos represents that limestone has got the finest
particles. In case of all powders, there are particles, which are glued together. SEM
micrographs illustrates that all the powders have similar geometrical features.
Limestone Aluminum dross
Brick powder Concrete powder

Fig. 2 SEM micrographs of powders
Determination of hydrophilic coefficient

Determination of hydrophilic coefficient is based on the comparison of polar and
apolar adsorption ability of the filler. This test determines the relationship between
mineral fillers and asphalt binder. Petroleum, like bitumen is an apolar liquid.
Hydrophilic coefficient (η) of fillers is determined by sedimentation method. 10 grams
of powders were weighed and put into 25 ml measuring cylinder. Half of the
measuring cylinders were filled with ethanol, the other half were filled with
petroleum, as well. 10 ml of ethanol and 10 ml petroleum were poured into the
cylinder, parallel. Powders and liquids were completely mixed together then the
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cylinders were filled with another 10 ml of liquids. After mixing the measuring
cylinders were closed. The volume of sedimentation of powders was determined
after 72 hours. Hydrophilic coefficient was determined by the ratio of the sedimented
particle volume in water to petroleum. Table 2 shows the results of hydrophilic test.
According to the hydrophilic coefficient test, limestone, aluminum dross and brick
powder are hydrophobic (η<1), while concrete powder is hydrophilic (η>1). The
three hydrophobic materials are able to generate a good relation with the binder, but
concrete powder is harder to create the good contact with bitumen. The optimal
hydrophilic factor is in the range of 0.7-0.85. As can be seen in the Table 2 that the
dross and brick powder have the optimal hydrophilic coefficient.
German Filler Test
German Filler Test is a method to reveal the oil adsorption capacity of powders. It
can be used to determine the cohesion between filler and bitumen through the oil
content. During the method oil fills the interparticle voids. The method is the
following (Fig 3.): 15 grams of oil hydraulic was mixed together with 45 grams of
filler. A ball was made from this mixture, and then another 5 grams of powder was
added to the mix and was thoroughly kneaded. The result is the amount of absorbed
powder.
Table 2 Hydrophilic coefficient of fillers Table 3 Results of German Filler Test
Hydrophilic Amount of dry
Fillers coefficient Fillers materials
[-] [g]
Limestone 0,59 Limestone 50
Aluminum dross 0,74 Aluminum dross 45
Brick powder 0,79 Brick powder 65
Concrete powder 1,21 Concrete powder 95
Fig. 3 Method of German Filler Test
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It can be concluded, that dross has the lowest value than the other three materials
however dross is very similar to limestone. Concrete powder and brick powder are
able to absorb higher amount of dry materials, so they have higher interparticle
voids, and can absorb higher amount of oil. This property is undesirable in road
construction, because of the higher bitumen consumption.
Conclusion
During the research work aluminum dross, brick powder and concrete powder were
investigated as a potential asphalt filler. The powders were analysed in order to
reveal their chemical elemental composition. According to scanning electron
microscopy tests it can be concluded, that all the powders have similar geometrical
features, which are desired in asphalt technology. The results of particle size
distribution tests are shown that all the powders have fine particles in a high amount,
especially limestone and concrete powder. Particle size distribution also effects on
the oil adsorption capacity. From this point of view concrete powder is not useful as
asphalt filler. Besides, concrete powder is hydrophilic material, therefore the use of
this material is not recommended. Taking into account the test results aluminum
dross and brick powder may be potential asphalt fillers. However, it should be noted
that standard asphalt tests are needed to confirm the usability of these waste
materials.
Acknowledgement: The described article was carried out as part of the EFOP-3.6.1-16-
2016-00011 “Younger and Renewing University – Innovative Knowledge City – institutional
development of the University of Miskolc aiming at intelligent specialisation” project
implemented in the framework of the Szechenyi 2020 program. The realization of this project
is supported by the European Union, co-financed by the European Social Fund.
References
[1] N. Ali, J. Chen, S. Simms et al.: Mechanistic evaluation fly ash asphalt concrete
mixtures, Journal of Materials in Civil Engineering, 1996, Vol. 8, p. 19-25,
https://doi.org/10.1061/(ASCE)0899-1561(1996)8:1(19)
[2] S. Likitlersuang, T. Chompoorat.: Laboratory investigation of the performances of
cement and fly ash modified asphalt concrete mixtures, International Journal of
Pavement Research and Technology, 2016, Vol. 9, p. 337-344,
http://dx.doi.org/10.1016/j.ijprt.2016.08.002
[3] K. Sobolev, I. F. Vivian, R. Saha et al.: The effect of fly ash on the rheological properties
of bituminous materials, Fuel, 2014, Vol. 116, p. 471-477,
http://dx.doi.org/10.1016/j.fuel.2013.07.123
[4] S. Wu, J. Zhu, J. Zhong et al.: Experimental investigation on related properties of
asphalt mastic containing recycled red brick powder, Construction and Building
Materials, 2011, Vol. 25, p. 2883-2887,
http://dx.doi.org/10.1016/j.conbuildmat.2010.12.040
[5] N. Bilgin, H. Yeprem, S. Arslan et al.: Use of waste marble powder in brick industry,
Construction and Building Materials, 2012, Vol. 29, p. 449-457,
http://doi.org/10.1016/j.conbuildmat.2011.10.011
[6] S. Bhusal, X. Li, H. Wen.: Evaluation of Effects of Recycled Concrete Aggregate on
Volumetrics of Hot-Mix Asphalt, Journal of the Transportation Research Board, 2011,
Vol. 2205, p. 36-39, http://doi.org/10.3141/2205-05
[7] M. Batayneh, I. Marie, I. Asi.: Use of selected waste materials in concrete mixes, Waste
Management, 2007, Vol. 27, p. 1870-1876, http://doi.org/10.1016/j.wasman.2006.07.026
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[8] J. M. Ried.: The use of alternative materials in road construction

https://www.viastrade.it/letteratura/materiali/TRL_TO_ALT_MAT.pdf Megtekintés ideje:
2018. 11. 25.
[9] E. Oluwasola, M. Hainin, M. M. R. Aziz.: Evaluation of asphalt mixtures incorporating
electric arc furnace steel slag and copper mine tailings for road construction,
Transportation Geotechnics, 2015, Vol.2, p. 47-55
http://dx.doi.org/10.1016/j.trgeo.2014.09.004
[10] F. Giustozzi, K. Mansour, F. Patti et al.: Shear rheology and microstructure of mining
material-bitumen composites as filler replacement in asphalt mastics, Construction and
Building Materials, 2018, Vol. 171, p. 726-735
https://doi.org/10.1016/j.conbuildmat.2018.03.190
[11] Z. Wang, C. Xu, S. Wang et al.: Utilization of magnetite tailings as aggregates in asphalt
mixtures, Construction and Building Materials, 2016, Vol. 114, p. 392-399
http://dx.doi.org/10.1016/j.conbuildmat.2016.03.139
[12] J. Xie SW, L. Pang, J. Lin, Z. Zhu.: Influence of surface treated fly ash with coupling
agent on asphalt mixture moisture damage, Construction and Building Materials, 2012,
Vol. 30 p. 340-346 https://doi.org/10.1016/j.conbuildmat.2011.11.022
[13] H. Yi, G. Xu, H. Cheng, J. Wang, Y. Wan, H. Chen.: An overview of utilization of steel
slag, Procedia Environmental Sciences, 2012, Vol. 16. p. 791-801
[14] G. Mailar, S. Raghavendra N, Sreedhara B.M, Manu D.S, P. Hiremath, Jayakesh K.:
Investigation of concrete produced using recycled aluminium dross for hot weather
concreting conditions, Resource-Efficient Technologies, 2016, Vol. 2, p. 68-80
https://doi.org/10.1016/j.reffit.2016.06.006
[15] P.E. Tsakiridis.: Aluminium salt slag characterization and utilization, Journal of
Hazardous Materials, 2012, Vol. 217-218, p. 1-10,
http://dx.doi.org/10.1016/j.jhazmat.2012.03.052
[16] Y. Guo, J. Xie, W. Zheng, J. Li: Effects of steel slag as fine aggregate on static and
impact behaviours of concrete, Construction and Building Materials, 2018, Vol, 192, p.
194-201, https://doi.org/10.1016/j.conbuildmat.2018.10.129
[17] M. Ahmaruzzaman.: A review on the utilization of fly ash, Progress in Energy and
Combustion Science, 2010, Vol. 36, p. 327-363
[18] R. Mistry, T. Roy.: Effect of using fly ash as alternative filler in hot mix asphalt,
Perspectives in Science, 2016, Vol. 8, p. 307-309
http://doi.org/10.1016/j.pisc.2016.04.061
[19] Chen, M., Lin, J., Wu, S. et al. (2011) Utilization of recycled brick powder as alternative
filler in asphalt mixture. Construction and Building Materials. Vol. 25, April 2011, pp.
1532-1536, http://dx.doi.org/10.1016/j.conbuildmat.2010.08.005
[20] Aliabdo, A., Hassan, H. (2014) Utilization of crushed clay brick in concrete industry.
Alexandria Engineering Journal. Vol. 53, March 2014, pp. 151-168,
http://dx.doi.org/10.1016/j.aej.2013.12.003
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CONVERSION OF BATCH-TO-GLASS ANALYSIS: APPLICATION

TO NUCLEAR WASTE
1,2 1 1 2
Miroslava Hujová , Jaroslav Kloužek , Richard Pokorný , Jozef Kraxner
1)
Laboratory of Inorganic Materials, Joint Workplace of the University of Chemistry
and Technology Prague, Technická 5, 166 28 Prague 6, and the Institute ofRock
Structure and Mechanics of the ASCR, vvi., V Holešovičkách 41, 182 09 Prague 8,
Czech Republic
2)
Department of Glass Processing, FunGlass,
Alexander Dubček UniversityofTrenčín, 911 01 Trenčín, Slovakia
e-mail: miroslava.hujova@tnuni.sk
Vitrification of nuclear waste, the process during which a waste feed is converted into a glass,
is a complicated technology consisting of many important processes. One of them is
the batch-to-glass conversion process itself, which takes place in a conversion layer called
the cold-cap. Formation of the cold-cap has been left unexplained for a long time. In this
report we explain the beginnings of conversion layer formation via the application of X-Ray
fluorescence (XRF). The cold-cap forms from a thin starting layer that self-promotes through
the entire volume, despite what would have been expected when looking at the chemistry of
the slurry feed. This mechanism influences the arrangement of the batch components in the
formed layer, and, therefore, the whole process of conversion.
Keywords: vitrification, cold-cap, X-ray fluorescence
Introduction
Nuclear waste in the Hanford Area is one of the largest environmental issues in the
Western hemisphere [1]. This waste is currently in the form of a suspension that is
stored inside of 177 underground, concrete-reinforced steel tanks. As these tanks
are ceasing to be reliable, and many leaks have happened in recent history, the
waste must be stabilized, in the form of glass, via a process called vitrification.
During this process, the waste is first divided into two main streams based on
composition: the high-level waste stream, HLW, which contains 95 % of the
radioactivity and the low activity waste stream, LAW, which is 90 % of the waste
volume. Then, the waste is mixed with glass forming and modifying additives and
fed, from the top, into a Joule-heated ceramic melter, which contains pre-heated
glass. As the liquid waste comes into contact with the molten glass, an interface is
formed. This interface is the conversion layer called the cold-cap [2].
In the past, the cold-cap phenomenon was investigated for different purposes and
properties. McCarthy et al. [3] described that the cold-cap could be separated into
four parts: (i) area of the liquid feed, (ii) the main cold-cap body, (iii) the foam layer,
(iv) the molten glass layer. These layers, or regions, and their main properties are
provided in Figure 1 with respect to their placement within the cold-cap.
Jahodná, Slovakia
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CONVERSION OF BATCH-TO-GLASS ANALYSIS: APPLICATION TO NUCLEAR WASTE
M. Hujová, J. Kloužek, R. Pokorný, J. Kraxner
Fig. 1 Regions within cold-cap first described by McCarthy et al. [3], and their main properties
Processing of the cold-cap is not always as straightforward as batch-to-glass

conversion processes used in the commercial glass making industry. The high
concentrations of volatile components, that are both toxic and radioactive, present in
the feed demand that the surface of the molten glass be fully covered during the
vitrification process in order to lessen the evaporation of harmful components into
the atmosphere [4]. However, several pilot melter runs report the formation of
uneven cold-caps, characterized by ridges and molds, that prevent fresh slurry from
spreading across the melter and instead piles on itself to create too high of cold-
caps which are surrounded by exposed molten glass pools [1].
This study discusses how the waste slurry chemistry can affect the formation of
faulty cold-caps and explains it by mimicking the cold-cap formation process under
laboratory conditions and by subsequent XRF analysis of the retrieved,
representative pieces.
Experimental
Slurry feed preparation
The feed used for this study was chosen from a series of HLW feeds (composition
provided in Table 1).
Table 1 Feed composition (in g) to make 1 kg of glass.
Compound Mass (g) Compound Mass (g)
Al(OH)3 371.79 Ni(OH)2 5.03
H3BO3 341.59 PbO 4.17
CaO 10.87 Fe(H2PO2)3 12.51
Fe(OH)3 74.38 NaF 15.00
Li2CO3 89.22 Na2CO3 106.57
NaOH 19.87 NaNO2 3.48
SiO2 221.45 NaNO3 12.40
Zr(OH)4∙0.65H2O 5.53 Na2C2O4 1.26
Na2SO4 3.60 CaSiO3 97.07
Bi2O3 11.67
Cr2O3∙1.5H2O 6.20 Total 1413.66
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The waste feed was prepared, as described in Schweiger et al. [5], by mixing the
chemicals in deionized water. To prepare feed with a tracer, 3 wt.% of
Na2WO4·9WO3 (sodium polytungstate, SPT) was added to the slurry.
Laboratory cold-cap formation
In waste glass melters, the slurry water evaporates either as it flows over the cold-
cap surface or deep boiling pools that are in different locations across the cold-cap
surface [1]. To replicate the conditions that occur during cold-cap formation in the
laboratory, we used 500 ml of HLW slurry, which was periodically poured 5-times in
100 ml aliquots into a circular aluminum-foil-lined mullite mold (10.5 cm in diameter).
This process prevented the feed from foaming out of the mold, which would have
happened if it was added all at once since the cold-cap formation involves vigorous
boiling of feed. The mold was heated on a hot plate (615 W max.) and did not
exceed 400 °C during the experiments. This method produced laboratory cold-cap
samples with a similar morphology (microstructure, open porosity, density) to
quenched cold-cap samples from a laboratory-scale melter as described by
McCarthy et al. [3] and Hujova et al. [2].
To determine the water content during cold-cap formation, surface subsamples were
taken and weighed before and after they were dried for 24 h in an oven at 105 °C.
To observe water spreading on the surface of the prepared laboratory cold-cap, and
to evaluate potential slurry-cold-cap intermixing, once the dry cold-cap sample was
prepared, 200 ml of slurry with SPT was poured onto the top of the sample and was
left to evaporate [6].
To analyze the produced laboratory cold-cap samples, selected elements were
measured with μ-XRF. Data were acquired using an Orbis PC μ-XRF analyzer
(EDAX, Inc., USA). The analyzer was equipped with a Mo reflection X-ray source
and silicon drift detector. All standard maps were acquired under the following
conditions: 30 kVp, 500 A, 3.2 μs amplifier, unfiltered beam, 30 m polycapillary
optic, ~120 m dwell spacing, and a 2 s dwell time. Optical images were acquired
with a Canon CanoScan 9000F flatbed scanner.
Results
Figure 2 shows the water content and visual appearance of a HLW laboratory cold-
cap at different times of sample formation. Immediately after the slurry was poured
into the mullite mold the cold-cap formation started by the vigorous boiling of feed.
During most of the cold-cap formation, the slurry feed was boiling and had a low
viscosity, but, around the 80th minute, the slurry began to thicken at the surface of
the sample. However, by inserting a stainless steel pick, it was found that a self-
promoting thin layer at the bottom of the mold was formed and was consequentially
spreading towards the surface. Once the slurry turned into thick mud from time 80-
100 min, vent-holes could be observed. Finally, at time 120 min, the HLW laboratory
cold-cap was fully dry with a cracked surface containing frozen vent-holes.
Jahodná, Slovakia
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a)
b)
Fig. 2 HLW cold-cap formation a) water content and b) visual observations with respect to
time
Figure 3 shows µ-XRF elemental scans for the laboratory cold-cap sample, into
which the tracer, SPT, was introduced with the second round of slurry pouring, after
the base cold-cap layer was dry. µ-XRF elemental maps suggest a random
distribution for most of the batch components. Tungsten, the element unique for the
tracer, was present only in the upper layer of sample. Na and P, water-soluble
elements demonstrate the formation of a concentration gradient from the present hot
surfaces (hot plate, dry sample surface) to the later formed parts of laboratory cold-
cap.
Figure 4 shows quantitative results obtained via µ-XRF from the laboratory cold-cap
sample. These results are in the agreement with the qualitative data. The elements
from glass forming chemicals and metal oxides are either distributed evenly or in
clusters, but always in a rather random fashion. On the other hand, present alkalis
(Na) and other water-soluble components (P) demonstrate the formation of a
concentration profile from the hot surfaces (hot plate or dry hot sample surface). The
tracer element, W, was not measured due to a missing standard for the analysis.
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Fig. 3 Optical image of HLW laboratory cold-cap sample and the respective µ-XRF
elemental maps for the batch components
Fig. 4
Quantitative µ-XRF
results for the
measured elements
in the direction from
the bottom of the
sample (0 mm)
towards its surface
(16 mm) The grey
zone illustrate the
interface layer with
the SPT tracer
Jahodná, Slovakia
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Discussion
The final HLW laboratory cold-cap, shown in Figure 5 b, resembles a rock, with
a denser material at the bottom of the sample (in the lower box) and with porous,
open-channelled structure at the top of the sample (the upper box). This structure is
well-corresponding to that of the actual cold-cap retrieved from laboratory scale
melters (Figure 5 a).
a)
b)
Fig. 5 a) Laboratory scale melter cold-cap, b) laboratory cold-cap. The upper boxes highlight
the high porosity part of the material. The lower boxes show the denser part of the
cold-cap body
The formation of a laboratory HLW cold-cap starts with a solidifying layer of feed
near the hot plate surface. This layer is then self-promoting throughout the entire
system, until it forms a cold-cap structure that resembles a rock (Figure 5). This
layer is present for all HLW cold-cap formation cases, despite the fact that, in
general, HLW slurries contain a high amount of water (up to 65 wt.% [1]) and
therefore, the sudden solidification) of the slurry pool would be the more probable
way of a cold-cap formation.
The solidification from the bottom of the boiling pool results in the concentration
gradient of alkalis. The mechanism suggested counts with the over-heating of the
“original” dry cold-cap layers, and the consequential drainage of molten salts during
the cold-cap formation. This results in a relatively alkali-rich cold-cap bottom (up to
30 wt.% of Na concentration), and an alkali-poor top, cold-cap (5 wt.% of Na,
compared to the 10 wt.% of Na as-batched). Furthermore, as observed and
suggested by Xu Kai [7], [8], the presence of sodium within the feed is always
connected to boron and lithium, as these elements are forming a preferential borate
phase. Despite the fact that our analytical method did not allow us to detect these
elements, previous studies performed on this topic can serve as a reliable proof.
The drainage of molten salts could explain the feed-to-glass conversion issues that
were observed during the pilot melter experiments. Some reports describe the
formation of ridges and molds, which prohibited spreading of the slurry across the
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surface of the glass-melt [1]. These structures, besides causing exposed molten
glass surfaces in the melter, seemed to convert into glass at a slower rate. This
could be caused by the observed drainage of molten salts towards the bottom of the
cold-cap. The separation of alkalis would leave behind the refractories present in the
HLW feed, which alone can only turn into melt very slowly at the melter operating
temperatures (1150 °C). Another effect of high alkali concentrations is the higher
foam evolution at the bottom of the cold-cap that acts as the insulating layer within
the one-dimensional heat transfer environment in which the cold-cap formation takes
place [9].
Conclusion
We replicated the conditions of cold-cap formation in a slurry-fed vitrification melter
by pouring a slurry feed simulant into a cylindrical mold heated from below. We used
a sodium polytungstate tracer to show that the slurry negligibly penetrated, or mixed
with, the previously formed hot, dry cold-cap. However, we observed the alkali
gradient within the obtained samples.
Both the fact that the slurry does not mix with the previously dried cold-cap crust,
and that water evaporates directly on the cold-cap’s top surface, can explain some
of the phenomena previously observed during the pilot tests. The explanation and
understanding of these phenomena opens up the possibility of avoiding some of the
cold-cap processing issues and securing a smooth feed-to-glass conversion
process.
Acknowledgements: This work was supported by the U.S. Department of Energy’s Waste
Treatment & Immobilization Plant Project of the Office of River Protection. Pacific Northwest
National Laboratory is operated for the Department of Energy by Battelle Memorial Institute
under contract DE-AC05-76RL01830. Miroslava Hujova acknowledges financial support from
specific university research (MSMT No 20-SVV/2018).
This paper is also a part of dissemination activities of the project FunGlass. This project has
received funding from the European Union´s Horizon 2020 research and innovation program
under grant agreement No 739566.
References
[1] K. S. Matlack, H. Gan, M. Chaudhuri, W. Kot, W. Gong, T. Bardakci, I. L. Pegg, and J.
Innocent, “DM100 and DM1200 Melter Testing with High Waste Loading Glass
Formulations for Hanford High-Aluminum HLW Streams, VSL-10R1690-1,” Vitreous State
Laboratory, The Catholic University of America, Washington, DC, 2010.
[2] M. Hujova, R. Pokorny, J. Klouzek, D. R. Dixon, D. A. Cutforth, S. Lee, B. P. McCarthy, M.
J. Schweiger, A. A. Kruger, and P. Hrma, “Determination of heat conductivity of waste
glass feed and its applicability for modeling the batch-to-glass conversion,” J. Am. Ceram.
Soc., vol. 100, no. 11, 2017.
[3] B. P. McCarthy, J. L. George, D. R. Dixon, M. Wheeler, D. A. Cutforth, P. Hrma, D. Linn,
J. Chun, M. Hujova, A. A. Kruger, and R. Pokorny, “Rheology of simulated radioactive
waste slurry and cold cap during vitrification,” J. Am. Ceram. Soc., vol. 101, no. 11, pp.
5020–5029, Nov. 2018.
[4] J. S. McCloy, B. J. Riley, A. Goel, M. Liezers, M. J. Schweiger, C. P. Rodriguez, P. Hrma,
D. S. Kim, W. W. Lukens, and A. A. Kruger, “Rhenium solubility in borosilicate nuclear
Jahodná, Slovakia
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waste glass: Implications for the processing and immobilization of technetium-99,”

Environ. Sci. Technol., vol. 46, no. 22, pp. 12616–12622, 2012.
[5] M.J. Schweiger, P. Hrma, C. J. Humrickhouse, J. Marcial, B. J. Riley, and N. E.
TeGrotenhuis, “Cluster formation of silica particles in glass batches during melting,” J.
Non. Cryst. Solids, vol. 356, p. 1359, 2010.
[6] M. Hujová, J. Klouzek, D. A. Cutforth, S. Lee, M. D. Miller, B. McCarthy, P. R. Hrma, A. A.
Kruger, and R. Pokorný, “Cold-cap formation from a slurry feed during nuclear waste
vitrification,” Ceram. Int., vol. 45, no. 5, pp. 6405–6412, Apr. 2019.
[7] K. Xu, P. Hrma, J. A. Rice, M. J. Schweiger, B. J. Riley, N. R. Overman, A. A. Kruger, and
E. Vance, “Conversion of Nuclear Waste to Molten Glass: Cold-Cap Reactions in
Crucible Tests,” J. Am. Ceram. Soc., vol. 99, no. 9, pp. 1–7, 2016.
[8] K. Xu, P. Hrma, J. Rice, B. J. Riley, M. J. Schweiger, and J. V. Crum, “Melter Feed
Reactions at T ≤ 700°C for Nuclear Waste Vitrification,” J. Am. Ceram. Soc., vol. 98, no.
10, pp. 3105–3111, 2015.
[9] S. Lee, P. Hrma, J. Kloužek, R. Pokorny, M. Hujová, D. R. Dixon, M. J. Schweiger, and A.
A. Kruger, “Balance of oxygen throughout the conversion of a high-level waste melter feed
to glass,” Ceram. Int., vol. 43, no. 16, 2017.
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PREPARATION OF LIGHTWEIGHT AGGREGATES FROM INDUSTRIAL

WASTE
Roman Bystrický, Miroslav Hnatko, Jaroslav Sedláček

1
Institute of Inorganic Chemistry - Slovak Academy of Sciences, Dúbravská cesta 9,
84104 Bratislava, Slovakia.
e-mail: roman.bystricky@savba.sk
Lightweight aggregates were synthesized from waste from steel and ferrosilicon production.
They were sintered at 1250 °C in Ar atmosphere to form SiC and liquid phase which help to
partially densify the aggregate. XRD analysis showed that the aggregate contains mainly SiC
-3
and aluminosilicates. The density of prepared aggregate was 1.253 g.cm and the
compressive strength was 5.13 MPa.
This approach provides a new opportunity to transform steel and ferrosilicon industrial waste
into a value added material for the production of lightweight aggregates for industrial
application.
Keywords: waste, lightweight aggregates, concrete
Introduction
Lightweight aggregates (LWAs) are granulated materials formed during the high-
temperature processing of mineral components, both raw and by-products, at
temperatures below 1300°C.
Due to the high porosity, lightweight aggregates are characterized by a low particle
–3 –3
density (ρ ≤ 2 g.cm ) and low loose bulk density (ρb ≤ 1.2 g.cm ) (STN-EN-13055).
These properties are followed by relatively better insulation properties compared to
natural aggregates, favors the use of LWAs in e.g., the building industry, road
construction, marine, and floating structures. The implementation of these highly
porous structures as construction and building materials, improve the thermal and
acoustic insulation properties of the final material [1].
The current state of knowledge indicates the applicability of different types of
secondary materials as possible substrates for the manufacturing of LWA-s. In
addition to the commonly used substrates for LWA production (clays and fly ash),
various types of wastes as alternative materials can be used. Moreover, with the
decreasing resources of high-bloating clays, the application of the raw materials
and/or waste in lightweight aggregate technologies is particularly relevant. It has
been shown that LWAs can be produced from waste sludge [2] and contain heavy
metals [3]. There are also reports about the application of additives, such as
polyethylene terephthalate bottles [4], paper sludge [5] or bottom and industrial
sediments [6]. The various type of wastes from metallurgy [7-9], mining (burned
and unburned shale, and other rocks) [10, 11] and power production (fly ash and
slag) [12-15] were also applied.
Jahodná, Slovakia
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25 -27 June, 2019 33
PREPARATION OF LIGHTWEIGHT AGGREGATES FROM INDUSTRIAL WASTE
R. Bystrický, M. Hnatko, J. Sedláček
The aim of this work was to prepare of LWA-s from waste from steel and ferrosilicon
production. Possibilities of SiC formation in the LWA-s were also studied. The final
density and compressive strength was monitored.
Experimental
In this study, waste with high amount of Si and Al produced in steel industry (USS),
waste with high amount of Si produced in ferroalloys industry (CaSi), carbon black
2 -1
(pigment grade, 1000 m .g ) were used as starting materials. The composition of
wastes is shown in Table 1.
Table 1 Major oxides in industrial waste in mass%

Waste Fe2O3 Al2O3 SiO2 MnO CaO K2O MgO
USS 3.98 32.69 51.37 – 1.60 3.33 1.88
CaSi – 1.03 75.33 1.52 17.5 0.58 1.52
4 different compositions were prepared from wastes (Tab. 2).
Table 2 Composition of starting mixtures

Sample WUSS6 [%] WCaSi [%] WC [%]
USS-CaSiC10 90.0 6.88 3.12
USS-CaSiC30 70.0 20.6 9.34
USS-CaSiC50 50.0 34.4 15.6
The powder mixtures were homogenized in homogenizer Dr.Fritsch PM10 at 80rpm

for 1hour.
Pellets were prepared using uniaxial pressing at 100 MPa.
Granules were made using disc granulator, where water with 2 mass% of sugar was
used as humidifier. The diameter of prepared granules varied from 3 to 5 mm.
Samples were heated at temperatures between 1200 and 1500 °C for 1 hour in Ar
atmosphere in graphite furnace (KCE-FP W100, FCT Systeme GmbH).
The densities of the samples were measured by Archimedes method in mercury.
The crystalline phases present in the heat treated samples were identified using X-
ray diffraction (XRD) (Panalytical Empyrean, Netherlands, Cu Kα radiation). Photos
were made by camera (Canon PowerShot SX520 HS). Compressive strength was
measured on universal testing machine (Lloyd instruments Lr5k plus).
Results
The formation of SiC is needed to achieve the high compressive strength of
prepared LWA-s. But densification of SiC is possible only in the presence of liquid
phase at temperatures below 1500 °C. With suitable ratio of main phases present in
the waste (SiO2, Al2O3, CaO) liquid phase can be reached at temperatures below
1500 °C according to ternary phase diagram of SiO 2-Al2O3-CaO [16]. For that
reason 3 different ratios of wastes were prepared. Carbon was added into the
mixtures for in situ preparation of SiC according to the reaction 1.
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L4
SiO2(s) + 3C(s) → SiC(s) + 2CO(g) (1)

Several experiments were done in the system USS-CaSi-C. The experiments were
done in the range of temperatures from 1200 °C to 1500 °C. First experiments were
carried out at 1500 °C. It was necessary to determine if it is possible to create the
SiC in the system where two wastes mixed with carbon black are used as starting
materials. The second reason was to determine if the system is able to partially
densify to increase the compressive strength of the samples.
First samples were made as pressed pellets with diameter of 12 mm.
The view of the samples after experiment at 1500 °C is on the photos (Fig. 1). As it
can be seen, the USS-CaSiC10 and USS-CaSiC30 were completely melted at this
temperature. USS-CaSiC50 was melted only partially.
a) b) c)
Fig. 1 Photos of a) USS_CaSiC10, b) USS_CaSiC30, c) USS_CaSiC50 after heat
treatment at 1500 °C
XRD patterns showed, that in the samples SiC, aluminosilicates are the main
components; Al2O3, Fe and SiO2 are present as minor phases (Tab. 3).
Melting of samples at 1500 °C confirm that in the samples can form a liquid phase
which can help to densify the samples with SiC formed.
Table 3 Phase composition of the samples after heat treatment at 1500 °C
Samples Phases determined by XRD

USS-CaSiC10 Al4.7Si1.3O9.7, Al2O3, C, SiC
USS-CaSiC30 Fe, Al4.7Si1.3O9.7, Al2O3, C, SiC
USS-CaSiC50 Fe, CaSi2Al2O4, SiO2, C, SiC
In the next experiments only USS_CaSiC10 and USS_CaSiC30 samples were used.
Experiments were carried out at temperatures between 1200 and 1500 °C to find the
lower temperature where liquid phase is formed in the sample. The lowest
temperature for USS_CaSiC10 was 1400 °C and for USS_CaSiC30 1200 °C. In the
Figure 2 it is shown that the sample (USS_CaSiC30) broke down during heating due
to CO gas released when SiC was formed according to the reaction 1.
XRD pattern was measured on this broken sample which confirmed the presence of
SiC, aluminosilicates, FeO, Fe3Si and SiO2 in the sample.
Jahodná, Slovakia
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PREPARATION OF LIGHTWEIGHT AGGREGATES FROM INDUSTRIAL WASTE
R. Bystrický, M. Hnatko, J. Sedláček
In next step granules were made from waste powder mixture to prepare LWA-s. It
was needed to test if prepared granules remain their shape during heating when CO
gas is released from them. The result is shown in the Figure 3. Granule remained
spherical shape but it had low strength and broke down during manipulation by
hand.
Fig. 2 The photo of USS-CaSiC30 after Fig 3 The photo of prepared granule USS-
heat treatment at 1200 °C CaSiC30 after heat treatment at
1200°C
Granules were then heat treated at 1220 °C and at 1250 °C where better strength
was achieved (Tab. 4). This can be explained by decreasing of viscosity of liquid
phase which allowed the better arrangement of SiC particles in the granules and
thus increase the density of prepared granules.
Table 4 Density and compressive strength of granules prepared at different temperatures

–3
Temperature ρ [g.cm ] Compressive strength [MPa]
1200 °C 1.134 2.84 ± 1.28
1220 °C 1.197 4.45 ± 1.96
1250 °C 1.253 5.13 ± 1.16
Conclusion
Lightweight aggregates were synthesized from industrial waste. XRD analysis
showed that the aggregate contains mainly SiC and aluminosilicates. The density of
–3
prepared aggregate was 1.253 g.cm and the compressive strength was 5.13 MPa.
There is a potential to increase the density and thus the strength in the next
experiments.
This approach provides a new opportunity to transform steel and ferrosilicon
industrial waste into a value added material for the production of lightweight
aggregates for industrial application.
Acknowledgment: This work was financially supported by the Slovak Grant Agency VEGA
Project No. 2/0152/18, APVV-15-0540 and CERANEA (Multifunctional Ceramic/Graphene
Coatings for New Emerging Applications). This work is also the result of the project
implementation: Effective control of production and consumption of energy from renewable
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L4
sources (ITMS code 26240220093) supported by the Research & Development Operational
Programme funded by the ERDF
References
[1] Nadesan, M. S., Dinakar, P., 2018. Influence of type of binder on high- performance
sintered fly ash lightweight aggregate concrete. Construct. Build. Mater. 176, 665–675.
[2] Cheeseman, C.R., Virdi, G.S., 2005. Properties and microstructure of lightweight
aggregate produced from sintered sewage sludge ash. Resour. Conserv. Recycl. 45 (1),
18–30.
[3] Huang, S-Ch., et al., 2007. Production of lightweight aggregates from mining residues,
heavy metal sludge, and incinerator fly ash. J. Hazard. Mater. 144 (1–2), 52–58.
[4] Choi, Y.-W., Moon, D.-J., Chung, J.-S., Cho, S.-K., 2005. Effects of waste PET bottles
aggregate on the properties of concrete. Cement Concr. Res. 35 (4), 776–781.
[5] Liaw, C.-T., Chang, H.-L., Hsu, W.-Ch., Huang, C.-R., 1998. A novel method to reuse
paper sludge and Co-generation ashes from paper mill. J. Hazard. Mater. 58 (1–3), 93–
102.
[6] Laursen, K., White, T.J., Cresswell, D.J.F., Wainwright, P.J., Barton, J.R., 2006.
Recycling of an industrial sludge and marine clay as light-weight aggregates. J. Environ.
Manag. 80 (3), 208–213
[7] Maslehuddin, M., Sharif, Alfarabi M., Shameem, M., Ibrahim, M., Barry, M., 2003.
Comparison of properties of steel slag and crushed limestone aggregate concretes.
Construct. Build. Mater. 17 (2), 105–112.
[8] Wang, G., Wang, Y., Gao, Z., 2010. Use of steel slag as a granular material: volume
expansion prediction and usability criteria. J. Hazard. Mater. 184 (1–3), 555–560.
[9] Yang, Ch., Cui, Ch., Qin, J., 2015. Recycling of low-silicon iron tailings in the production
of lightweight aggregates. Ceram. Int. 41 (1), 1213–1221.
[10] de Gennaro, R., et al., 2005. Neapolitan yellow tuff as raw material for lightweight
aggregates in lightweight structural concrete production. Appl. Clay Sci. 28 (1–4), 309–
319.
[11] Mueller, A., Sokolova, S.N., Vereshagin, V.I., 2008. Characteristics of lightweight
aggregates from primary and recycled raw materials. Construct. Build. Mater. 22 (4),
703–712.
[12] Baykal, G., Döven, A. G., 2000. Utilization of fly ash by pelletization process; theory,
application areas and Research results. Resour. Conserv. Recycl. 30 (1), 59–77.
[13] Chen, H.-J., Wang, S.-Y., Tang, Ch.-W., 2010. Reuse of incineration fly ashes and
reaction ashes for manufacturing lightweight aggregate. Construct. Build. Mater. 24 (1),
46–55.
[14] Geetha, S., Ramamurthy, K., 2010. Environmental friendly technology of cold-bonded
bottom ash aggregate manufacture through chemical activation. J. Clean. Prod. 18 (15),
1563–1569.
[15] Kockal, N. U., Ozturan, T., 2011. Characteristics of lightweight fly ash aggregates
produced with different binders and heat treatments. Cement Concr. Compos. 33 (1),
61–67.
[16] Mao, H., Hillert, M., Selleby, M., Sundman, B., 2006. Thermodynamic Assessment of the
CaO–Al2O3–SiO2 System. J. Am. Ceram. Soc., 89 [1] 298–308.
Jahodná, Slovakia
th th
25 -27 June, 2019 37
SLOVMAG, A.S. LUBENÍK
ČLEN MAGNEZIT GROUP
VIAC AKO 60 ROKOV SKÚSENOSTÍ

s výrobou žiaromateriálov
STAVIVÁ
magnéziové, magnéziovo-spinelitické, magnéziovo-chromité,
magnéziovo-uhlíkové
HMOTY
dusacie, torkrétovacie, zásypové, malty, troskotvorné prísady,
opravárenské hmoty, kaustická magnézia
www.slovmag.sk marketing@slovmag.sk
L5
ELECTRICAL CONDUCTIVITY IN Ca DOPED LaAlO3 PEROVSKITES

PREPARED BY BALL MILLING
a b b
Martin Fabián , Blanca I. Arias-Serrado , Aleksey A. Yaremchenko ,
c,d d a
HristoKolev , Mária Kaňuchová , Jaroslav Briančin
a
Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, 40 01
Košice, Slovakia
b
CICECO-Aveiro Institute of Materials, Department of Materials and Ceramic
Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
c
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev St.,
Bldg.11, 1113 Sofia, Bulgaria
d
Technical University of Košice, Letná 9, 04200 Košice, Slovakia
e-mail: fabianm@saske.sk
The aim of the work is to show electrochemical properties including ionic/electronic transport
in mechanosynthesized Ca doped LaAlO3 perovskites. As-prepared powders and sintered
ceramics were characterized by XRPD, XPS and SEM. Electrochemical studies showed that
partial oxygen-ionic conductivity in prepared La1-xCaxAl 3-δ increases with calcium content up
-3 -1
to 10 at.% in the lanthanum sublattice and then levels off at ~6 ×10 S.cm at 900 °C.
La1-xCaxAlO3-δ ceramics are mixed conductors under oxidizing conditions and ionic
conductors with negligible contribution of electronic transport in reducing atmospheres.
Keywords Perovskite, LaAlO3, Conductivity, Solid electrolyte, Ball milling
Introduction
Solid oxide fuel cell (SOFC) technology is considered as one of the most promising
ways to generate electrical energy in the near future. The economic feasibility of fuel
cells is directly related to the decrease in operating temperature, which is
established mainly by the electrolyte’s properties. Thus, new electrolyte materials
operating at relatively low/intermediate (IT) temperatures have been investigated
extensively and perovskite-type materials are considered promising for electrolytes
in IT-SOFCs [1]. Recently, lanthanum metal oxides with a perovskite structure have
attracted much attention because of their possible application as electrode or
electrolyte materials for IT-SOFCs [2–4]. Recent results from literature point out that
structural properties, morphology of products and dopant concentration has great
influence on electric properties of LaAlO 3-based oxides [5–11]. Among perovskite
type ceramic materials doped with various elements, calcium-substitued lanthanum
aluminate (La1-xCaxAlO3-δ/LCAO) has been proposed as an attractive candidate for
IT-SOFC electrolyte [12].
To the best of our knowledge there are few papers describing synthesis of LaAlO 3.
In this context, the primary objective of this paper is to introduce a new preparation
method of Ca-substituted LaAlO3 nanoparticles via a mechanochemical route.
Although the mechanosynthesis of LaAlO3 has already been reported by Zhang and
Saito [13], it should be noted that the formation of desired compound has been
Jahodná, Slovakia
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25 -27 June, 2019 39
ELECTRICAL CONDUCTIVITY IN Ca DOPED LaAlO3 PEROVSKITES PREPARED BY BALL MILLING
M. Fabián, B.I. A.rias-Serrado, A. A. Yaremchenko, H. Kolev, M. Kaňuchová, J. Briančin
achieved after relatively long time of ball milling. Moreover, in our present study we
provide rapid mechanosynthesis and detailed structural study on as-prepared and
subsequently sintered Ca-substituted LaAlO3 samples.
Experimental part
Ca-substituted LaAlO3 powders were prepared by mechanochemical method. Solid
precursors, lanthanum oxide (La2O3, 99.9 % purity, Aldrich), aluminium oxide (Al2O3,
99.9 % purity, Aldrich) and calcium oxide (CaO, 99.9 % purity, Aldrich) were used for
the mechanosynthesis. For each composition, a mixture (5 g) of precursors taken in
appropriate proportions was milled for various times (up to 30 min) in a high-energy
3
planetary ball mill Pulverisette 6 (Fritsch, Germany). A grinding chamber (200 cm in
volume) and balls (10 mm in diameter) made of tungsten carbide were used. The
ball-to-powder weight ratio was 40:1. Milling experiments were performed in an
ambient atmosphere at 600 rpm. The as-prepared powders were pressed into
several disks of 16 mm diameter and 2 mm thickness at 270 MPa. Polyetheylene
glycol (PEG) 10 000 was used as a plasticizer. The pellets were sintered at 1450°C
for 12 h in air (except LaAlO3 sintered at 1700°C).
The structure of as-prepared powders and sintered samples was investigated by X-
ray powder diffractometry. XRPD patterns were collected using a D8 Advance
diffractometer (Brucker, Germany) with the Cu Kα radiation in the Bragg-Brentano
configuration. Rietveld analyses of XRPD data of the as-prepared and sintered
samples were performed in the space group Pm-3m using Fullprof computer
program. The morphology of the LCAO powders and sintered pellets were observed
through a high resolution scanning electron microscopy (FE-SEM) (Mira III, Tescan,
Czech Republic). Total electrical conductivity () was determined by impedance
spectroscopy (Agilent 4284A precision LCR meter) using ceramic samples with
applied porous Pt electrodes.
Results
The formation of LaAlO3 was followed by XRPD. As it is shown in Fig. 1a the XRPD
pattern of the starting (unmilled) mixture is characterized by sharp diffraction peaks
corresponding to La2O3 and La(OH)3. After 3 min of intensive ball milling, the Bragg
reflections decrease in intensity and broadened. On the other hand, new Bragg
reflections belonging to LaAlO3 are formed. After 30 min all the diffraction peaks can
be attributed to the LaAlO3 only. XRPD patterns of mechanosynthesized
La1-xCaxAlO3-δ (0 ≤ x ≤ 0.2) solid solutions are shown in Fig. 1b. The effective
incorporation of calcium into the perovskite-type structure of LaAlO3 results in slight
shift of all characteristic XRPD reflections to the higher angular positions (lower
values of d spacing), indicating a lattice contraction of La1-xCaxAlO3-δ with increasing
2+
Ca content. XRPD patterns of La1-xCaxAlO3-δ (0 ≤ x ≤ 0.2) sintered at 1723 K in air
(not shown in the paper) revealed that perovskite phase is formed, even if
considerable amount of secondary phase (LaAl11O18, hexagonal S.G. P63/mmc), for
LaAlO3 without calcium is also present.
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L5
The study of the microstructure was carried out to estimate the density, shape and
size of the grains (Figs. 2a and 2b). The density of sintered pellets determined by
Archimedes method exceed 95 % of theoretical values (except to LaAlO 3; ρ = 67 %).
Fig. 1 a) XRPD patterns of the La2O3, La(OH)3 and γ-Al2O3 mixture milled for various times
(up to 30 min) illustrating the mechanochemical synthesis of the La 1-xCaxAlO3-δ solid
solutions; the milling times, tM, are shown in the figure; b) XRPD patterns
ofmechanosynthesized La1-xCaxAlO3-δ ((0 ≤ x ≤ 0.2)) solid solutions
Fig. 2 SEM images of the sintered pellets of La1-xCaxAlO3-δ for a)x = 0; b) x = 0.05
Theinsets show corresponding grain size distribution
The results of electrical measurements showed that undoped LaAlO 3 is an insulator

-1
with electrical conductivity as low as 3.4×10-5 S.cm at 900 °C in air (Fig. 3) and
-1
corresponding activation energy of 148 kJ.mol . These observations are generally in
Jahodná, Slovakia
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ELECTRICAL CONDUCTIVITY IN Ca DOPED LaAlO3 PEROVSKITES PREPARED BY BALL MILLING
M. Fabián, B.I. A.rias-Serrado, A. A. Yaremchenko, H. Kolev, M. Kaňuchová, J. Briančin
agreement with the literature data, although the reported conductivity values scatter
-6 -3 -1
in a wide range from 1.1×10 to 1.4×10 S.cm at 900 °C in air; this implies a
strong influence of the phase and elemental impurities, porosity and microstructural
characteristics.
Fig. 3 Temperature dependence of total electrical conductivity of La1-xCaxAlO3- δ ceramics

inair
Analysis of the impedance spectroscopy data showed that electrical properties of

mechanosynthesized La1-xCaxAlO3-δ ceramics at temperatures below ~800 °C are
dominated by the grain boundary resistivity (Fig. 4a).
Fig. 4 a) Temperature dependence of total, bulk and grain boundary conductivity of x = 0.10
ceramics in air;; b) Temperature dependence of bulk conductivity of La1-xCaxAlO3-δ
ceramics in the low-temperature range in air
Dotted lines are an extrapolation to higher temperatures
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L5
Grain boundary conductivity has a higher activation energy compared to the bulk
conductivity, and extrapolation indicates that the bulk contribution to the total
resistivity is predominant in the high-temperature range. Fig. 4b compares bulk
conductivities of La1-xCaxAlO3-δ ceramics at 330-680 °C. As for total conductivity,
bulk conductivity in this temperature range increases slightly with increasing calcium
content from 5 to 10 at.% in the A sublattice, and is essentially composition-
independent for x>10.
Conclusion
Ca doped LaAlO3 perovskites were synthesized by high-energy ball milling of initial
precursors. XRPD analyses showed formation of perovskite phase after 30 min of
high-energy ball milling. Sintering at 1450 °C resulted in dense ceramics with
relative density above 95 %. FE-SEM/EDX investigations indicated homogeneity of
the sintered samples with average cation composition very close to the nominal.
Substitution by calcium was found to increase the total electrical conductivity by 2-3
orders of magnitude compared to undoped LaAlO 3 in air. In La1-xCaxAlO3-δ (x =
0.05-0.20) series. The contribution of the grain boundaries to the overall
conductivity was revealed.
Acknowledgement: This work was supported by the Slovak Research and Development
Agency APVV (contracts SK-PT-18-0039 and 15-0438) and the Slovak Grand Agency
(contract No. 2/0055/19). BIAS and AAY would like to acknowledge financial support by the
FCT, Portugal (project CARBOSTEAM/POCI-01-0145-FEDER-032295) and project CICECO-
Aveiro Institute of Materials (FCT ref. UID/CTM/50011/2019), financed by national funds
through the FCT/MCTES and when appropriate co-financed by FEDER under the PT2020
Partnership Agreement.
References
[1] Malavasi, L., Craig Fisher, A.J., Saiful Islam, M., Chem. Soc. Rev.39 (2010) 4370.
[2] Chen, T.Y., Fung, K.Z., J Alloy Compd 368 (2004) 106.
[3] Fu, Q.X., Tietz, F., Lersch, P., Stöver, D., Solid State Ionics 177 (2006) 1059.
[4] Kilner, J.A., Barrow, P., Brook, R.J., Norgett, M.J., J Power Sources 3 (1978) 67.
[5] Nguyen, T.L., Dokiya, M., Wang, S., Tagawa, H., Hashimoto, T., Solid State Ionics 130
(2000) 229.
[6] Park, J.Y., Choi, G.M., Solid State Ionics 154 (2002) 535.
[7] Lybye D., Poulsen F.W., Mogensen, M., Solid State Ionics 128 (2000) 91.
[8] Villas-Boas, L.A., de Souza D.P.F., Mater. Res. 16 (2013) 982.
[9] Fu, Q., Tietz, F., Stöver, D., Solid State Ionics 177 (2006) 1819.
[10] Fung, K.-Z., Chen, T.-Y., Solid State Ionics 188 (2011) 64.
[11] Kuščer, D., Hanžel, D., Holc, J., Hrovat, M., Kolar, D., J. Am. Ceram. Soc. 84 (2001)
1148.
[12] Ishihara, T., Perovskite Oxide for Solid Oxide Fuel Cells, Springer Science+Business
Media, LLC 2009.
[13] Zhang Q., Saito, F., J. Am. Ceram. Soc. 83 (2000) 439.
Jahodná, Slovakia
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L6
TERAHERTZ TIME-DOMAIN SPECTROSCOPY OF THE BORON DOPED

ZnO MATERIALS
1 1 2 1,3
Daniel Furka , Samuel Furka , Mira Naftaly , Mária Čaplovičová ,
1,4
Marián Janek
1
Comenius University, Faculty of Natural Sciences, Ilkovičova 6, Mlynská dolina,
842 15 Bratislava, Slovak Republic
2
National Physical Laboratory, Hampton Rd, Teddington, Middlesex TW11 0LW,
United Kingdom
3
STU Centre for Nanodiagnostics, Slovak University of Technology, Vazovova 5
4
Slovak University of Technology, Faculty of Chemical and Food Technology
Radlinského 9, 812 37 Bratislava, Slovakia
e-mail: furkadaniel@gmail.com
Nanoparticles of Zinc Oxide doped with boron were prepared by co-precipitation hydrothermal
synthesis. Increasing amount of dopant can affect their morphology due to the different lattice
micro-stresses, what can lead to the changes in optical and dielectric properties. Optical and
dielectric properties are important parameters of prepared material, determining the possibility
of use in production of solar cells, optoelectronics and sensors. Most important parameters
describing optical behavior are refractive index and absorption coefficient. Time domain
terahertz spectroscopy was used to investigate far infrared optical response of doped ZnO
nanoparticles in present study. The aim of our work was to prepare and describe the method
of co-precipitation synthesis of boron doped ZnO nanoparticles and characterization of the
frequency dependent refractive index and absorption coefficient of prepared material based
on ZnO with different mol fraction of boron.
Keywords: Zinc oxide, Doping, THz-TDS, Far-infrared, ZnO, Boron.
Introduction
Zinc Oxide (ZnO) is an interesting semiconductor with valence band width in the
range of 3.1 eV - 3.3 eV [1,2]. Sufficient electromechanical response along with the
absence of the center of symmetry in the Wurtzite-like structure of ZnO leads to its
piezoelectric and pyroelectric properties. Improved electron conductivity due to the
presence of oxygen vacancies and disorders in the deposition of the zinc atom
causes improvement of electron conductivity. Doping means the incorporation of the
small amount of the atoms from adjacent group of elements that leads to
disturbances in its crystal lattice. The presence of small amount of boron in the ZnO
crystal lattice leads to the changes in electron density due to the incorporation of
B2O3 into the crystal lattice. The large exciton coupling energy (46 to 73 meV) allows
the utilization of ZnO in the production of optoelectronic components such as LED
diodes, lasers, biosensors [3]. Absorption of electromagnetic radiation and creation
of electrone hole pairs with defined life-times allows the use of ZnO nanoparticles as
a photocatalyst.
Jahodná, Slovakia
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TERAHERTZ TIME-DOMAIN SPECTROSCOPY OF THE BORON DOPED ZnO MATERIALS
D. Furka, S. Furka, M. Naftaly, M. Čaplovičová, M. Janek
The nanoparticle morphology can be influenced easily by presence of additives

during their synthesis [4]. Additives cause preferential crystal growth in a certain
crystallographic plane, but they are not incorporated into the nanoparticle structure.
Well-defined and doped ZnO nanoparticles with different morphology combined with
other supporting components such as clay nanolayers and/or organic dyes, can find
utilization in a gas sensing, photocatalytic or electronic applications. From these
reasons, the study of boron oxide as dopant on the resulting optical and dielectric
properties of ZnO was investigated as a possible electron donor component in the
solid phase structure.
Materials and Methods
For the production of pure and doped nanoparticles, hydrothermal synthesis was
used, using zinc acetate dihydrate (Zn(Ac) 2·2H2O) as starting ZnO precursor.
Hydrothermal synthesis allows to control the size of prepared nanoparticles by the
rate of precursor addition, by adjusting the concentrations of the components of the
synthesis mixture, by affecting the temperature and by synthesis time [5]. The basic
2-
building block of ZnO crystals is the complex anion [Zn(OH) 4] . The amount of this
-
anion in the reaction mixture depends on the concentration of OH ions during the
ligands exchange and the degree of hydrolysis of the organic precursor in solution
[4]. To modify the morphology of particles synthesized, the growth additive
triethylenetetraamine (TETA) was used in the reaction mixture. TETA as ligand
2+
molecule changes the coordination of Zn cations, which leads to a slow down
and/or hindering the ZnO growth along the crystallographic axis 𝑎 and 𝑏. The
crystals grow preferably in the direction of the crystallographic axis 𝑐 resulting in the
elongated-spindle-like particle morphology [6]. In the case of co-precipitation boron
doping of the ZnO nanoparticles during the synthesis, the boric acid was reported to
be suitable precursor substance in this hydrothermal reaction. [7]
During the synthesis two types of particle morphologies I) pseudohexagonal and II)
elongated-spindle-like nanoparticles were prepared. The boron concentrations
varied in reaction mixture and included pure un-doped nanoparticles used as
reference materials. The mol fraction 𝑥 of boron was increasing toward zinc at levels
of 0.5, 1.0, 5.0, 10.0, 15.0 and 20.0 molar %. Separated, washed and dried ZnO
nanoparticle powders were then cold pressed using isostatic pressure of 10 MPa.
Pressed pellets were sintered at 900°C for 2 hours using a temperature ramp of
-1
5°C.min for heating and cooling regime. Prepared pellets were used to determine
their crystal structures and morphology using RTG diffraction analysis (XRD), SEM
for micro structure visualization, infrared spectroscopy and Time domain terahertz
spectroscopy (THz-TDS) for determining the optical properties in far infrared regime.
Results and Discussion
The structure of pure ZnO nanoparticles was confirmed by RTG powder diffraction
analysis with typical diffractions at 2θ° corresponding to (hkl) for 37.30° (100),
40.38° (002), 42.56° (101), 52.24° (102), 56.06° (210), 66.94° (110), 74.72° (103),
82.58° (112). Diffraction pattern confirmed the expected Wurtzit-like structure of pure
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®
and boron doped ZnO using Match 3 software. Furthermore, in the boron doped
pseudo-hexagonal nanoparticles the shift of diffraction pattern with increasing boron
content towards the lower angles was found. This shift means that crystal lattice
may be expanded due to the micro-stresses of the ZnO unit cell, however in boron
doped elongated-spindle-like nanoparticles synthesized in the presence of TETA,
diffraction pattern shift toward higher angles with increasing boron content was
found. Opposite shift can point out on the opposite micro-stresses considered as a
possible compressing of the unit cell. Calculations of the lattice parameters and unit
®
cell volume were provided by Match 3 software.
−1
The IR spectrum shows a characteristic absorption band between 400cm and
−1
590cm due to two transverse stretching modes of ZnO according to the E2h
mode. This absorption peak can be split into two maxima correlate with TO-phonon
frequency and the LO-phonon frequency [8]. For the pseudo-hexagonal
−1
nanoparticles doped with boron, the absorption band at 551cm assigned to B(3)–
O deformations along with the absorption band at 879cm for B(3)–O symmetric
-1
vibration were found [8, 9]. The IR spectrum of elongated-spindle-like nanoparticles

−1
of ZnO doped with boron shows a characteristic absorption band between 400cm
−1
and 590 cm due to two transverse stretching modes of ZnO according to the E2h
-1
mode [8], one deformation mode of B(4) – O at 495 cm and one symmetric vibration
−1 -1
of B(3) – O [9]. The last two absorption bands at 3324 cm and 3563 cm were
assigned to the OH groups on the surface of ZnO. Absorption bands correlated to
the B2O3 included in Table, were described by Jun et al. [9]. Correlation to the
H3BO3 was not confirmed.
Based on results of the IR spectra shown in Table, it can be assumed the
incorporation of B2O3 into the crystalline phase of ZnO (Tab.1.).
Table 1 Absorption bands of pure and doped ZnO and Zn100-xBxO in FTIR
ZnO Zn100-xBxO H3BO3 B2O3
-1 -1 Zn-O Zn - O
410 cm – 490 cm
strong, wide strong, wide
-1 δ (B(4) – O) δ (B(4) – O)
495 cm
strong, wide strong, wide
-1 δ (B(3) – O) δ (B(3) – O)
551 cm
strong, narrow strong, narrow
-1
879 cm vsym (B(3) – O) vsym (B(3) – O)
-1
*885 cm strong, wide strong, wide
-1 -1
2900 cm –3700 cm Surface O – H Surface O – H
* Found slight, wider shift for like elongated - spindle –nanoparticles

** Grey – found in pseudo-hexagonal nanoparticles of doped ZnO
** Blue- Found in elongated-spindle-like nanoparticles of doped ZnO
Pellets of ZnO material were measured using THz-TDS. Frequency dependent

refractive index 𝑛(𝜔) and absorption coefficient 𝛼(𝜔) were calculated from obtained
transfer function. The average refractive index of material sintered from pseudo-
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hexagonal particles was in the interval from 2.61 to 2.66 with a standard deviation of
0.05 at 1THz (Fig. 1a). The averaged refractive index values of the pellets sintered
from the elongated-spindle particles was in the interval 3.34 to 3.38 with standard
deviation of 0.05 at 1 THz (Fig. 1b). This value differs significantly from material
prepared from pseudo-hexagonal nanoparticles. The refractive index of bulk ZnO
crystal is around 2.7 [10].
Pseudo-hexagonal nanoparticles Elongated-spindle nanoparticles

a) b)
(B2O3 / ZnO, x=0.200) 3.348 ± 0.0002 ( @ 1 THz ) (B2O3 / ZnO, x=0.200) 2.615 ± 0.0002 ( @ 1 THz )
(B2O3 / ZnO , x=0.150) 3.388 ± 0.0001 ( @ 1 THz ) (B2O3 / ZnO , x=0.150) 2.624 ± 0.0001 ( @ 1 THz )
nZnO
(B2O3 / ZnO, x=0.010) 3.349± 0.0002 ( @ 1 THz ) (B2O3 / ZnO, x=0.010) 2.617 ± 0.0001 ( @ 1 THz )
(B2O3 / ZnO , x=0.005) 3.382± 0.0002 ( @ 1 THz ) (B2O3 / ZnO , x=0.005) 2.619± 0.0002 ( @ 1 THz )
(Pure ZnO) 3.334 ± 0.0002 ( @ 1 THz ) (Pure ZnO) 2.643 ± 0.0001 ( @ 1 THz )
0.4 0.8 1.2 1.6 2.0 2.4 0.4 0.8 1.2 1.6 2.0 2.4
Frequency / THz Frequency / THz
Fig. 1 Frequency dependent refractive index of pure and doped ZnO material
Pure and boron doped pellets of ZnO based on the nanoparticles of pseudo-
hexagonal morphology showed a transparent behaviour in the THz region of
electromagnetic radiation (Fig. 2a).
Pseudo-hexagonal nanoparticles Elongated-spindle nanoparticles

30 15
(B2O3 / ZnO, x=0.200) (B O / ZnO, x=0.010) a) (B2O3 / ZnO, x=0.200) b)
2 3
(B2O3 / ZnO , x=0.150) (B2O3 / ZnO , x=0.005) (B2O3 / ZnO , x=0.150)
(B2O3 / ZnO , x=0.100) (Pure ZnO) (B2O3 / ZnO , x=0.100)
(B2O3 / ZnO , x=0.050)
24 12 (B2O3 / ZnO , x=0.050)
(B2O3 / ZnO, x=0.010)
(B2O3 / ZnO , x=0.005)
(Pure ZnO)
Alpha / cm-1
18 9
12 6
6 3
0 0
0.4 0.8 1.2 1.6 2.0 2.4 0.4 0.8 1.2 1.6 2.0 2.4
Frequency / THz Frequency / THz
Fig. 2 Frequency dependent absorption coefficient of pure and doped ZnO material
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Pure and boron doped pellets of ZnO based on the nanoparticles with elongated-
spindle-like morphology also showed the transparent behaviour in the THz region of
electromagnetic radiation (Fig. 2b). In a both samples, the absorption coefficient
𝛼(𝜔) gradually increased respective to the increasing frequency of THz waves.
These results indicate that the morphology and mol fraction of boron in the material
based on pure and boron doped ZnO nanoparticles can influence resulting optical
behaviour in desired manner (Fig. 3).
25
20
Alpha / cm-1
15
Hexagonal morphology
10
5
Elongated-spindle-like morphology
0
x=0% x=5% x=10% x=15% x=20%
Zn100-xBxO / %
Fig. 3 Absorption coefficient as a function of dopant concentration
Conclusion
The effect of boron doping on morphology, structural and optical properties of pure
ZnO and Zn100-xBxO nanoparticles synthesized by the hydrothermal synthesis was
investigated. In the same time, the effect of the presence of TETA additive during
the synthesis of ZnO nanoparticles on their resulting morphology and optical
properties in far infrared was shown.
Acknowledgements: We would like to express our gratitude to the Mgr. Erik Šimon for the
XRD measurements. We are thankful for the financial support of Grant for PhD students and
young UK researchers (UK/163/2017 and UK/403/2018).
References
[1] Klingshirn C. (2007): ZnO, Material, Physics and Applications. Chem. Phys. Chem., 8,
782-803.
[2] Han. J., Chen.W., Zhang.J., He M.X., Azad A.K., Ray S., Zhao Y. and Zhang W., (2008):
Piers Online, 4(3), 391-395.
[3] Meyer. B.K., et. al. (2004): Bound exciton and donor–acceptor pair recombinations in
ZnO, Phys. Stat. Sol., Vol:241b/pp.231– 260.
[4] Furka D. (2016): Hydrothermal synthesis of ZnO nanoparticles and their dielectric
properties in THz region (Diploma thesis) Comenius University in Bratislava, in Slovak.
Jahodná, Slovakia
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25 -27 June, 2019 49
[5] Zelechovska. K. (2014) Methods of ZnO nanoparticles synthesis, BioTechnologia, vol.

95(2)/ pp.150-159.
[6] Dag. S., Wang.S., Lin-Wang.W. (2011): Nano Letters, Vol. 11, 2348-2352.
[7] Senol. S. D., et al. (2015) Effect of boron doping on the structural, optical and electrical
properties of ZnO nanoparticles produced by the hydrothermal method, Ceramics
International, Vol 41/ pp. 11194–11201.
[8] S. Hayashi., N. Nakamori., H. Kanamori. “Generalized theory of average dielectric
constant and its application to infrared absorption by ZnO small particles,” Journal of the
Physical Society of Japan, vol. 46, no. 1, pp. 176–183, 1979.
[9] Jun., et al. (1995) FT-IR and Raman spectroscopic study of hydrated borates,
Spectrochimica Acta, Vol. 51A, No. 4, pp. 519-532.
[10] Bond, W., Measurement of the refractive indices of several crystals, J. Appl. Phys, Vol.
36/p1674-1677(1965).
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GLASSES IN THE PbO-Bi2O3-Ga2O3 SYSTEM WITH ADDITION OF Ag2O

AND Sb2O3 FOR ELECTRO-OPTIC LIGHT MODULATORS
1 1 2 1
Kristyna Jilkova , Martin Mika , Petr Kostka , Frantisek Lahodny ,
3
Richard Bures
1)
University of Chemistry and Technology, Department of Glass and Ceramics,
Technická 5, 166 28 Prague, Czech Republic
2)
Laboratory of Inorganic Materials, joint workplace of the University of Chemistry
and Technology Prague and the Institute of Rock Structure and Mechanics of the
CAS, V Holešovičkách 41, 182 09 Prague 8, Czech Republic
3)
University of Chemistry and Technology Prague, Department of Metals and
Corrosion Engineering, Technická 5, 166 28 Prague 6, Czech Republic
e-mail: Krisyna.Jilkova@vscht.cz
The key component for the construction of fast electro-optic light modulators operating in the
VIS and NIR parts of the spectrum is an optical material with a sufficiently high electro-optic
coefficient. The PbO-Bi2O3-Ga2O3 heavy-metal oxide glass system was selected as a suitable
and cost effective candidate material with high quadratic electro-optic (Kerr) coefficient. In
order to enhance electro-optic properties of the glass, silver and antimony oxides were added
into the system. Optical properties of two series of samples (with and without addition of
Ag/Sb) were investigated using the UV-VIS-NIR, FT-IR and M-line spectroscopy. The electro-
optic coefficients were measured using an electro-optic measurement system assembled in
our lab.
Keywords: heavy-metal oxide glass, electro-optic coefficients; electro-optic modulators
Introduction
Electro-optic (EO) modulators are photonic devices exploiting the EO effect caused
by a change of the refractive index induced by direct current or low-frequency
electric field applied to an optical material [1, 2]. If the refractive index changes in
direct proportion to the applied electric field, the (Pockels) EO effect is linear [1, 3].
The refractive index can also change in proportion to the square power of the
applied electric field, and in this case it is a non-linear/quadratic (Kerr) EO effect.
This effect becomes more important at higher electric field strengths. Fig. 1 (a)
shows schematically the Kerr EO effect. In transversal modulators (Fig. 1 (b)), the
electric field is applied perpendicularly to the direction of light propagation.
The most commonly used optical materials in EO modulators are inorganic EO
compounds such as NH4H2PO4 (ADP) [4], KH2PO4 (KDP) [5], LiNbO3 [3,6,7], LiTaO3
[8] and special polymers [9,10] exhibiting high linear Pockels coefficients. The
values of EO linear coefficient 𝑟 for several optical materials are shown in Table 1.
Crystalline optical materials showing high linear coefficients can be obtained in high
purity and homogeneity. Their main disadvantage is a limited shape forming
capacity. The use of specially poled organic polymers with EO coefficients an order
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GLASSES IN THE PbO-Bi2O3-Ga2O3 SYSTEM WITH ADDITION OF Ag2O AND Sb2O3 FOR ELECTRO-OPTIC
LIGHT MODULATORS K. Jilkova, M. Mika, P. Kostka, F. Lahodný, R. Bures
of magnitude higher than those of inorganic materials is limited by their lower

thermal stability, poor mechanical properties and/or faster material aging [11].
a) b)
Fig. 1 (a) Kerr effect (on the left); (b) transversal modulator (on the right)
Table 1 The values of linear EO coefficients for selected optical materials

EO coefficient 𝑟 For wavelength 𝜆
Optical material -12 -1
[10 m×V ] [nm]
r33 = 32.2
LiNbO3 [3] r22 = 6.81 633
r13 = 10.0
r41 = 22.2+/-0.2
632.8
r63 = 8.14+/-0.1
NH4H2PO4 (ADP) [4]
r41 = 22.9+/-0.2
488.0
r63 = 8.07+/-0.1
KH2PO4 (KDP) [5] r63 = 8.77+/-0.1 632.8
r33 = 30.5
LiTaO3 [8] 632.8
r13 = 8.14
LD-3 [9] r33 = 18 633
PMMA-AMA, BMI and AJC146 [10] r33 = 170 1550
Glasses are interesting for their ease of preparation and outstanding shape forming
capacity, low costs, good forming ability, good transmittance in the VIS and NIR
parts of the spectrum, high refractive index, and chemical durability. The EO Kerr
effect in glasses [2,12,13] has been already investigated in common glass systems
+
based on SiO2, such as SiO2-Na2O, SiO2-K2O or SiO2-PbO with and without Tl ,
5+ 5+
Nb , and Ta ions [2]. However, these glasses exhibit much lower non-linear (Kerr)
EO coefficient in comparison to the glasses containing heavy-metal oxides (HMO)
as follows from Table 2.
HMO glasses create a matrix suitable for incorporation of metal nanoparticles whose
presence leads to an increase of EO coefficients [12,13]. Electron shells of heavier
elements are easily polarizable, which makes them well responsive to the applied
electric field. The metallic nanoparticles embedded in the matrix makes the EO
response of the material even more sensitive. HMO glasses in the PbO-Bi2O3-Ga2O3
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system have a good glass-forming ability, high transmittance band from the visible
up to the mid-infrared region, and high refractive index [13].
Table 2 Non-linear EO coefficients for selected glass systems [2].

EO coefficient 𝑏 ×10
12 -2
Chemical composition (wt.%) [m×V ]
36SiO2-34Nb2O5-30Na2O -2.80
73SiO2-13Ta2O5-14K2O -0.57
76SiO2-9Tl2O-15K2O 0.30
54SiO2-41Tl2O-5PbO 0.96
60Tl2O-40SiO2 1.10
48PbO-14Bi2O3-10Ga2O3-14Tl2O-14CdO 1.40
In this work, base glasses in the PbO-Bi2O3-Ga2O3 system and those modified by
the addition of Ag2O and Sb2O3 were prepared and characterized. The optical
properties were measured using the UV-VIS-NIR, FT-IR and M-line spectroscopy
and the EO coefficients were measured using a self-assembled EO system.
Experimental and results
Base glasses in the 57.14 PbO – 17.86 Bi2O3 – 25.00 Ga2O3 system and newly
developed glasses with the addition of 0.42-1.22 Ag2O and 0.38-0.56 Sb2O3
(composition in mol.%) were prepared by conventional melt-quenching in a PtRh
crucible with a lid in an electric furnace at 1000 °C for 65 min. The melt was mixed
twice during melting – after 30 and 45 min. The glasses were cast into a preheated
(120 °C) stainless-steel mould and placed in mineral wool to slowly cool down to
room temperature. Samples were subsequently cut, ground and polished for optical
and EO measurements. The thickness of the samples for optical measurements was
6mm and the dimensions of prisms for EO measurements were 20.2±0.4mm in
length and 5.02±0.03 mm in height. As follows from transmittance measurements,
the investigated glasses are transparent from 550 nm to 7.4 µm (Fig. 2b).
Fig. 2 (a) transmittance of the samples PBG0,1,4 in the VIS part of the spectrum (on the left);
(b) transmittance of the PBG0,1,4 samples in the IR part of the spectrum (on the right)
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GLASSES IN THE PbO-Bi2O3-Ga2O3 SYSTEM WITH ADDITION OF Ag2O AND Sb2O3 FOR ELECTRO-OPTIC
LIGHT MODULATORS K. Jilkova, M. Mika, P. Kostka, F. Lahodný, R. Bures
The maximum transmittance of 75 % was found at 1 µm for the PBG0 base glass
without addition of Ag2O and Sb2O3 and the lowest transmittance of 34 % at 1 µm
was shown by the PBG1 glass with the highest amount of Ag2O (1.3 mol.%)
(Fig.2a).
The measured refractive index values of all glasses reach their maximum of 2.5 at
473 nm and decrease with increasing wavelength. The EO system for the
measurement of EO coefficients was designed and assembled in our lab – it
consists of a laser source (650 nm), a polariser, an analyser, a photodiode, an
amplifier, a high voltage source (5–30 kV), a signal generator, an oscilloscope and
a computer. Polarised light from the laser diode is passing through the measured
sample. Applied high voltage (5–30 kV) changes the refractive index of the sample
and the change in transmittance induced by the applied electric field is compensated
for by the rotation of the analyser. The EO coefficients b were calculated from the
measured rotation angle according to equations (1) and (2):
𝑉
𝐸=𝑑 (1)
𝑏 = 2𝛩/(𝜋𝑙𝐸 2 ) (2)
where 𝑉 is the voltage, 𝑑 is the distance between two electrodes, 𝐸 is the electric
field strength, 𝛩 is the angle of rotation of the analyser, 𝑙 is the length of optical path
(±0.01 mm) and 𝑏 is the EO coefficient.
The calculated values of EO coefficients 𝑏 varied from 7.47 for the PBG0 base glass
-12 -2
to 7.77×10 m×V for the PBG1 glass with the highest added amount of Ag2O (see
Table 3).
Table 3 The calculated values of EO coefficients b of samples PBG0-4
12 -2
Sample EO coefficient 𝑏 ×10 [m×V ]
PBG0 7.58
PBG1 7.47
PBG2 7.66
PBG3 7.77
PBG4 7.72
Conclusion
The base glasses in the PbO-Bi2O3-Ga2O3 system and newly developed glasses
with an addition of Ag2O and Sb2O3 were successfully prepared. The measurements
of transmittance in the VIS and IR parts of the spectrum show that the glasses are
transparent in a wide band ranging from 550 nm to 7.4 µm. The measured values of
the refractive index reached their maximum at 473 nm for all investigated glasses.
-12 -2
The calculated values of EO coefficients b varied from 7.47 to 7.77×10 m×V and
are sufficiently high for construction of light EO modulators.
For further details see our recent article in J. Non-Cryst Solids 518 (2019) 51-56.
Acknowledgement: The authors acknowledge financial support obtained from specific

university research programme MSMT No. 21-SVV/2018 and the Technology Agency of the
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Czech Republic for the financial support under the project no. TH01010567/2016 and P.
Kostka acknowledges the Czech Science Foundation for the financial support under the
project no. 19-07456S.
References
[1] Saleh, B.; Bahaa, E. A.; Teich, C. M., 2nd ed.; Hoboken, N.J.: Wiley Interscience, 2007.
[2] Borrelli, N. Electric field induced birefringence in glasses. Physics and Chemistry of
Glasses 12 (4) (1971) 93-6.
[3] Weis, R S,Gaylord, T. K. Lithium niobate: Summary of physical properties and crystal
structure. Applied physics A-Materials Science & Processing 37 (4) (1985) 191-203.
[4] Li, ZD., Xiangjin Huang, XJ., Wu, DX., Xiong, K. Large crystal growth and measurement
of electro-optical coefficients of ADP. Journal of Crystal Growth 222 (3) (2001) 524-527.
[5] Rosner, R. D., Turner, E. H., Kaminov, I. P. Clamped Electrooptic Coefficients of KDP
and Quartz. Applied optics 6 (4) (1967) 778-778.
[6] Twu, R.-C., Hong, H.-Y., Lee, H.-H. An optical homodyne technique to measure
photorefractive-induced phase drifts in lithium niobate phase modulators. Optics Express
16 (6) (2008) 4366-4374.
[7] Wooten, E. L., Kissa, K. M., Yi-Yan, A. A review of lithium niobate modulators for fiber-
optic communications systems. IEEE Journal of Selected Topics in Quantum Electronics
6 (1) (2000) 69-82.
[8] Casson, J. L., Gahagan, K. T., Scrymgeour, D. A., et al. Electro-optic coefficients of
lithium tantalate at near-infrared wavelengths. Journal of the Optical Society of America
B-Optical Physics 21 (11) (2004) 1948-1952.
[9] Tang, HJ., Tabaoda, JM., Cao, GH., Li, LQ., Chen, RT. Enhanced electro-optic
coefficient of nonlinear optical polymer using liquid contact poling. Applied physics letters
70 (5) (1997) 538-540.
[10] Enami, Y., Derose, C. T., Mathine, D., et al. Hybrid polymer/sol–gel waveguide
modulators with exceptionally large electro–optic coefficients. Nature Photonics 1 (3)
(2007) 180-185.
[11] Liu, JL., Xu, GM., Li, FG., et al. Recent advances in polymer electro-optic modulators.
RSC Advances 5 (21) (2015) 15784-15794.
[12] Zhavoronkov, N., Driben, R., Bregadiolli, A., Nalin, M., Malomed, B. A. Observation of
asymmetric spectrum broadening induced by silver nanoparticles in a heavy-metal oxide
glass. EPL 94 (3) (2011) 37011.
[13] Golis, E., Kityk, I. V., Wasylak, J., Kasperczyk, J. Nonlinear optical properties of lead-
bismuth-gallium glasses, Materials Resarch Bulletin 31 (9) (1996) 1057-1065.
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HYDROGENATION OF CARBON MATRIX IN W-C:H COATINGS

DURING HYBRID PVD-PECVD SPUTTERING BY ERDA
1 1 2 2
František Lofaj , Margita Kabátová , Jozef Dobrovodský , Matúš Beňo ,
2
Dušan Vaňa
1
Institute of Materials Research of the Slovak Academy of Sciences, Košice
2
Advanced Technologies Research Institute, Faculty of Materials Science and
Technology in Trnava, Slovak University of Technology in Bratislava, Trnava,
Slovakia
e-mail: flofaj@saske.sk
The investigation of the plasma polymerization processes with acetylene and methane during
hybrid PVD-PECVD of W-C:H coatings using direct current (DCMS) and High Power Impulse
Magnetron Sputtering (HiPIMS) combined with the Elastic Recoil Detection Analysis (ERDA) /
Rutherford Back Scattering (RBS) techniques for the measurement of hydrogen and carbon
concentrations revealed that free carbon matrix hydrogenation occurs via incorporation of
CxHy radicals from hydrocarbon precursor gas. Methane as a precursor resulted in lower
carbon and slightly higher hydrogen concentrations than acetylene in the analogous DCMS
and HiPIMS coatings. Then, the hardness dependencies on the hydrocarbon type (methane
vs. acetylene) and deposition technique (DCMS vs. HiPIMS) indicated that the lost memory
effect is not valid in the hybrid PVD-PECVD W-C:H coatings.
Keywords: hybrid PVD-PECVD, W-C:H coatings, hydrogenation, hybridization,
Introduction
Friction behavior of the amorphous carbon coatings, a-C(:H), also called diamond-
like carbon coatings (DLC), is strongly influenced by the presence of hydrogen.
Hydrogen incorporation in the amorphous carbon structure is important for its
stabilization, reduction of residual stress and of various other properties, especially
coefficient of friction (COF) and wear resistance [1-3]. In the case of transition metal
(W, Ti, Cr, etc.) doped amorphous carbon coatings, similar and even wider effects
can be achieved [4-13]. The reactions between the metal and carbon result in the
development of nanograins of corresponding carbides, which are distributed in the
a-C:H matrix. In the case of a suitable ratio between the contents of nanocrystalline
carbide phase and amorphous matrix, nanocomposite structures with considerably
improved hardness can be obtained [14]. Among the nanocomposite coatings, the
W-C:H system attracts attention due to an extended range of mechanical and
tribological properties and a subsequently wide potential of practical applications [4-
13]. Nanocomposite W-C:H coatings are usually deposited by hybrid PVD-PECVD
magnetron sputtering from a WC (or W and C in the case of dual sputtering) target
in an atmosphere containing hydrocarbon gasses CxHy, (e.g. x = 1 and y = 4 for
methane; x = 2 and y = 2 for acetylene, etc.) used as a source of carbon and
hydrogen for the growth of the matrix [8-13, 15-19]. Plasma generated by WC
sputtering strongly interacts with the hydrocarbon gas and it decomposes into
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HYDROGENATION OF CARBON MATRIX IN W-C:H COATINGS DURING HYBRID PVD-PECVD SPUTTERING
BY ERDA F. Lofaj, M. Kabátová, J. Dobrovodský, M. Beňo, D. Vaňa
different –CxHy (x, y = 1,2,3..) fragments, which may recombine prior to its deposition
of the substrate and chamber walls. Thus, the growth of the W-C:H occurs via
simultaneous deposition of WC and hydrocarbon fragments and the hydrogenation
of the carbon matrix is a consequence of incorporation of C xHy [3, 15-18]. The level
of hydrogenation depends on the type of hydrocarbon gas, its amount and the
energy of the impinging particles [3, 17-19]. Apparently, when acetylene, C2H2, with
H:C ratio 1:1 is used as a precursor gas, it will provide less hydrogen than methane,
CH4, where the H:C ratio is 4:1 [3]. Subsequently, the differences in the H/C ratio
originating from various hydrocarbons may be expected to affect properties of the
corresponding coatings.
It is well known that the hardness and coefficients of friction in a-C:H coatings [3, 10,
20-22] and in W-C:H coatings [1, 4-13, 18] strongly depend on the hydrogen
concentration and environment. Hardness usually decreases and the effects of
hydrogenation on COF overlap with the effects of environment. Donnet et al. [20]
reported COFs below 0.01 in vacuum, when the hydrogen concentration in a-C:H
coatings exceeded 42 at.%. Erdemir et al. also reported strong dependence of COF
on hydrogen content with the possibility of achieving superlubricity in highly
hydrogenated carbon coatings in a dry nitrogen atmosphere [22]. The mechanisms
considered for low friction assume the formation of the passivation layer between
the sliding contacts from the dangling -bonds on carbon surface passivated by
hydrogen [20-22]. At a sufficiently high hydrogen concentration, full passivation of 
bonds would produce only weak van der Waals interactions between sliding
surfaces resulting in a dramatic reduction of friction force. When hydrogen in the
passivation layer is replaced by oxygen and/or –OH in dry and/or humid air, stronger
interactions between sliding surfaces would increase COFs in the a-C:H coatings
[20-22]. However, only few studies on the relationships between hydrocarbon
additions, level of hydrogenation and corresponding COF in W-C:H coatings were
published up to now. Makowka et al. [8] measured the concentration of hydrogen in
DCMS W-C:H coatings deposited with CH4 and H2 additions by SIMS and correlated
it with tribological properties. Nouvellon et al. [9] recently studied analogous W-C:H
coatings deposited using asymmetric bipolar pulsed DCMS of W target in Ar - C2H2
atmosphere and the level of hydrogenation was deduced from XPS studies.
However, no direct correlations to hardness, COF and wear were provided. Our
earlier works on hybrid PVD-PECVD W-C:H coatings [11-13, 18] were focused on
the application of High Power Impulse Magnetron Sputtering (HiPIMS) and High
Target Utilization Sputtering (HiTUS) and on the optimization of deposition
conditions, especially C2H2 addition, to maximize hardness and minimize COF.
Although the level of hydrogenation on hardness and COFs was investigated in
DCMS, HiPIMS and even HiTUS W-C:H coatings made with acetylene additions, the
details of the hybrid deposition from the viewpoint of the mechanism of
hydrogenation were analyzed only for HiTUS [18]. Therefore, the aim of the current
work was to investigate the hybrid PVD-PECVD processes leading to hydrogenation
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in DCMS and HiPIMS W-C:H coatings deposited with methane and to compare
them with those with acetylene additions.
All the coatings were deposited on polished disc (diameter - 25 mm, thickness -
3mm) substrates made from hardened bearing 100Cr6 steel and on (100) Si wafer
fragments with an approximately 200 nm thick Cr bond layer. Both DCMS and
HiPIMS depositions were performed in Cryofox Discovery 500 (Polyteknik,
Denmark) system with an average power of 350 W on the WC target (diameter -
76.2 mm). In the case of HiPIMS, a frequency of 150 Hz and impulse length of
175µs resulted in a duty cycle of 2.62 %. The sputtering atmosphere consisted of
25 sccm (standard cubic centimeters per minute) Ar and of variable additions (0 ÷
10) of C2H2, CH4 and H2 (5, 10 and 20 sccm) in a constant flow regime. The
pressure in the chamber was monitored by a baratron. The concentration of
hydrogen, carbon and tungsten across the depth profile of the studied coatings were
measured by Elastic Recoil Detection Analysis (ERDA)/Rutherford Backscattering
+
(RBS) using He ions with the energies of 4.65 MeV and 5.8 MeV at the ion beam
analysis end station of a 6 MV Tandetron. The data evaluation was performed in
SIMNRA 7.02 modelling software. The calculated hydrogen concentrations were
related to the hydrogen content in the reference HDPE polyethylene standard.
Primary information about plasma polymerization processes in plasma can be
obtained from the measurements of changes of total pressure of the reactive
atmosphere used during the deposition. The change of such pressure, p = p – po,
was defined as the difference between the pressure with plasma discharge, p, and
the initial pressure without discharge, po [3]. The results are summarized in Fig. 1
and Fig. 2 for methane vs. acetylene and DC vs. HiPIMS plasma, respectively. It
should be noted that the curves corresponding to 10 sccm and 20 sccm H2 additions
were intentionally shifted by 0.2 and 0.4 sccm CH4/C2H2 flow compared to 0 sccm H2
in all plots to distinguish among the overlapping curves.
Obviously, plasma polymerization caused negative p in all studied cases. Such
result is different from that in a-C:H [3], where negative p was reported for
acetylene while methane additions were characterized by positive p. The meaning
of the negative p values is that the ionized species and additional gaseous
fragments generated by the plasma polymerization reactions from the carrier and
from precursor gases were consumed faster than their production rate [3]. This
would be possible when the growth of the coatings is controlled by the supply of the
hydrocarbon fragments, not by the attachment of the fragments to the growing
surface. The main fragments contributing to the growth in DCMS and HiPIMS are
not exactly known. In the model studies of the growth of a-C:H, beams of –CH3
radicals were used [15]. In our recent work on HiTUS W-C:H coatings with acetylene
additions, residual gas analysis (RGA) suggested that the primary sources were
C2H, C2 and CH radicals with unsaturated  bonds. However, the contributions of –
CH2 and -CH3 and/or direct hydrogen bonding with carbon at the interface were
Jahodná, Slovakia
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25 -27 June, 2019 59
found to be necessary to achieve the level of hydrogenation measured

experimentally [18]. Analogous RGA study on DCMS and HiPIMS processes was
not performed due to the absence of RGS on the corresponding deposition system.
0.00 0.00
-0.02 +20 H2
-0.02
0 H2 0 H2
+5 H2
-0.04 -0.04 +10 H2
p , Pa
-0.06
p , Pa
-0.06
+5 H2
-0.08 -0.08
+10 H2
-0.10 +20 H2 -0.10
DCMS plasma 350 W DC plasma 350 W
-0.12 25 sccm Ar + x sccm CH4 + y sccm H2 -0.12 25 sccm Ar + x sccm C2H2 + y sccm H2
0 2 4 6 8 10 12 0 2 4 6 8 10 12
a) b)
CH4 flow, sccm C2H2 flow, sccm
Fig. 1 Changes of total pressure of the reactive atmosphere composed of Ar + CH 4+H2 – a)

and Ar + C2H2+H2 –b), due to polymerization reactions in plasma driven by direct
current magnetron sputtering ofWC target
The dependencies corresponding to10sccm and 20 sccm H2 additions were
intentionally shifted by 0.2 and 0.4 sccm CH4/C2H2 flow for better visibility.
0.01 0.01
0.00 0.00
+10 H2 +5 H2 +5 H2
+20 H2
-0.01 +0 H2 -0.01 0 H2
p , Pa
p , Pa
-0.02 -0.02
+10 H2
+20 H2
-0.03 -0.03
-0.04 HiPIMS plasma 350 W -0.04 HiPIMS plasma 350 W

25 sccm Ar + x sccm CH4 + y sccm H2 25 sccm Ar + x sccm C2H2 + y sccm H2
-0.05 -0.05
0 2 4 6 8 10 12 0 2 4 6 8 10 12
a) CH4 flow, sccm
b)
C2H2 flow, sccm
Fig. 2 Comparison of the changes of total pressure of the reactive atmosphere composed
ofAr + CH4+H2 – a) and Ar + C2H2+H2 –b), due to polymerization reactions
inHiPIMSplasma
The dependencies corresponding to 10 sccm and 20 sccm H2 additions were
A closer look on p behavior with methane and acetylene (Fig. 1a vs. Fig. 1b)
revealed significant differences. In the former case, p approximately linearly
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decreases up to -0.04 Pa at 8 sccm CH4 addition even with additions of hydrogen.

At 10 sccm CH4, p rapidly changed to -0.13 Pa. In contrast, acetylene additions
caused changes of p below -0.03 Pa in the whole range of precursor gas
additions. Additions of hydrogen made p even smaller and closer to the resolution
limit of the baratron (> 0.005 Pa).
The behavior of p in HiPIMS plasma exhibited negligible dependence both in
methane- and acetylene - containing atmospheres and the maximum p was
≤0.015 Pa. This means that the difference between the supply of plasma
polymerization products and their consumption for the coating growth is several
times lower than in DCMS case with methane (Fig. 1a). Based on these results,
higher deposition rates would be expected in DCMS for CH 4 than for C2H2 additions.
Fig. 3a and 3b show the average deposition rates obtained in the studied coatings.
DCMS resulted in ~3 times higher deposition rates than in HiPIMS with both
methane and acetylene additions, respectively. Despite aforementioned
expectations, the deposition rates with methane were practically always lower than
those with acetylene. The reason seems to be related to the absolute amount of
carbon in the corresponding precursor: at the same gas flow, the amount of carbon
in C2H2 would be twice higher than in CH4. Moreover, a saturation limit can be seen
in coatings made with acetylene. The physical reasons for the existence of such
saturation were attributed to the energy in the plasma, which is consumed on the
ionization, sputtering and polymerization reactions [18]. The absence of this
saturation in the case of methane additions (Fig. 3a) seems to be a consequence of
an insufficient range of methane additions in the current study.
1.50 1.50
W-C:H coatings
Average deposition rate, nm/s
Average deposition rate, nm/s
1.25 1.25
25 sccm Ar + x CH4
DCMS
DCMS
1.00 1.00
HiPIMS
0.75 0.75
HiPIMS
0.50 0.50
+ 10/20 sccm H2
0.25 0.25 W-C:H coatings
25 sccm Ar + x C2H2
0.00 0.00
0 1 2 3 4 5 6 7 8 9 10 11 12 13 0 1 2 3 4 5 6 7 8 9 10
a) CH4 flow, sccm b) C2H2 flow, sccm
Fig. 3 Comparison of average deposition rates of the studied W-C:H coatings prepared
withdifferent hydrocarbon precursors (methane vs. acetylene) using DCMS and
HiPIMS
Fig. 4 summarizes the ERDA/RBS measurements in the studied HiPIMS W-C:H

coatings in terms of average concentrations of C, W and H in dependence on the
precursor additions. Methane additions up to 6 sccm caused gradual increase of H
Jahodná, Slovakia
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25 -27 June, 2019 61
concentration up to ~28 at.%. At higher CH4 additions, hydrogen concentration

remained approximately the same. Hydrogenation occurred fully at the expense of
W concentration and carbon concentrations remained approximately constant at
around 65 at.% within the whole range of methane flows. The influence of hydrogen
additions depended on the methane additions. At 2 sccm CH4, additions of 10 sccm
and 20 sccm H2 led to increase of hydrogen concentration in the coating from 6 at.%
to 17-18 at.% and it was accompanied by a decrease of carbon concentration. At
8sccm CH4, hydrogen additions had no effects. These results suggest the possibility
of a limit for hydrogenation and two different mechanisms for hydrogenation –
directly from hydrocarbon fragments (at the expense of W) and directly from
hydrogen (at the expense of carbon).
80 80
70 C 70 C
Atomic concentration, at. %
Atomic concentration, at. %
+20sccm H2
60 60
+10/20 H2 HiPIMS HiPIMS

50 50
350 W 350 W
40 W 25 Ar + x CH4 + y H2 40 25 Ar + x C2H2 + y H2
+20sccm H2
+20 H2 30
30
H H
20 20
+10 H2 10
10 W
0 0
0 2 4 6 8 10 12 0 1 2 3 4 5 6 7
a) b) C2H2 (and H2) flow, sccm
CH4 (and H2) flow, sccm
Fig. 4 Atomic concentrations of H, C and W in the HiPIMS W-C:H coatings deposited

byhybrid PVD-PECVD from methane (+ hydrogen) – a) and acetylene (+ hydrogen) –
b) containing reactive atmospheres from ERDA/RBS measurements
The dependencies corresponding to 10 sccm and 20 sccm H2 additions were
The additions of acetylene produced similar dependencies but different absolute

concentrations (Fig. 4b): ≤ 75% in the case of carbon, and hydrogen concentrations
were lower than 20 at.%. The addition of hydrogen into atmosphere increased the
hydrogenation close to 30 at.% level also at the expense of carbon. As expected
from a higher C:H ratio, acetylene provided more carbon and less hydrogen but the
hydrogenation limit close to 30 at.% seems to be existing even in this case. The
saturation limit of 50 at.% was predicted for a-C:H coatings from a random covalent
network model [23]. In W-C:H coatings, a part of carbon is bound to tungsten and
therefore, less carbon is available for hydrogenation. The saturation limit of 30 at.%
seems to be reasonable.
The effects of hydrogenation on hardness of the studied coatings are illustrated in
Fig. 5. In the case of methane additions, almost overlapping and steadily decreasing
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hardness values from 27 – 30 GPa at 0 sccm to ~9 GPa and 14 GPa at 12 sccm

CH4 can be seen in DCMS and HiPIMS coatings, respectively (Fig. 5a). When these
data are combined with that in Fig. 4a, hardness decrease occurred even if carbon
and hydrogen concentrations were approximately constant (> 6 sccm CH 4). On the
other hand, decreased concentrations of W at this range of methane flows mean
that the amount of free carbon increased. Thus, the degradation of hardness has to
be a result of the increase of free carbon content rather than that of hydrogenation.
In the case of acetylene and DCMS, higher hardness was obtained at 0 sccm CH 4
and lower hardness at 8 sccm than in the coatings made with methane. However,
the hardness of the HiPIMS coatings remained at around 20 GPa within the whole
range of acetylene additions (2 – 8 sccm). Thus, hardness seems to depend not
only on free carbon and hydrogen contents but also on additional structural
parameters.
40 40
35 W-C:H coatings
Si substrate
30 30
25 sccm Ar + x CH4
25
HiPIMS
HIT, GPa
HIT , GPa
20 20
HiPIMS
15
10 10
DCMS
DCMS W-C:H coatings
5 Si substrate
25 sccm Ar + x C2H4
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7 8
a)
CH4 flow, sccm b) C2H2 flow, sccm
Fig. 5. Hardness dependencies on precursor gas flow of the studied DCMS and HiPIMS W-
C:H coatings deposited with the additions of methane – a), and acetylene – b).
In the literature [3], the levels of branching and cross-linking of the carbon structure
was considered. Apparently, HiPIMS and acetylene provided better combination of
all these parameters than DCMS and/or methane, which resulted in higher
hardness. At the same time, the obtained differences confirm that the „lost memory
effect“ claiming that the resulting properties are independent of the hydrocarbon gas
type [24], is not valid in the studied W-C:H coatings.
Conclusions
The investigations of the influence of two types of hydrocarbon precursor gas in
hybrid PVD/PECVD deposition of W-C:H coatings revealed that although their
mechanical properties are primarily determined by the amount of free amorphous
carbon, its hydrogenation is also an important factor. Carbon hydrogenation occurs
via incorporation of CxHy radicals from hydrocarbon precursor gas. Methane as a
precursor resulted in lower carbon and slightly higher hydrogen concentrations than
acetylene in the analogous DCMS and HiPIMS coatings. Then, the hardness
Jahodná, Slovakia
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25 -27 June, 2019 63
dependencies on the hydrocarbon type (methane vs. acetylene) and deposition

technique (DCMS vs. HiPIMS) indicated that the lost memory effect is not valid in
the hybrid PVD-PECVD W-C:H coatings.
Acknowledgements: The support provided by the projects APVV 15-0168, APVV-17-0320,

APVV-17-0049 and VEGA 2/0017/19 is acknowledged. The equipment used in the work was
acquired from the projects “Research Centre of Advanced Materials and Technologies for
Recent and Future Applications” PROMATECH, ITMS: 26220220186 and “University
Scientific Park Campus MTF STU – CAMBO” ITMS: 2622022079.
References
[1] J.C. Sánchez-López, A. Fernández, in B. Bhushan (Ed.), Handbook of Modern
Tribology, CRC Press, Boca Raton, 2008, pp. 311-338.
[2] J. Vetter, Surf. Coat. Technol. 257 (2014) 213-240.
[3] D. Thiry, A. De Vreese, F. Renaux, J.L. Colaux, S. Lucas, Y. Guinet, L. Paccou, E.
Bousser, R. Snyders, Plasma Process Polym. 13 (2016) 316-323.
[4] M.D. Abad, M.A. Muñoz-Márquez, S. El Mrabet, A. Justo, J.C. Sánchez-López, Surf.
Coat. Technol. 204 (2010) 3490 – 3500.
[5] K. Fuchs, P. Rödhammer, E. Bertel, F.P. Netzer, E. Gornik, Thin Solid Films 151 (1987)
383-395.
[6] A. Czyzniewski, Thin Solid Films 433 (2003) 180-185.
[7] J. Nazon, M. Herbst, M.C. Marco de Lucas, S. Burgeois, B. Domenichi, Thin Solid Films
591 (2015) 119-125]
[8] M. Makowka, W. Pawlak, P. Konarski, B. Wendler, Diamond. Relat. Mat. 67 (2016) 16-
25.
[9] C. Nouvellon, R. Belchi, L. Libralesso, O. Douhéret, R. Lazzaroni, R. Snyders, D. Thiry,
Thin Solid Films 630 (2017) 79-85.
[10] A.A.Voevodin, J.P. Neil, S.V. Prasad, J.S. Zabinski, J. Vac. Sci. Technol. A 17 (1999)
986-992.
[11] F. Lofaj, M.Kabátová, M. Klich, D. Vaňa, Ceram. Int. 45 (2019) 9502-9514.
[12] F. Lofaj, M. Kabátová, M. Klich, D. Medveď, V. Girman, Cerâmica 65 (2019) 58-69.
[13] F. Lofaj, L. Kvetková, P. Hviščová, M. Gregor, M. Ferdinandy, J. Eur. Ceram. Soc. 36
(2016) 3029-3040.
[14] S. Veprek, R.F. Zhang, M.G.J. Veprek-Heijman, S.H. Sheng, A.S. Argon, Surf. Coat.
Technol. 204 (2010) 1898-1906.
[15] A.von Keudell, M. Meier, C. Hopf, Diam. Relat. Mat. 11 (2009) 969-975.
[16] W. Jacob, Thin Solid Films 326 (1998) 1-42.
[17] Schwarz-Selinger, A. von Keudell, W. Jacob, J. Appl. Phys. 86 (1999) 3988 -3996.
[18] F. Lofaj, M. Kabátová, L. Kvetková, J. Dobrovodský, V. Girman, Surf Coat. Technol.,
submitted.
[19] H. Yasuda, Luminous Chemical Vapor Deposition and Interfaces, Marcel Dekker, New
York, 2005.
[20] C. Donnet, A. Grill, Surf. Coat. Technol. 94-95 (1997) 456-462.
[21] A.A. Voevodin, J.P. O’Neill, J.S. Zabinski, Thin Solid Films 342 (1999) 194-200.
[22] A. Erdemir, Surf. Coat. Technol. 146-147 (2001) 291-297.
[23] J.C. Angus, F. Jansen, J. Vac. Sci. Technol. 6 (1988) 1778-1782.
[24] C. Wild, J. Wagner, P. Koidl, J. Vac. Sci. Technol. A 5 (1987) 2227-2230.
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HARDNESS AND FRICTION IN HiTUS W – C:H COATINGS

DEPOSITED WITH ACETYLENE AND METHANE
Lenka Kvetková, Margita Kabatová, František Lofaj, Alexandra Kovalčíková

Slovak Academy of Science, Watsonova 47, Košice, Slovakia
e-mail: lkvetkova@saske.sk
The aim of the work was to compare the mechanical properties of W-C:H coatings with
acetylene and methane addition. In the studied coatings, a gradual increase in the content of
the amorphous carbon matrix was observed with the increased additions of acetylene or
methane. Acetylene seems to produce more free carbon than methane due to a higher C:H
ratio. Raman spectroscopy was used to estimate the amount of free carbon from the intensity
-1 3
of “D” and “G” graphite peaks and T peak at around 1200 cm was related to sp
3
hybridization. Higher intensity of T peak suggested a possibility of higher sp hybridization in
the W-C:H coatings with methane additions. Methane additions in HITUS W-C:H coatings
resulted in slightly higher hardness and a lower coefficient of friction than in the coatings with
acetylene due to lower contents of carbon at the same precursor gas flow.
Keywords: W-C:H coatings, High Target Utilization Sputtering (HiTUS), Raman spectroscopy
Introduction
Nanocomposite W-C:H coatings consist of sub-stoichiometric WC1-X nanocrystals
embedded in the amorphous carbon matrix [1-2]. The mechanical, as well as friction
properties of such nanocomposite coatings are principally determined by the ratio
between the contents of hard nanocrystalline carbide phase and free carbon in the
matrix. In the case of dual sputtering, carbon content is controlled via the power ratio
applied to sputter from W and C targets. This method produces hydrogen-free W-C
coatings. Hydrogenated W - C:H coatings are produced by hybrid PVD – PECVD,
when hydrogenated carbon matrix originates usually from CH 4, C2H2, are added into
Ar plasma [3-4]. Hydrogenation results in residual stress reduction and in a
significant decrease of the coefficient of friction (CoF) [5]. The level of hydrogenation
depends on the type of hydrocarbon gas. Acetylene, C 2H2 with the ratio of C : H of
1:1 can be a less effective source for hydrogenation than methane, CH 4, with C:H
ratio of 1:4 [6]. This paper focuses on the relationships between hydrocarbon gas
type, hardness and coefficient of friction in the HiTUS made W:C-H coatings.
The substrates for studied W-C:H coatings were hardened 100Cr6 steel, Al 2024
alloy and Si wafer. They were polished and ultrasonicated in acetone and ethanol for
5 min. Additionally, the substrates were plasma cleaned for 30 minutes.
Subsequently, around 200 nm Cr interlayer was deposited followed by W-C:H
coating deposition. Coatings were deposited in the HiTUS S 500 (Plasma Quest
Ltd., UK) system with the WC targets at working pressure of ≥ 5 Pa consisting of Ar
atmosphere with the variable additions of C2H2 or CH4. They were deposited from
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HARDNESS AND FRICTION IN HiTUSW–C:H COATINGS DEPOSITED WITH ACETYLENE AND METHANE
L. Kvetková, M. Kabatová, F. Lofaj, A. Kovalčíková
WC target at the constant radio-frequency power on a remote plasma source (1500

W), power on target (500 W), Bias (5 W), Ar flow (120 sccm) and deposition time (90
min).The only variables were the flows of acetylene (0, 3, 5, 8, 10 sccm) and
methane (0, 2, 4, 6, 8, 10, 12 sccm) in the Ar atmosphere.
The morphology, structure and thicknesses of the coatings were observed on the
cross sections of the fractured coating in the scanning electron microscope (model
Auriga Compact, Zeiss, Germany). Free carbon phase was investigated by the
Raman spectroscopy (XploRA, Horiba, Yvon Jobin) using a laser with the
wavelength 𝜆1 = 532 nm. The nanoindentation (model G200 Agilent, USA) tests
were performed in CSM mode with a sharp diamond Berkovich tip on a set of 16
indents. The hardness and indentation modulus depth profiles were obtained from
each indent and the final values correspond to the average from at least 9 valid
measurements. The dry friction behaviour of the studied coatings was investigated
at room temperature in a standard tribometer (model HTT, Switzerland) in the ball-
on-disc configuration with 100Cr6 ball. The tests were performed on the coatings
deposited on steel substrate in air at room temperature. Normal load of 1 N was
used in these tests. The corresponding wear tracks were observed by optical
microscopy (model Axio Observer, Zeiss, Germany).
Coating structure
Figures 1a and 1b show the morphology of fractured surfaces in the coatings
deposited with C2H2 and CH4 addition. In both cases, dense, featureless and
homogeneous fracture surfaces were observed implying either amorphous or
nanocomposite structures.
.
3 sccm Acetylene 4 sccm Methane
400nm
400nm
Fig. 1 Fracture cross sections of W-C:H coatings deposited with (a) C2H2 and (b) CH4
addition.
Fig 2 shows the X-ray diffraction spectra of HiTUS W-C:H coatings on Al alloy
substrates deposited with comparable additions of acetylene and methane. The
peaks from the coatings were much wider and less intensive than those from the
substrate. The most intensive peaks were observed in pure W-C coatings deposited
without any additions of reactive gases. They were attributed to fcc WC1-X and
possibly also to W 2C.Their intensity decreased with C2H2 and CH4 additions. The
gradual widering of peaks in XRD spectra implied the presence of nanocrystals
and/or the amorphizations of their structures.
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Al substrate and holder

8000
HiTUS W-C:H coatings HiTUS W-C:H coatings

1800W/500W
6000
Intensity, arb.
Intensity, a.u.
8 CH4 - 0 H2
4000
10 C2H2
4 CH4 - 0 H2
5 C2H2
2000 2 CH4 - 0 H2
3 C2H2
0 CH4 - 0 H2
0 C2H2
30 35 40 45 50 55 60 65 70 75 80 85 30 35 40 45 50 55 60 65 70 75 80 85
WC1-x (20-1316) (111) (200) 2 theta (220) (311) WC1-X (111) (200) 2 (220) (311)
W2C (35-0776) (101) (100) (201) W2C (101) (100) (201)
Fig 2 XRD diffraction spectra of W-C:H coatings as a function of (a) C2H2 flow and (b) CH4
flow
Raman spectroscopy
Raman spectroscopy was used to estimate the amount of free carbon from the
intensities of “D” and “G” graphite peaks [7,8]. The intensities of these peaks
increased with the increase of acetylene and methane additions (Fig. 3). Raman
-1
spectra were deconvoluted into D, G and one additional peak at around 1200 cm ,
marked as T peak (Fig 4). T peak was in tetrahedral amorphous carbon coatings
3
and attributed to the presence of carbon with sp hybridization [3,4,8]. Its relative
3
intensity was higher in the coatings made with methane. Thus, higher sp
hybridization from methane can be expected.
1600 4000
HiTUS W-C:H coatings HiTUS W-C:H coatings
10 sccm C2H2
12 sccm CH4
10 sccm CH4
Intensity, a.u.
Intensity, a.u.
5 sccm C2H2
8 sccm CH4
3 sccm C2H2
4 sccm CH4
2 sccm CH4
0 sccm C2H2
0 0
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
-1 -1
Raman Shift, cm Raman Shift, cm
Fig. 3 Raman spectra of W-C:H coatings with various additions of (a) C2H2 and (b) CH4
Jahodná, Slovakia
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25 -27 June, 2019 67
250 350
HiTUS D HiTUS
1379
5 sccm C2H2 4 sccm CH4 D
1391 G
1551
Intensity, a.u.
Intensity, a.u.
G
1582
T
T 1182
1162
0 0
1000 1200 1400 1600 1800 1200 1400 1600
-1 -1
Raman Shift, cm Raman Shift, cm
Fig. 4 Deconvolution of the Raman spectra of W:C-H coatings with (a) 5 sccm C2H2
addition and (b) 4 sccm CH4 addition.
Hardness and coefficient of friction of W-C:H coatings

The results of hardness measurements of W-C:H coatings with acetylene and
methane flow are summarized in Fig. 5. The addition of 2 sccm methane caused an
increase of hardness from 27.1 GPa to 30,9 GPa. Further increase of methane flow
resulted in a gradual decrease of hardness to around 8 GPa. The hardness values
in the coatings made with acetylene were 2 – 7 GPa lower, only at 10 sccm C2H2
hardness of 14 GPa was achieved. The differences in hardness can be associated
3
with higher content of free carbon and lower sp content in the coatings made with
acetylene compared those with methane at the same precursor gas flow, implied
from Fig 3 and Fig 4.
32
30
28
26
Hardness (GPa)
24
22
20
CH4
18
16
14
12 C2H2
10
8
6
4
2
0 2 4 6 8 10 12
C2H2 and CH4 (sccm)
Fig. 5 Dependence of hardness of HiTUS W-C coatings on acetylene and methane
additions.
Figure 6 illustrates typical time dependence of the coefficient of friction in the W-C:H
coating made with 8 sccm C2H2. The main feature is extremely long run – in period.
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Steady values with the lowest COF were achieved only after 9h of sliding at 10cm/s.
Despite no direct experimental evidence is available, similar studies [5, 6, 9]
suggested the formation of a transfer layer during long run-in which result in reduced
Figure 7 summarizes the effect of acetylene and methane additions on the
coefficient of friction. Both materials exhibit similar behavior but the absolute values
of COF are lower in the coatings with methane additions. COF-s of C2H2 made
coatings gradually reduced from 0.9 to 0.5 (at 10 sccm C 2H2 addition) whereas they
were around 0,3 in the coatings deposited with 12 sccm CH4 addition. This result
suggests that free carbon content, which should be lower in methane made
coatings, is not the only parameter affecting friction behavior of the studied W-C:H
coatings.
1,0
0,9
Coefficient of Friction 0,8
0,7
C2H2
0,6
0,5
CH4
0,4
0,3
0 2 4 6 8 10 12
C2H2 or CH4 flow (sccm)

Fig.6 Friction curve in W-C:H coating Fig. 7 Coefficient of friction of W-C coatings
with8 sccm CH4 addition as a function of acetylene and
methaneadditions
Conclusion
Investigation of the structure, Raman spectra, hardness and friction behavior of
HiTUS W-C:H coatings as a function of acetylene and methane additions revealed:
1 a gradual increase of the content of amorphous carbon matrix with the increased
addition of acetylene or methane. Acetylene seems to produce more free carbon
than methane due to higher C:H ratio.
3
2 Raman spectroscopy suggested a possibility of higher sp hybridization in the W-
C:H coatings made with methane addition due to higher intensities of T peak,
3
related to sp .
3 Methane additions in HITUS W-C:H coatings resulted in slightly higher hardness
and lower COFs than in the coatings made with acetylene due to lower contents
of carbon at the same precursor gas flow.
Acknowledgements: The financial support provided by the projects APVV-17-0320, APVV-

15-0168, APVV-17-0049 and PROMATECH, ITMS 26220220186, is acknowledged.
Jahodná, Slovakia
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References
[1] A. Czyzniewski, Deposition and some properties of nanocrystalline WC and
nanocomposite WC/a-C:H COATINGS, Thin Solid Films 320 (1998) 192-197.
[2] M.D.Abad Tailored synthesis of nanostructured WC/a-C coatings by dual magnetron
sputtering. Surf. Coat Technol. 204 (2010) 3490 – 3500.
[3] C. Nouvellon, WC/C:H films synthesized by an hybrid reactive magnetron
sputtering/Plasma Enhanced Chemical Vapor Deposition process: An alternative to
Cr(VI) based chromium plating, Thin Solid Films 630 (2017) 79-85.
[4] M.Makowka, Hydrogen content influence on tribological properties of nc-WC/a-C:H
coatings, Diamond Relat. Mat. 67 (2016) 16-25.
[5] C. Donnet, A. Erdemir, Tribology of diamond-like carbon films: Fundamentals and
applications, Springer, New York, USA (2008) 1.
[6] A. Erdemir, O.L. Eryilmaz, I.B. Nilufer, G.R. Fenske, Effect of source gas chemistry on
tribological performance of diamond-like carbon films, Diam. Rel. Mat. 9 (2000) 632-637.
[7] A.C. Ferrari and J. Robertson, Phys. Rev. B. 61 (20), (2000) 14095.
[8] C. Casiraghi, A. C. Ferrari, and J. Robertson, Raman spectroscopy of hydrogenated
amorphous carbons, in Phys. Rev. B27 (2005), 1-14.
[9] Scharf, T. W. and Singer, I. L., “Monitoring Transfer Films and Friction Instabilities with
In Situ Raman Tribometry,” Tribology Letters, 14, 1, 2003, 3-8.
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SHORE HARDNESS AND YOUNG’S MODULUS OF ALUMINA

PORCELAIN MIXTURE FIRED AT 300 °C – 1250 °C
1 2 2 2 2
Marek Mánik , Filip Obert , Ján Ondruška , Tomáš Húlan , Igor Štubňa
1
Building Testing and Research Institute, Braneckého 2, 949 01 Nitra, Slovakia
2
Department of Physics, Constantine the Philosopher University in Nitra, Tr. A.
Hlinku 1, 949 74 Nitra, Slovakia
e-mail: istubna@ukf.sk
The simple apparatus for measuring the Shore hardness (HS) was designed and constructed.
It uses the hardened steel ball as an indentor. The relative standard uncertainty of measuring
the HS is 4.6 %. The Young’s modulus (YM) and HS of the alumina porcelain mixture fired at
different temperatures (300 °C – 1250 °C) showed two parts. The first is for temperatures
< 800 °C where HS and YM are low and the second part is for temperatures > 800 °C where
HS and YM increase exponentially due to sintering. Dehydroxylation of kaolinite influences
YM negligibly and HS increases in a small measure. For the temperatures, the relation
between HS and YM is approximately constant. For the higher temperatures, this relationship
can be described with an exponential function.
Keywords: Shore hardness, Young’s modulus, ceramics
Introduction
The hardness is defined as the measure of a material's resistance to deformation by
surface indentation. Hardness is generally characterized by strong intermolecular (or
interatomic) bonds, but the behavior of solid materials under force is complex;
therefore, there are different kinds of hardness, and consequently, different methods
for its measurement. The static hardness is measured by the tests after Brinell,
Rockwell, Vickers or Knoop. This hardness is determined by measuring the
permanent depth or area of the indentation. The same force and its duration must be
used for every test [1]. Dynamic methods are indirect; they use the relation between
the hardness and loss of the kinetic energy of the indentor which drops down on the
sample from the known fixed height. The rebound height is less than original height
due to energy loss. The registered quantity is the height of the bounce of the
indentor (diamond-tipped hammer or steel ball). This type of hardness (Shore
hardness, rebound hardness, dynamical hardness) is associated with the elasticity
of the material [2]. The device used to take this measurement is known as
scleroscope. It consists of a diamond-tipped hammer or steel ball, falling in a vertical
graduated glass tube from a fixed height. A similar tester is Leeb´s device to provide
a portable hardness test for metals [3]. The Shore scleroscope is not only small and
mobile, but it also leaves no impressions on the tested surface.
The ratio ℎ𝑓 (rebound height) to ℎ0 (original height) is a measure of the Shore
hardness
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SHORE HARDNESS AND YOUNG’S MODULUS OF ALUMINA PORCELAIN MIXTURE FIRED AT 300 °C –
1250 °C M. Mánik, F. Obert, J. Ondruška, T. Húlan, I. Štubňa
hf
HS  K , (1)
h0
where 𝐾 is numerical coefficient depending on the chosen scale: 𝐾 = 140
4
(𝐻𝑆𝐷 hardness, 𝐻𝑆𝐷 = 100 belongs to hardened steel) or 𝐾 = 10 /65 (𝐻𝑆𝐶
hardness) are used for hard materials such as metals or ceramics. Eq. (1) can be
rewritten for a restitution coefficient v f / v0 , where v f  2 gh f and v0  2gh0 ,
so we obtain
2
 vf 
HS  K   . (2)
 v0 
The hardness of ceramics is determined by their chemical and mineral compositions
and microstructure characteristics: porosity, grain size, grain boundaries. It is always
in force a relation h f  h0 due to energy loss for plastic deformation (which plays a
small role in ceramics) and generation of the vibrations in the indentor and sample.
The aim of this work is a short description of the apparatus and measuring the Shore
hardness and Young’s modulus of alumina porcelain mixture fired at temperatures
300 °C – 1250 °C as well as determining the relationship between the Shore
hardness and Young’s modulus.
Experimental
The simple apparatus was designed and constructed for measuring the Shore
hardness. It consists of a vertical stand with an electromagnet on its upper end and
a pad for the sample on its lower end. The indentor (hardened steel sphere  5 mm)
is kept by the electromagnet at the height ℎ0 = 255 mm. When the indentor hits the
sample, the microphone, located close to the hit point and connected to a computer,
detects the free damped sound vibrations. The indentor hits the sample again after
the rebound. The program (written in MATLAB) finds the first maximum of both
sound vibrations (Fig. 1) and calculates the time interval 2t   t between them.
The height of the rebound is h f  gt / 2 , so we obtain h f  g (t ) / 8 and Eq. (1)
2 2
gets a form
g (t ) 2 (t ) 2
HSD  140  171.67 . (3)
8 h0 h0
The uncertainty analysis of the hardness measurement with the ascribed apparatus
was performed in [4]. Sources of the uncertainty such as repeatability of measuring
the height ℎ0 and ℎ𝑓 , and time 𝑡, admissible errors of the digital measuring
instruments, air resistance, deviation of the sample from the horizontal position, as
well as vibration of the sample were taken into account. The relative standard
uncertainty of measuring the Shore hardness is 4.6 %.
As mentioned above, the impact generates free damped vibrations of the sample. If
the sample has cylindrical or prismatic form and the indentor hits the antinodal point
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of the fundamental flexural vibrations, Young’s modulus can be determined [5, 6].
Since the vibrations are damped (see Fig. 1), the coefficient of the internal damping
can be also determined [5]. Such combine experiment, where the hardness and
Young’s modulus were measured, was performed in [7].
Fig. 1 Sound recording of two consequence indentor hits
Samples for hardness test were made from a wet porcelain plastic blank (diameter
300 mm) delivered by the ceramic plant PPC Čab. The samples consist of 36 wt.%
of kaolin, 30 wt.% of Al2O3, 12 wt.% of fireclay and 22 wt.% of feldspar. The
chemical composition of the mixture is given in Table 1.
Table 1 Chemical composition of samples (in wt %)
LOI SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2O Na2O

4.93 40.22 48.99 0.81 0.20 0.23 0.27 3.60 0.59
The blank was cut into the prismatic samples. Then the samples were dried in the
open air. The dry samples were smoothed by the fine sandpaper to reach
dimensions of 10×30×30 mm for Shore hardness (HS) and 10×10×130 mm for
Young’s modulus (YM). After that, the sets of three samples were fired at
temperatures of 300, 400, 425, 450, 475, 500, 550, 600, 700, 800, 900, 1000, 1100,
1200 and 1250 °C with heating and cooling rate of 5 °C/min. The measurements
were performed at room temperature.
The HS was measured on the apparatus described above and YM was measured
using the impulse excitation method described in [6].
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The results of the measurement of YM after selected firing temperatures are visible
in Fig. 2. Dehydroxylation of kaolinite (400 °C – 700 °C) influenced YM only slightly
increasing its values. The values of YM are low up to 800 °C which can be
considered as a start of the sintering. For the temperatures > 800 °C, YM increased
exponentially according to a relationship between YM and firing temperature
E  0.242 exp(0.0049 t ) , 𝑅2 = 0.9977.
160
140
Young modulus / GPa
120
100
80
60
40
20
0
200 400 600 800 1000 1200 1400
firing temperature / °C
Fig. 2 Relationship between Young’s modulus and firing temperature
The relationship between HS and firing temperature is depicted in Fig. 3. The

increase of HS is well visible in the dehydroxylation region (400 °C – 500 °C) and
then the increase continues and obeys an exponential law
SHD  9.769 exp(0.0016 t ) , 𝑅2 = 0.9899 above 800 °C.
90
80
70
Shore hardness / -
60
50
40
30
20
10
0
200 400 600 800 1000 1200 1400
firing temperature / °C
Fig. 3 Relationship between Shore hardness (𝐻𝑆𝐷) and firing temperature
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As was mentioned above, HS is linked to elastic properties of the measured

material, consequently, the relationship between YM and HS can be found. This was
derived from the results shown in Fig. 2 and Fig. 3, see Fig. 4. The part of 𝐸(𝑆𝐻𝐷),
which belongs to sintering, can be expressed as E  2.207 exp 0.0535 (SHD) , 𝑅2
= 0.9838.
140
120
Young modulus / GPa
100
80
60
40
20
0
10 20 30 40 50 60 70 80
Shore hardness / -
Fig. 4 Relationship between Shore hardness and Young’s modulus
Conclusions
The simple apparatus for measuring the Shore hardness was designed and
constructed. It uses the hardened steel ball as an indentor which falls down on the
sample. The time interval between two falls of the indentor serves for determination
of the ratio (initial height) : (rebound height), which is base of the Shore hardness.
The relative standard uncertainty of measuring the Shore hardness is 4.6 %.
The Young’s modulus and Shore hardness of the alumina porcelain mixture fired at
different temperatures (300 °C – 1250 °C) showed two parts. The first is for
temperatures < 800 °C where both quantities are low, and the second is for
temperatures > 800 °C where both quantities increase exponentially.
Dehydroxylation of kaolinite influences Young’s modulus negligibly and increases
Shore hardness in a small measure.
Both quantities are related to each other. For the low hardness (up to 𝑆𝐻𝐷 = 40), i.e.
for low temperatures, the relation between them is approximately constant. For
higher hardness (i.e. higher temperatures) this relationship can be described with an
exponential function.
Acknowledgement: This work has been supported by the grants VEGA 1/0425/19 and
VEGA 1/0810/19 of the Ministry of Education of Slovak Republic.
References
[1] H. Chandler: Hardness Testing, 2nd Edition, ASM International, Materials Park OH,
1999
Jahodná, Slovakia
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25 -27 June, 2019 75
[2] S. Maki, T. Yamamoto: Computer Simulation of Micro Rebound Hardness Test. Procedia
Engineering, 81 (2014) 1396-1401
[3] ASTM A956: Standard Test Method for Leeb Hardness Testing of Steel Products.
[4] M. Mánik, F. Obert, J. Ondruška, I. Štubňa: Meranie tvrdosti Shoreho metódou. In: Proc.
Conf. 30th DIDMATTECH 2017, Part 1, Trnavská univerzita, Trnava, 2017, p. 10-18
[5] ASTM E1876-09: Standard test method for dynamic Young’s modulus, shear Modulus
and Poisson’s ratio by impulse excitation of vibration
[6] I. Štubňa, T. Húlan, A. Trník, L. Vozár: Uncertainty in the determination of Young´s
modulus of ceramics using the impulse excitation technique at elevated temperature.
Acta Acustica United with Acustica, 104 (2018) 269-276
[7] V.M. Baranov, J.V. Miloserdin: Vysokotemperaturnye ispytanija reaktornych
materialov. Atomizdat, Moskva 1978
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MICROSTRUCTURE CHARACTERISTICS, TRIBOLOGY AND NANO-

HARDNESS OF HVOF AND PLASMA SPRAYED NiCrRe COATINGS
1,6 1 2 2
Dávid Medveď , Michal Ivor , Tomasz Chmielewski , Dariusz Golański ,
3 3 3
Marcin Chmielevski , Katarzyna Pietrzak , Agata Strojny-Nedza ,
5 1
DanielKottfer , Ján Dusza
1
Institute of Materials Research, Slovak Academy of Science, Watsonova 47,
04 0 01 Košice, Slovakia
2
Warsaw University of Technology, Warsaw, Poland
3
Institute of Electronic Materials Technology, Warsaw, Poland
4
Technical University of Košice, Faculty of Materials, Metallurgy and Recycling,
Institute of Materials, Letná 9, 042 00 Košice, Slovakia
5
Technical University of Košice, Faculty of Mechanical Engineering,
Department of Mechanical Technologies and Materials, Mäsiarska 74,
040 01 Košice, Slovakia
6
The Technical University of Košice, Faculty of Materials, Metallurgy and Recycling,
Metallurgy Institute, Letná 9, 042 00, Slovakia
e-mail: dmedved@saske.sk
The aim of this investigation is to study the microstructure characteristics, mechanical and
tribological behaviour of NiCrRe coatings deposited by Plasma and HVOF(High Velocity Oxy-
Fuel) spray processes at the atmospheric pressure on boiler steel substrate. These coatings
were characterized by means of a scanning electron microscopy, and Energy-dispersive X-
ray spectroscopy. The wear resistance of HVOF and Plasma sprayed NiCrRe coatings has
been investigated under dry sliding conditions at applied load 5, 10, and 20 N in air. The
continuous stiffness measurement (CSM) method was used for investigation of nanohardness
using Agilent G200 Nano-indenter in order to determine the mechanical properties of the
coatings. Microstructural observations pointed out that the NiCr layers with white isles of
Rhenium possessed porosity, oxidized, un-melted and semi-melted particles, and inclusions.
The results for NiCrRe Plasma sprayed coating are approximately followings: thickness of the
layer 450 µm, indentation modulus 158±24,4 GPa, hardness 3,74±0,76 GPa and the
coefficient of friction 0,45. The results for the VHOF coating are approximately followings:
thickness of the layer 870 µm, indentation modulus 237,6 ±10,2 GPa, hardness 6,3
±0,68GPa and the coefficient of friction 0,40.
Keaywords: NiCrRe coating, HVOF, Plasma, Mechanical properties
Introduction
In power generation plants, especially those co-fired with biomass, the operating
temperature is often limited in order to reduce severe chlorine-induced corrosion,
solid particle erosion and slagging, as these factors may cause unexpected plants
shutdowns and high maintenance costs. Weld overlays are used to prevent
corrosion of the boilers steel tubes but this can be a costly solution. Alternatively,
special coatings are also used to improve boilers performance extends their lifetime
in the highly corrosive combustion environments.
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MICROSTRUCTURE CHARACTERISTICS, TRIBOLOGY AND NANO-HARDNESS OF HVOF AND PLASMA
SPRAYED NiCrRe COATINGS D. Medveď et.al. ,
The coatings should mitigate corrosion processes and erosion in boiler pipes and,
thus, increase the maintenance intervals, operating temperature and boiler’s
efficiency [1÷3]. Besides technical merits, these new material systems should have
insignificant ecological footprint across company operations, supply chains and
product lifecycles, and remain economically acceptable for mass applications in
boilers in power plants. To meet these requirements, we used Plasma spraying and
HVOF (High Velocity Oxy Fuel) processing for NiCrRe coating on a boiler steel
substrate. The Rhenium is an alloying additive that improves the heat resistance of
alloys, creep and high-temperature oxidation resistance. Alloys with the addition of
rhenium are widely used in the aerospace industry (nickel superalloys) and in power
industry [4÷6].
The main objective of this study is to investigate the microstructure development,
hardness, indentation modulus and wear resistance of new coating materials for the
steel combustion boilers in power generation plants.
Experimental materials and methods
The substrate material was 16Mo3 boiler steel. The chemical composition of this
steel corresponds to norm EN 10028-2:2009.
The feedstocks for coatings deposition were commercially available powders:
Oerlikon Amdry 4535 nickel-chromium powder (The chemical composition of the
powder is shown in Table 1.) enriched with 1 % of pure metallic Rhenium (ECOREN
S.A., purity of 99.99 %, average grain size of about 4 μm). They were milled in high
energy ball mill. Thermal spraying coating techniques were used. The first technique
was Plasma spraying and the other was HVOF (High Velocity Oxy Fuel). HVOF
technique consists of bombarding substrate with coating molecules at very high
velocities.
Table 1 Chemical composition of Oerlikon Amdry 4535 [7]
Ni [%] Cr [%] Si [%] Fe [%] Mn [%] Others (max) [%]
Balance 19.5 0.75 0.25 0.25 0.4
Investigation methods
The microstructure of the materials was studied with a scanning electron microscope
(ZEISS AURIGA). Tribology measurements were carried out on UMT 3 (Bruker)
equipment using the ball-on-flat technique. The wear behaviour of the experimental
materials was studied during dry sliding in air. The tribological partner was a highly
polished (roughness Ra < 0.10 μm according to ISO 3290) SiC ball with a 6 mm
diameter. Three applied loads 5, 10 and 50 N, were used with the aim to study the
influence of different applied loads on the wear characteristics. The sliding speed
was 0.1 m/s and the sliding distance 500 m. The experiments were realized at room
temperature at the relative humidity of 30 ±5%. The material losses (volume of the
wear tracks) due to wear were measured by the PLu Neox 3D Optical Profiler,
ahigh precision confocal microscope by SENSOFAR, and the specific wear rates
(𝑊𝑆 ) were then calculated in terms of the volume loss (𝑉) per distance (𝐿) and
applied load (𝐹𝑁 ), according to the equation:
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𝑉 𝑚𝑚3
𝑊𝑆 = 𝐹 [ 𝑁.𝑚 ] (1)
𝑁 .𝐿
The mechanical properties of the prepared NiCrRe coatings were tested using an
Agilent G200 Nanoindenter equipped with a diamond Berkovich tip. Indents were
arranged in arrays of 5 × 5 (i.e. 25 indentations per sample) using a Continuous
Stiffness Measuring (CSM) mode with a maximum penetration depth of 1500 nm
and a distance between the indents of 50 μm. The CSM mode allowed the
simultaneous registration of depth, load and stiffness during each test from which
the hardness (𝐻) and Young’s modulus (𝐸) depth-profiles were automatically
calculated according to the Oliver-Pharr method.
The characteristic microstructures of the investigated substrate-coating system is
illustrated in Fig.1,2. As is visible, the Plasma sprayed coating thickness is approx.
450 μm, coating contains number of pores and there is significant borderline
between substrate 16Mo steel and NiCrRe coating formed by Plasma. The thickness
of NiCrRe HVOF coating is approx. 870 μm. The HVOF coating exhibits lower
among of porosity compared to Plasma sprayed coating.
a b
Fig.1 Thickness of NiCrRe Plasma sprayed (a) and HVOF (b) coatings on 16Mo3 steel
Microstructural observations (Fig. 2.) pointed out that the NiCr layer with several
micrometres white isles of Rhenium possessed porosity, oxidized, un-melted and
semi-melted particles, and inclusions.
The coefficients of frictions for the investigated NiCrRe coatings and 16Mo3 steel,
obtained from the wear test at loads of 5 N, 10 N and 20 N, are illustrated in Fig. 3.
The average values of the COF were very similar. In case of NiCrRe coating small
and systematic influence of the applied load was found on the values of the COF:
with increasing load, the COF NiCrRe was slightly increasing; and on the other
hand, for 16Mo3 steel, it was the same.
The wear rates of the investigated Plasma sprayed coating, HVOF sprayed coating
and 16Mo3 steel substrate are shown in Tab. 2 and the characteristic wear track at
loads of 5 N, 10 N and 20 N are illustrated in Fig. 4.
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Fig. 2 Microstructure of HVOF sprayed NiCrRe coating - a, Plasma sprayed coating - b
Fig. 3 Coefficient of friction of investigated

NiCrRe Plasma sprayed coating
(a),HVOF sprayed coating, (b) and
16Mo3 steel at applied loads of 5 N,
10 N and 20 N
The average wear rates of NiCrRe Plasma sprayed coating and substrate steel
tested at the applied load 10 N were very similar. At the applied load 5 N was
average wear rate of NiCrRe Plasma sprayed coating significantly lower than in
case steel substrate, but on the other hand, at applied load 20 N was average wear
rate of steel substrate significantly lower than in case of NiCrRe coating. The
average wear rates of NiCrRe coating sprayed by HVOF technique compare with
NiCrRe coating sprayed by Plasma and steel substrate were lower at all applied
loads.
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Fig. 4 The average wear rates of NiCrRe

Plasma sprayed coating (a), NiCrRe
coating sprayed by HVOF
technique (b) and steel substrate
16Mo3 at loads 5 N, 10 N, 20 N
Table 2 Hardness, elastic modulus and specific wear rates at applied load 5 N, 10 N and 20 N
Specific wear Specific wear Specific wear rate
Mudulus Hardness
Sample rate (5N load) rate (10N load), (20N load)
[GPa] [GPa] 3 3 3
[mm /N.m] [mm /N.m] [mm /N.m]
-6 -6 -6
Steel 223,5±8,7 2,55±0,25 5,7 x 10 5,7 x 10 6,8 x 10
NiCrRe -6 -6 -6
158±24,4 3,74±0,76 2,2 x 10 4,5 x 10 10,8 x 10
(Plasma)
NiCrRe 237,6 -6 -6 -6
6,3 ± 0,68 1,54x10 3,14x10 5,96x10
(HVOF) ±10,2
Indentations were made on both coatings and substrate to reveal true hardness.
Table 2 shows a significantly higher hardness of NiCrRe Plasma sprayed coating
(3,74 ±0,76 GPa) in comparison to the 16Mo3 steel substrate (2,55 ±0,25 GPa). It
probably caused lower wear rates of NiCrRe coatings at lower loads. On the other
hand steel substrate had higher indentation modulus (223,5 ±8,7 GPa) in
comparison to the NiCrRe coating (158 ±24,4 GPa). The HVOF sprayed coating is
the hardest material compare with other materials (NiCrRe sprayed coating and
steel substrate). The measurement results can also be compared in the graph in
Fig.5.
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Fig. 5 Indentation modulus and hardness of NiCrRe coatings formed by Plasma (a) and
HVOF (b) processing route
Conclusions
The aim of the present investigation was to study the microstructure characteristics,
hardness and wear characteristics of NiCrRe coating on 16Mo3 steel, process by
plasma spray and HVOF routes. The main results are:
 The thickness of and the plasma sprayed layer was approximately 450 µm, the
HVOF sprayed layer approximately 870 µm.
 The plasma sprayed NiCr layer with white isles of rhenium possessed porosity,
oxidized, un-melted and semi-melted particles, and inclusions, the chemical
composition of HVOF layer was based on nickel, chromium-with white isles of
rhenium.
 The average values of the indentation modulus, hardness and coefficient of
friction of plasma sprayed layer were EIT = 158 ±24,4 GPa, HIT =3,74 ±0,76 GPa
COF = 0,45 and the HVOF layer EIT = 237,6 GPa, HIT = 6,3 GPa and COF = 0.4,
respectively.
 HVOF sprayed technique results better results in comparison to plasma sprayed
technique in all fields of this research.
Acknowledgements: The work was supported by the project Slovak Grant Agency for
Science, grant No. 2/0163/16 by APVV-15-0469 and by the project MNT- ERA, NiCrRe.
References
[1] M.F .Morks, C.C. Berndt: Applied Surface Science. 256 (2010) 4322–4327.
[2] H. Hamatani, N. Shimoda, S. Kitaguchi: Science and Technology of Advanced Materials..
4 (2003) 197–20.
[3] M.A. Uusitalo, P.M.J. Vuoristo, T.A. Mantyla: Surface and Coatings Technology. 161
(2002) 275–285.
[4] S. Venetskii, Rhenium, Metallurgist. 15(04) (1971) (Russia).
[5] V. Kindrachuk, N. Wanderka, J. Banhart, D. Mukherij, D. Del Genovese, J. Rosler: Acta
Materialia. 56 (7) (2008) 1609-1618. DOI:10.1016/j. actamat.2007.12.010.
[6] L. Huang, X.F. Sun, H.R. Guan, Z.Q. Hu: Surface and Coatings Technology. (2006) 6863-
6870. DOI:10.1016/j.surfcoat. 2005.10.037
[7] https://www.oerlikon.com/ecomaXL/files/metco/oerlikon_DSMTS-
0109.2_Ni20Cr_Powders.pdf&download=1
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XPS CHARACTERIZATION OF EuNbO4 THIN FILM

PREPARED BY SOL-GEL METHOD
1 2 3 1
Helena Bruncková , Mária Kaňuchová , Hristo Kolev , Ľubomír Medvecký
1
Institute of Materials Research, SAS, Košice, Slovakia
2
Technical University, FBERG, Košice, Slovakia
3
Institute of Catalysis, Bulgarian Academy of Sciences, Sofia, Bulgaria
e-mail: hbrunckova@saske.sk
Transparent europium niobate EuNbO4 (ENO) thin film (~100 nm) was prepared by sol-
gel/spin-coating process on alumina substrates with PbZrO 3 (PZ) interlayer and annealing at
1000°C. Surface chemistry was investigated by X-ray photoelectron spectroscopy (XPS). The
3+ 2+
XPS demonstrated two valence states of Eu (Eu /Eu ) in powder precursor as
nanophosphor for lighting and display technologies. Eu concentration (at.%) decreases from
11 % in precursor to 2 % in film considering the substrate contains C, Al, Si, Pb and Zr
elements (40 %) at Nb (6 %) and O (52 %). The X-ray diffraction (XRD) analyses verified
formation of the monoclinic (M-EuNbO4), and tetragonal (T-EuNb5O14) phases in precursor
3+
and film. Single valence state of Eu was confirmed in ENO film designed for the application
in environmental electrolytic thin film devices.
Keywords: sol-gel, thin films, EuNbO4, polymorphs; XPS.
Introduction
Europium niobate EuNbO4 (ENO) ceramics and film have possess mixed types of
conduction processes, including protonic, ionic, and electronic conduction which is
determined by fabrication conditions and these materials are promising for sensors,
solid fuel cell electrolytes and high-temperature proton conductors [1,2]. For ENO,
there are two crystalline forms, the low temperature M-phase isostructural with
monoclinic form of the fergusonite and the T-phase corresponding to tetragonal
scheelite [3,4].
X-ray photoelectron spectroscopy (XPS) of element core levels is among the most
prominent methods applicable for chemical bonding characterization in complex
compounds [5,6]. Niobates are characterized by a set of binding energies (B E)
related to maxima of Nb 3d and O 1s lines. The valence state of europium and the
Eu 3d core level XPS spectra of EumNbxOy compounds and Eu2O3 thin film were
studied [7,8]. The splitting of the 3d core level in 3+ and 2+ states interpreted Cho et
6 7
al. as a consequence of Eu 4f and Eu 4f final state configurations [9]. The ENO
compounds seem to be interesting due to possible existence of mixed valence state
of Eu ions.
In this paper, we prepared EuNbO4 (ENO) precursor by sol-gel method. XPS
measurements have been done in order to investigate the chemical composition and
bonding state of ENO phosphor powder. We also report the surface chemistry of
ENO thin film prepared by spin-coating and annealed at 1000 °C. We have
Jahodná, Slovakia
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XPS CHARACTERIZATION OF EuNbO4 THIN FILM PREPARED BY SOL-GEL METHOD
H. Bruncková, M. Kaňuchová, H. Kolev, Ľ. Medvecký
3+
performed a more detailed investigation of the chemical state of the Eu (Eu and
2+
Eu ) in ENO.
Experimental
EuNbO4 (ENO) precursor was prepared by sol-gel method [10]. The ENO powder
precursor was annealed at 1000 °C for 1 hour in air. The Al2O3 substrate was spin-
coated with PbZrO3 (PZ) sol precursor at 2000 rpm for 30 s (PZ interlayer) followed
by drying and calcining at 400°C for 3 min. EuNbO4 thin film was prepared from the
ENO sol precursor synthesized in the stoichiometric ratio and deposited on PZ/Al 2O3
substrate. Final ENOF film was annealed at 1000°C for 1 hour in air [10].
The surfaces of samples were analysed by X-ray photoelectron spectroscopy (XPS).
Photoelectron spectroscopy was performed using XPS instrument (SPECS)
equipped with PHOIBOS 100 SCD and non-monochromatic Al/Mg twin X-ray
source. The data were analysed by SpecsLab2 CasaXPS software (Casa Software
Ltd). The XPS spectra of Nb, O and Eu were compared with NIST XPS Database.
The XPS was employed to evaluate the surface chemical composition and the
oxidation states of individual elements in the powder and thin film. The XPS
spectrum of EuNbO4 powder in a wide energy range are shown in Fig. 1a. Besides
carbon, no foreign impurities were found in samples. The survey XPS scans
commonly showed Eu 3d, Eu (Auger), Eu 4d, O 1s, C 1s, Nb 3d and Nb 3p peaks.
Fig. 1a also presents all peaks related to the ENO: Eu 3d between 1120 and
1190eV, Nb 3p at 367 and 382 eV, Nb 3d at 207 and 209 eV. Peaks related to
oxygen (O 1s) bonds were observed at around 530 eV and peaks corresponding to
O KLL Auger´s line at 973 eV were identified for niobate [11]. The XPS survey
spectra of ENOF thin film, substrate Al2O3 and PZ interlayer in a wide energy range
are shown in Fig. 1b,c,d. Spectra indicate elements Al, Si from substrates, Pb, Zr,
from interlayer, Eu, Nb from film, C and O on the film surfaces.
The Eu 3d core-level XPS spectra of EuNbO4 powder and thin film and deconvoluted
of spectra are shown in Fig. 2 and 3. The features of Eu 3d5/2 and Eu 3d3/2 are fitted
with combined Gaussian-Lorentzian functions which reveals 3+ state of Eu (at
binding energy 1134.2 eV) with a satellite peak corresponding to 2+ state
(1127.1eV) for Eu 3d5/2 core level, whereas fitting of Eu 3d3/2 shows presence of 3+
state (1164.2 eV) and satellite peak at 1154.5 eV (2+) [7,8]. Cho and Oh [9] labeled
4 6
prominent peaks as 3+ due to the trivalent 3d f configuration (from bulk) while they
labeled other weaker peaks located at a lower BE than the main peak as 2+, which
4 7
corresponds to the divalent 3d f configuration (from surface).
3+ 2+
The contents of Eu and Eu states were 9 at.% and 1 at.%, respectively in the
3+
ENO powder and 2 at.% of Eu in the ENO film (Table 1 and 2). The presence of
2+
Eu states may induce oxygen vacancies in Eu2O3 [12]. High-resolution XPS
spectrum of the Eu 3d core level for the ENOF film is shown in Fig. 3. The doublet at
3+
1134.4 and 1164.2 eV can be attributed to Eu 3d5/2 and 3d3/2 core levels,
respectively.
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Fig. 1 XPS survey spectra of (a) EuNbO4 (ENO) precursor, (b) ENOF thin film,
(c) Al2O3 substrate and PZ interlayer.
The analysis of peak positions and binding energies in the XPS spectra in the region
corresponding to the 3d5/2 and 3d3/2 core levels of Eu ion (2 at. %) confirms that Eu
3+ 5+
characterizes single Eu oxidation state. The peaks of Nb 3d centered at 206.7
and 209.5 eV can be assigned to 3d 5/2 and 3d3/2 states, respectively. The
deconvoluted spectrum of O 1s verifies triplet at 527.8, 530.0 and 532.1 eV. The
main intense peak centered at 530.0 eV is attributed to the Eu-O and Nb-O in ENO
3+
powders [41]. The oxygen ions in the films are bonded to the Eu ions.
Tables 1-2 represent a comparison of Eu, Nb, and O relative concentrations (at.%)
in EuNbO4 precursor (Table 1) and ENOF thin film (Table 2). The Nd/Nb/O ratio was
determined to be 0.7:1.0:4.1 (in precursor) and 0.3:1.0:8.9 (in film).
Jahodná, Slovakia
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Fig. 2 HR XPS spectra of Eu 3d, Nb 3d and O 1s and deconvolution peaks for EuNbO4
(ENO) precursor
Fig. 3 HR XPS spectra of Eu 3d, Nb 3d and O 1s and deconvolution peaks for ENOF thin film
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Table 1 Surface relative concentration (at.%) of EuNbO4 powder after annealing at 1000°C
for 1 hour
C 1s
Element O 1s Eu 3d Nb 3d
(hydrocarbons+CO32-)
Conc.
9 66
(at. %)
Eu Nb-O non
Bond C-H C=O 11 16
MNN Eu-O lattice
Conc.
7 2 3.7 51.4 10.9
(at. %)
73 10
Conc.
- 17
(at. % )
4 57 12 1 9
1127.1 1134.2 206.7
BE (eV) 285.0 289.8 527.8 530.0 532.1
1157.1(Eu2+) 1164.2 (Eu3+) 209.4 (Nb5+)
Eu:Nb:O = 0.7:1.0:4.1  = 30 eV  = 2.7 eV
Table 2 Surface relative concentration (at.%) of EuNbO4 film after annealing at 1000 °C for
1hour
C 1s Eu Nb Pb Zr Al Si
Elem. (adventitious O 1s
3d 3d 4f 3d 2p 2p
hydrocarbons)
Conc.
20 52 2 6 2 2 6 10
(at.%)
Nb-O Eu,
Bond C-H C-O OH-
Eu-O Nb-O
Conc.
13 7 23 24 5
(at.%)
1134.4 206.8 138.5 182.2
BE
285.0 286.8 530.0 531.9 533.6 1164.4 209.5 143.3 184.6 74.5 102.6
(eV)
(Eu3+) (Nb5+) PbO ZrO2
Eu:Nb:O= = = = =
0.3:1.0:8.9 30 eV 2.7 eV 4.87eV 2.4eV
Conclusion
The EuNbO4 (ENOF) thin film (~100 nm) was fabricated by sol-gel/spin-coating
method on Al2O3 substrate with PZ interlayer (~50 nm) and annealed at 1000 °C.
X-ray photoelectron spectroscopy (XPS). XPS results demonstrate the existence of
3+ 2+
Eu and Eu ions in EuNbO4 precursor. The Eu 3d5/2 peak consists of strong
3+ 5 2+
features characteristic of Eu (1134.2 eV) with electron configuration (4f ) and Eu
6 3+
(1127.1 eV) with electron configuration (4f ). The molar concentration of Eu in
2+
ENO was higher (9.0 at.%) than Eu (1.0 at.%) .
3+
The XPS demonstrated one valence state of Eu (Eu ) in thin film. The relative
concentration of Eu on surface of ENO (10.0 at.%) precursor was higher than thin
film (2 at.%). Presently, europium niobates have been observed with XPS, and
Jahodná, Slovakia
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further accumulation of experimental results is beneficial for the design of new

effective electrolytic materials.
Acknowledgement: This work was supported by the Grant Agency of the Slovak Academy of
Sciences through project No. 2/0036/17.
References
[1] Atuchin, V.V., Borisov, S.V., Pervukhina, N.V., Zhang, Z.: Int. J. Appl. Phys. Math. 1
(2011) 38-42.
[2] Voloshyna, O., Boiaryntseva, I., Spassky, D., Sidletskiy, O.: Solid St. Phenom. 230
(2015) 172-177.
[3] Siqueira, K.P.F., Lima, P.P., Ferreira, R.A.S., Carlos, L.D., Bittar, E.M., Matinaga, F.M.,
Paniago, R., Krambrock, K., Moreira, R.L., Dias, A.: J. Phys. Chem. C 119 (2015) 17825-
17835.
[4] Siqueira, K.P.F., Moreira, R.L., Dias, A.: Chem. Mater. 22 (2010) 2668-2674.
[5] Teterin, Y.A., Bondarenko, T.N., Teterin, A.Y., Lebedev, A.M., Utkin, I.O.: J. Electron
Spectrosc. Relat. Phenom. 96 (1998) 221-228.
[6] Atuchin, V.V., Grivel, J.C., Zhang, Z.: Chem. Phys. 360 (2009) 74-78.
[7] Mercier, F., Alliot, C., Bion, L., Thromat, N., Toulhoat, P.: J. Electron Spectrosc. Relat.
Phenom. 150 (2006) 21-26.
[8] Kumar, S., Prakash, R., Choudhary, R.J., Phase, D.M.: Mater. Res. Bull. 70 (2015) 392-
396.
[9] Cho, E.J., Oh, S.J.: Phys. Rev. B 59 (1999) 15613-15616.
[10] Brunckova, H., Mudra, E., Medvecky, L., Kovalcikova, A., Durisin, J., Sebek, M., Girman,
V.: Mater. Des. 134 (2017) 455-468.
[11] Dutta A., Saha S., Kumari P., Sinha T.P., Shannigrahi S.: J. Solid State Chem. 229
(2015) 296-302.
[12] Khare, A., Choudhary, R.J., Phase, D.M., Sanyal, S.P.: J. Appl. Phys. 109 (2011)
123706.
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Mária Kavanová, Alexandra Kloužková

Department of Glass and Ceramics, University of Chemistry and Technology
Prague, Technická 5, 166 28 Prague, Czech Republic
e-mail: maria.kavanova@vscht.cz
The main reason of using surface coatings is, in addition to aesthetic requirements, an
increase of the resistance of the surface in corrosive environments. Glazes may be applied to
various types of ceramic substrates i.e. chemical reactors, dental implants, ceramic whiteware
and tiles, porcelain, insulators, ceramic roofing etc. All these products are expected to be
highly resistant to various types of degradation processes such as corrosion by environment
or thermal stresses developed during production or usage. Defect formation is the main and
the most obvious sign of all these undesirable changes of the ceramic body - surface finishing
system. The measurement of thermal expansions of contemporary and historical glaze -
ceramic body systems by several types of thermal analyses confirmed that the obtained data
are suitable for the calculation of stress relations in real glazed ceramic products. The most
common types of historical glaze defects were caused by poor system selection or improper
storage conditions.
Keywords: ceramic coating, degradation, defect, corrosion environment, ceramic surface
Introduction
Engobes, glazes or enamels are characteristic types of surface finishing applied on
a ceramic substrate. Glazes are the most used and common coatings that modifies
the surface of ceramic products. To serve its purpose a glaze as a stable glassy
substance consisting predominantly of silica modified by alkali and other elements
must be free from defects. After firing of glazed ceramics, the final desired properties
of surface coating are achieved. Ceramic coatings could be divided not only by the
appearance, then by the function that they perform, by presence of an important
chemical component, according to the preparation method, by fusibility or main
colourant, also by type of a ceramic substrate. The basic criterion of the usage of
surface finishing on ceramic materials is the increase of resistance to aggressive
environmental conditions. Preparation of a fusible glaze, which is devoid of faults,
has an appropriate value of coefficient of linear thermal expansion and suitable for a
specific ceramic substrate is the critical requirement to prepare a stable glaze -
ceramic body system.
The properties of a glaze itself, a substrate (i.e. a ceramic body), an interlayer and a
final glaze - substrate system should be evaluated in order to ensure the
compatibility of the glaze and the substrate, the required quality of the glazed
ceramic product after firing and the appropriate properties of the surface finishing. A
lengthy diffusion process and sintering between the glaze layer and the substrate
during firing are influenced by firing conditions, viscosity of the glaze layer during
firing, reaction with furnace atmosphere, chemical and mineralogical compositions of
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M. Kavanová, A. Kloužková
the glaze and the ceramic body. These parameters affect the stability and
applicability of the final product at the same time [1].
The factors that influenced the degradation and chemical stability of surface finishing
of ceramic material can be classified into three main categories. The first group of
factors is the environmental one, where the main agents are temperature, relative
humidity, concentration of pollutants in the environment and duration of action. The
other factors that influence the long-term stability of ceramic products are physical
conditions of degradation (e.g. dynamic or static conditions, S/V, pH etc.), and most
importantly, the state of ceramic materials itself (thermal history, surface conditions,
homogeneity, composition etc.) plays an important role. [1-6]
Defects of a ceramic body or a glaze are checked and eliminated, because they are
the main cause of financial loss in ceramic industry and small ceramic workshops
[7].
In general, defects formed within the layer of the surface finishing can be divided
into four main groups [8]:
• structural (crazing, flatness etc.),
• surface (pinholes, cracks, bubbles or specks),
• aesthetic (mainly due to impurities [9]),
• procedural (due to poor manipulation).
Faults of ceramics may occur at any production stage and frequently relates to
several parallel origins. However, the knowledge of the form of glaze weakness and
use of ceramic product is necessary to evaluate surface defects and to suggest the
best curing process to reduce fault occurrence. Defects of surface ceramic finishing
are of different origin and source and the understanding of potential causes and their
removals is critical [10]. Surface finishing faults are divided into defects that arise
due to the inappropriate interaction of coating and ceramic substrate, surface
defects of coating and flaws due to biological colonization.
Defects due to interaction of glaze and its substrate are results of the mismatch of
parameters of the glaze and the ceramic body. Typical crazing or peeling are
defects that arises during production process or use of the final glazed ceramics and
are caused by inappropriate residual stresses or by changes in one of the two
layers.
Surface defects result mostly from interaction of the glaze layer and the surrounding
environment. The last type of defects are special case of degradation divided into
biophysical degradation that induce mechanical damage of ceramics by penetration
of biological factors and subsequent high compressive stresses and biochemical
degradation that cause corrosion by organic or inorganic acids produces by
organisms.
The main aim of this work was to study various types of degradation of ceramic
surface finishing and to evaluate the origin or source of the defects. The first part
deals with the evaluation of surface degradation of contemporary glazed tiles and
determination of stress relations. The second part was focused on identification of
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defects of several kinds of historical glazed tiles using optical (OM) and scanning
electron microscopy (SEM). The origin of these faults was detected.
Experimental part
A combination of following analytical techniques was used for identification of defect
sources and origins:
 Determination of chemical compositions of surface finishing, substrate and
possible corrosion products was performed by X-ray fluorescence analysis. The
+
fully automatic sequential WD-XRF spectrometer ARL 9400 XP was used and
measured data were evaluated by software Uniquant 4.
 X-ray diffraction was used as initial characterization methods to provide the
information about mineralogical compositions. Crystalline phases were
determined by X-ray diffractometer PANanalytical X´Pert PRO with Bragg-
Bretano parafocusing geometry using CuKα radiation at an angle 5-70° 2θ.
Evaluation was carried out by PANanalytical High Score Plus 3.0 software
package and a database of reference samples.
 Optical and scanning electron microscopy was used for the study of
morphology of surface finishing and determination of defects and their types.
Microscopic observations were performed using polarizing optical microscope
Olympus BX51, stereomicroscope Olympus SZ61 and scanning electron
microscope Tescan Vega 3 LMU.
 Evaluation of changes in material properties due to thermal load was carried
out by thermal analyses especially simultaneous thermal analysis in TG-DTA
mode, dilatometry and thermomechanical analysis. STA was performed by
Linseis STA PT 1600/1750°C HiRes system, dilatometry was measured by
Linseis L75 HS 1600C PT dilatometer and thermomechanical analysis by TMA
CY04R analyser.
Microscopic observations together with data measured by thermal analyses and
calculated stress relations confirmed that surface degradation of contemporary
glazed tiles was caused by residual stresses. Figure 1A shows defect formation of
contemporary stove tile H.
A B
Fig. 1 Defects due to interaction of glaze and its substrate: A - crazing and B - peeling
Jahodná, Slovakia
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M. Kavanová, A. Kloužková
Inappropriate tensile stress in the glaze lead to crazing extending from the surface of
the glaze to the glaze - ceramic body interface. This type of degradation could be
supported be moisture expansion.
However, the failure pattern observed within the surface of the glaze GB (Figure 1B)
was indicated by intense compressive stress. A larger mismatch in thermal
expansion induced peeling or shivering of the glaze. Stresses generated within the
glaze exceeded the strength of adhesion between the glaze and its substrate.
A B
Fig. 2 Surface defects of glazes caused

by:
A - mechanical abrasion,
B - specking and
C- surface texture and bubble
C formation
On the other hand, glaze - ceramic body systems in Figure 2 with moderate stress
relations were degraded due to interaction with surrounding. The glaze of the
historical tile S5 (Figure 2A) was severely degraded by mechanical abrasion during
exposition to abrasive environment of a waste pit. Specking is a specific type of
interaction with environment caused by contamination of a surface by extraneous
material often during production. Impurities were deposited within the surface of the
glaze R4 during firing (Fig. 2B). The most common types of surface degradation of
historical fragments originate from the underlying material of the ceramic body.
Large temper grains could expand and cause the delay crack formation on a
surface. This type of degradation was detected within the glaze GHB of historical
floor tile (Fig. 2C).
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Conclusion
The study showed that defects developed by mismatch in thermal expansion of
glaze and its substrate could be detect within the surface of historical glazed
ceramics, but also is one of the main causes of degradation of contemporary
ceramics. Relative expansion curves measured by thermal analyses and
calculations of stress relations could be used for the prediction of the concordance
of glaze - ceramic body systems. Moreover, microscopic observations of surface
layers of selected ceramic systems together with all the measured data lead to the
detection of defects and their origins.
Acknowledgement: This work has been financially supported by the project of the Ministry of
Culture Czech Republic DG18P02OVV028 “Technology of Treatment and Identification of
Degradation Processes of Ceramic Finds from Hradčany Palaces – Methods of Restoration
and Conservation of Porous and Dense Ceramics and Porcelain”.
References
[1] TAYLOR, J.R. and A.C. BULL. Ceramics Glaze Technology. Oxford: Pergamon Press,
1986. ISBN 0-08-033466-0.
[2] Eppler, R.; Obstler, M. Understanding Glazes; The American Ceramic Society:
Westerville, Ohio, 2005.
[3] LI, J., J. LIANG, F. WANG and L. WANG. The role of firing process on bubble formation
in a glaze layer of sanitary ware. Thermochimica Acta. 2014, 588, 75-80. DOI:
10.1016/j.tca.2014.03.024.
[4] CLARK, D.E. a B.K. ZOITOS. Corrosion of Glass, Ceramics and Ceramic
Superconductors: Principles, Testing, Characterization and Applications. USA: Noyes
Publications, 1992. ISBN 0-8155-1283-X.
[5] LEHMAN, R.L. Lead Glazes for Ceramic Foodware. 1. Rutgers University USA: The
International Lead Management Center, 2002.
[6] MCCAULEY, Ronald A. Corrosion of Ceramics. New York: Marcel Dekker, 1995. ISBN
0-8247-9448-6.
[7] SFARRA, S., S. PERILLI, D. PAOLETTI and D. AMBROSINI. Ceramics and defects:
Infrared thermography and numerical simulations—a wide-ranging view for quantitative
analysis. Journal of Thermal Analysis and Calorimetry. 2016, 123(1), 43-62. DOI:
10.1007/s10973-015-4974-5.
[8] Applied Ceramic Technology: Volume II. 1. Imola: SACMI IMOLA s.c. a r.l., 2002. ISBN
88-88108-55-6.
[9] CARLINI, M., S. CASTELLUCCI, E. ALLEGRINI, B. GIANNONE, S. FERRELLI, E.
QUADRAROLI and M.T. SAURINI. Ceramic flaws: Laboratory tests and analysis using
Scanning Electron Microscope to identify surface defects. Journal of the European
Ceramic Society. 2014, 34(11), 2655-2662. DOI: 10.1016/j.jeurceramsoc.2014.01.009.
[10] GULEVIČ, O., V. KOUBA, et al. Technická keramika, glazury a keramické barvy. Praha:
SNTL, 1969.
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Žaneta Dohnalová, Martina Šnajdarová

Department of Inorganic Technology, Faculty of Chemical Technology,
University of Pardubice, Studentská 95, 532 10 Pardubice, Czech Republic,
e-mail: zaneta.dohnalova@upce.cz
Present work deals with the synthesis and evaluation of physical and chemical properties of
SrSn1-xAxO3 perovskite pigments, where A represents doping elements - Fe, Mn, V. These
compounds were prepared by modified solid state synthesis at high temperature. The main
attention was focused to observing the colour properties of the prepared compounds and their
sun light resistance. Also thermal stability, particle morphology and granulometric composition
of the pigments were analysed.
Keywords: perovskite, ceramic pigments, solid state reaction
Introduction
In recent years, legislation and society have placed great emphasis on the
environmental aspects of chemical productions. The production of inorganic
pigments is no exception and their ecological and hygienic safety is being examined.
Current worldwide research in the field of inorganic pigments is directed by three
basic directions that are characterized by 3E: efficiency, economics and ecology [1].
The quality of inorganic pigments is dictated by their properties and characteristics,
which are collectively referred to as pigment application properties [2,3]. The most
important characteristics in terms of use of powder materials as inorganic pigments
are physico-chemical and technological properties. An important parameter is their
colour. Some other physical properties, such as particle size and shape, refractive
index, and others are also related to colour properties. Particularly useful in terms of
dispersibility of pigments for different application environments, particle size
distribution, specific gravity and critical volume concentration of pigments are
important indicators. From the application point of view, thermal stability determining
the suitability of pigments for high temperature applications in ceramic glazes and
enamels [4] and resistance to sunlight and weather conditions are also important
indicators [5].
For a long time, the research of the Department of Inorganic Technology of the
University of Pardubice has focused on the environmentally safe synthesis routes
and at the same time on the synthesis of thermally and chemically stable inorganic
pigments that could replace the previously used pigments with not very attractive
environmental impacts. In the present work new mixed metal oxides with perovskite
structure were synthetized by solid state reaction and their potential use as the
inorganic pigments were tested.
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Ž. Dohnalová, M. Šnajdarová
Experimental part
The perovskite compounds of general formula SrSn 1-xAxO3 (where A = Fe, Mn, V
and x = 0.05-0.2) were prepared by modified solid-state reaction at high heating
temperatures using SrC2O4, SnC2O4 and dopants in form of Fe2O3, V2O5, MnCO3 as
initial materials [6]. In a typical synthesis initial reagents and surfactant polyethylene
glycol (PEG)-400 were put in a mortar grinder (Pulverisette 2, Fritsch GmbH,
Germany), and the mixture was fully ground for 30 min. The reaction mixture
gradually became damp, and then a paste formed quickly. The reaction mixture was
kept at room temperature for 24 h. Nanocrystalline powders with perovskite structure
were obtained via calcining at 950 -1300 °C for 12 hours.
The phase composition of the calcination products was studied by X-ray diffraction
analysis. The diffractograms of the samples were obtained by using a MiniFlex 600
diffractometer (Rigaku, Japan) working in Bragg-Brentano (/2) geometry with 1D
d/teX Ultra: silicon strip detector and K filter. The data were collected within 2
-1
angle from 10-80 ° at a step size of 0.02 °and speed of 10 °.min using CuK line.
CuKα1 (𝜆=0.15418 nm) radiation was used for the angular range of 2 < 35° and
CuKα2 (𝜆=0.15405 nm) for the range of 2 >35 °. The identification of individual
phases was based on the matching of the obtained diffraction patterns with the data
contained in the JCPDS database [7].
The thermal stability of final pigments was tested using a heating microscope
EM201-15 (Hesse Instruments, Germany). The samples in form of tablets were
gradually heated from room temperature to 1500 °C and a change of sample areas
-1
was detected. The heating rate was 10 K.min .
Particle size distribution of the samples was measured using a Mastersizer 2000/MU
(Malvern Instruments, UK). The equipment employs a scattering of incident light on
particles. The signal was evaluated on the basis of Mie theory. Specific surface area
was evaluated based on BET isotherm by equipment NOVA 1200e (Quantachrome
Instruments, Germany).
The colour properties of all prepared pigments were objectively evaluated by
measuring of spectral reflectance using a spectrophotometer ColourQuerst XE
(HunterLab, USA). The measurement conditions were the following: an illuminant
D65, 10° complementary observer and measuring geometry d/8°. The colour
properties of the samples were estimated in terms of the CIE L*a*b* system.
The assessment of resistance to day light of coloured pigments was tested
according to the general methods of the test for pigments described in ISO standard
787-15:1986. The samples were exposed to simulated sunlight in a Q-Sun Xenon
-2
Test Chamber, model Xe 1 (Lab. Products, USA) for 456 h at 0.51 W.m @ 340 nm.
The results of XRD analysis of the samples SrSn0.95A0.05O3 (A=Fe, Mn, V) after
calcination at 950 °C indicate that solid state reaction between initial reagents does
not result in a single-phased system (Table 1). The SrSn0.95Fe0.05O3 powder after
calcination at 950 °C contains rest of the unreacted reagent such as SnO 2 and
besides the perovskite SrSnO3 phase contains also spinel phase Sr2SnO4. Increase
Jahodná, Slovakia
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L 14
the calcining temperature at 1200 °C is connected with the decomposition of spinel

phase and formation of SrSnO3 type solid solution. Although diffraction lines of any
Fe compound were not detected at the diffractograms, it is supposed that the Fe
ions were built into the perovskite structure. Lattice parameters of the solid solution
SrSn0.95Fe0.05O3 after calcination at 1300 °C are: a = 0.57000 nm, b = 0.80608 nm
and c = 0.57002 nm. In the case of synthesis of the SrSn0.95Mn0.05O3, the situation
was almost analogous. While the calcining temperature 950 °C brought synthesis of
two perovskite phases SrSnO3 and SrMnO3 (Table 1), increase of temperature at
1200 °C caused formation of single phase solid solution SrSn 0.95Mn0.05O3 with lattice
parameters a = 0.57010 nm, b = 0.80625 nm a c = 0.57013 nm. Partial substitution
of Sn ions by V ions in perovskite structure of strontium stannate led to the formation
of two or three phase systems (Table 1).
Table 1 The effect of calcining temperature on phase composition of powders

Temperature
Pigment Detected phases
[°C]
950 SnO2, Sr2SnO4, SrSnO3
SrSn0.95Fe0.05O3 1200 SrSnO3 type solid solution
1300 SrSnO3 type solid solution
950 SrSnO3, SrMnO3
SrSn0.95Mn0.05O3 1200 SrMnO3 type solid solution
1300 SrMnO3 type solid solution
950 SrSnO3, Sr2VO4, VO2 and SnO2
SrSn0.95V0.05O3 1200 SrSnO3, VO2
1300 SrSnO3, Sr3V2O7, Sr2VO4
The results of colour parameters of powdered pigments (after calcination at

1300°C) and the effect of sunlight irradiation on their change are summarised in
Table 2. Light stability of pigments is defined as the resistance of materials to
discoloration caused by the action of direct sunlight. The change of the colour
properties of the powders is expressed by values of total colour difference after
-2 -2
exposition to a radiation load of 315 kJ.m , respective 664 kJ.m . Colour of
SrSn0.95Fe0.05O3 pigment is khaki green. An exposition of the powder to sunlight
irradiation caused its darkening, decrease amount of green colour hue and increase
of yellow colour hue. The total colour difference of powder (E*CIE) after irradiation is
higher than 1.5 and it expresses that the colour change is easy visible. Colour of the
pigment SrSn0.95Mn0.05O3 is dark brown. The colour of this pigment is very resistant
to sunlight action and its change after irradiation is not perceptible by human eye.
The total colour difference value after exposure to sunlight radiation (E*CIE) is less
than 0.5. The less attractive colouration of host perovskite structure was obtained by
partial substitution of tin ions by vanadium ions. Colour of the powder is very light
yellow-beige and its resistant to sunlight irradiation is also very bad (E*CIE  6). The
th
Ž. Dohnalová, M. Šnajdarová
origin of less attractive colour properties of vanadium doped perovskite SrSnO 3 is its
multi-phase composition. In the past, SrSn0.95V0.05O3 pigment was prepared by
classical ceramic route and subsequent calcination of initial reaction mixture (SrCO 3,
SnO2 and V2O5) at high temperature. Colour of the pigment prepared by such route
was intense yellow [8].
Table 2 The effect of sunlight irradiation on the change of colour parameters of powders
Time H
Pigment -2 L* a* b* E*CIE
[h] [kJ.m ]
SrSn0.95Fe0.05O3 0 0 68.25 -2.18 13.12 —
216 314.7 67.07 -1.42 14.14 1.74
456 664.20 66.28 -1.08 14.10 2.46
SrSn0.95Mn0.05O3 0 0 50.47 10.26 14.09 —
216 314.7 50.12 10.54 13.93 0.48
456 664.20 50.15 10.47 13.91 0.42
SrSn0.95V0.05O3 0 0 86.00 -0.53 6.69 —
216 314.7 79.68 1.28 7.43 6.62
456 664.20 79.18 1.47 7.33 7.14
Technological important properties such as particle size, specific surface area and
thermal stability of powder are summarised in Table 3. Particle sizes of pigments
less than 10 m is optimum for applications of pigment to organic binder system and
also for application into ceramic glazes. Wider particle size distribution of V doped
SrSnO3 can be done by the multi-phase composition of sample. Thermal stability of
powders was measured by heating microscope. The sintering of powders stared at
temperature higher than 1250 °C. High thermal stability of pigments predicts that the
powders SrSn0.95Fe0.05O3 and SrSn0.95Mn0.05O3 can be used for colouration of
ceramic glazes.
Table 3 Granulometric composition, specific surface area and thermal stability of powders
Pigment d50 d10 - d90 SBET Tsint
2 -1
[m] [m] [m .g ] [°C]
SrSn0.95Fe0.05O3 0.60 1.77-9.91 3.46 1270
SrSn0.95Mn0.05O3 0.63 2.34-9.24 2.04 1250
SrSn0.95V0.05O3 0.91 5.30-33.70 0.77 1260
Conclusion
Present work contains results related to the synthesis of perovskite pigments based
4+
on structure of SrSnO3 in which a part of Sn ions was substituted by iron,
manganese and vanadium ions. The pigments were synthetized by modified solid
state reaction between strontium and tin oxalates and transition metal oxides in the
presence of surfactant polyethylene glycol. Formation of single phase solid solution
in the case of Fe and Mn substitution was detected after calcination at 1200 °C.
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Colour of SrSn0.95Fe0.05O3 powder is khaki green and pigment SrSn 0.95Mn0.05O3 is

dark brown. Preparation of SrSn0.95V0.05O3 perovskite pigment by this synthesis
route was not successful. Thermal stability and particle size distribution of powders
are suitable for testing of pigments for colouration of ceramic glazes.
References
[1] G. Pfaff: Special effect pigment, Vincentz Network (2008).
[2] E.B. Faulkner, R.J. Schwartz: High performance pigments, Wiley-VCH Verlag GmbH &
Co. KGaA (2009).
[3] G. Pfaff: Inorganic pigments, De Gruyter (2017).
[4] F. Bondioli: Inorganic pigments to colour ceramic materials: State of the art and future
trends (Chapter 13), Dyes and Pigments: New research, Nova Science Publishers, Inc.
(2009).
[5] G. Buxbaum: Industrial inorganic pigments, Wiley-VCH Verlag GmbH & Co. KGaA
(2005).
[6] K. Zhou, W. Wu, Y. Li, X. Wu, S. Liao: J Therm Anal Calorim (2013) 114:205–212.
[7] Joint Committee on Powder Diffraction Standards. International Centre of Diffraction
Data. Swarthmore: JCPDS; 1983.
[8] L. Adolfová, Ž. Dohnalová, P. Šulcová: J Therm Anal Calorim (2013) 113:161–167.
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CHARACTERIZATION OF PIGMENTS AND DYES OF SURFACE

FINISHING USING RAMAN SPECTROSCOPY
1 1 1 2
Mária Kavanová , Alexandra Kloužková , Pavla Dvořáková , Radka Šefců
1
Prague, Technická 5, 166 28 Prague 6
2
Chemical-technological Laboratory, National Gallery Prague, U Milosrdných 17,
110 00 Prague 1
e-mail: maria.kavanova@vscht.cz
Different types of Raman spectroscopy techniques were used to the study of surface finishing
and their main component of ceramic products. It was proved that Raman analysis is the best
applicable technique for identifying the main components of different types of surface
treatments.
Keywords: Raman spectra, FT-Raman, Raman microscopy, pigments, surface finishing
Introduction
Several analytical techniques including Raman spectroscopy are widely used for the
identification of pigments, raw materials and ceramics in conservation science.
Archaeological and historical glazed ceramic fragment are often characterised by a
combination of analyses to obtain an overall identification of the sample. Raman
spectroscopy was applied as a non-destructive technique, which could provide the
information about pigments, dyes and surface coatings. FT-Raman has been also
successfully used to identify colouring agents within the surface of glazes.
Ceramic products are widely surface treated, their surfaces are coated by different
types of surface finishing (e.g. enamels, engobes, glazes, lusters, graphite coatings,
ceramic colours and pigments or mechanical decorations etc.). Coatings are applied
on green ceramic body, one-fired ceramic product or as another decoration of low-
fired ceramics. Dense surface finishing like engobes or glazes are fixed on the
surface by thermal load. [1-4]
Organic dyes and resin together with organic-inorganic pigments and inorganic
pigments (e.g. cochineal, Maya Blue, hematite etc.) were widely used as surface
coating of since the beginning of ceramic production. Only small remains of these
surface finishing persist on surface of ceramic fragments, however they could be
very well identified by Raman techniques [5].
The main aim of this work was to identify different types of surface finishing of
ceramics by Raman techniques. Four types of laser wavenumbers (532, 623, 785
and 1064 nm) were used for measurements of pigments, dyes and glazes, which
have been partially covered by corrosion products. The appropriate choice of laser
has an important impact on experimental capabilities as sensitivity and spatial
resolution. Sample behaviour has the essential effect on the optimisation of
measurement technique.
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CHARACTERIZATION OF PIGMENTS AND DYES OF SURFACE FINISHING USING RAMAN
SPECTROSCOPY M. Kavanová, A. Kloužková, P. Dvořáková, R. Šefců
Experimental part
Three types of analytical instruments, which are equipped with several different laser
wavenumber, were used for collection of Raman spectra:
 The carbon content and identification of the form in which it is present in
surface finishing of ceramic findings from the Hallstatt period was analysed by
Raman microspectroscopy. The Labram HR (Jobin Yvon) dispersive
spectrometer with 632 nm laser was used for analysis in a spectral range of
-1
100 - 4000 cm .
 Surface finishing of ceramic storage container found during archaeological
research of Salm Palace was studied by dispersive Raman microscope Nicolet
DXR with confocal microscope. The spectrometer is equipped with 623 nm and
785 nm lasers. The maximum power used was 50 mW or 40 mW respectively.
 Pigments of green glaze of Renaissance technical ceramic bowl from waste pit
at Prague Castle were identified by micro-Raman spectroscopy using a
dispersive Raman microscope Nicolet DXR and by FT-Raman spectroscopy
using a FT-IR spectrometer iS50 Nicolet equipped with FT-Raman module.
Analyses were performed using a 785 nm diode laser, maximum power of 5 -
7mW with acquisition time of 5 minutes and using a 1064 nm laser with
maximum power 50 - 500 mW. Measurements took place in the range between
-1 -1
3300 and 50 cm . The spectral resolution was 4 cm .
 Glazes of unique large-format tiles with relief colourful decors from
archaeological finds of Hradčany Palaces were studied by Labram HR
spectrometer Jobin–Yvon and by dispersive Raman microscope Nicolet DXR.
Analyses were performed using 532 nm laser wavenumber in the range 100 -
-1 -1
4000 cm and using 785 nm diode laser in the range 50 - 3300 cm .
All measured Raman spectra were evaluated using software Omnic.
Raman spectroscopy was used to identify different types of carbon coating applied
on the surface of ceramic terrine T29 and bowl T30 from Hallstatt period found in
Tišice and Renaissance storage container SP form archaeological find of Salm
Palace in Prague.
The analyses confirmed that the surface finishing of prehistoric fragments of
ceramics were high gloss ceramic surface reminiscent of graphite burnishing [6].
This decoration technique was widely used in Central Europe during Bronze and
Iron Age and is called graphite coating. Within surface layer applied on the surface
of Renaissance container SP was identified different phase of carbon. The coating
was formed as a definite layer during firing process from charring organic material.
Amorphous carbon coating was identified as carbon black surface finishing of
sample SP, which is characterized by two broad bands at about 1360 and
-1
1590cm . These two types of carbon-based coating could be well distinguished by
Raman spectroscopy (Fig. 1).
th
L 15
Fig. 1 Comparison
ofmeasured Raman
spectraand reference
spectra
A - Raman spectra
ofsample SP and
B - Raman spectra
ofsurface of samples
T29 and T30
FT-Raman and dispersive Raman instruments were used for the measurement of
Raman spectra of green and yellow glaze of Renaissance ceramics. In both glazes
-1
were observed yellow grains with Raman signals at 132 and 138 cm , which could
be attributed to Pb-Sn-based compounds known as lead-tin yellow or to Pb-Sb
-1
based compounds known as Naples yellow. Raman band 334 and 508 cm in
Figure 2B were identified as Naples yellow bands and correspond to a reference
spectra of Naples yellow (Pb(SbO3)2, Pb(SbO4)2). The identification of Naples yellow
in green glaze was affected by bands of other phases in the glaze mainly band 146
-1
and 207 cm which are attributed to anatase.
Conclusion
The paper presents Raman spectra of surface finishing of historical ceramic
fragments, which were measured by three different Raman instruments using four
types of laser wavenumbers. The data collected proved great efficiency of surface
layer identification by Raman spectroscopy. Two specific types of carbon coating of
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CHARACTERIZATION OF PIGMENTS AND DYES OF SURFACE FINISHING USING RAMAN
SPECTROSCOPY M. Kavanová, A. Kloužková, P. Dvořáková, R. Šefců
different origin were identified within the surface of tile prehistoric ceramic fragments
from Hallstatt period and Renaissance container. Moreover, the Raman spectra of
green and yellow glazes of Renaissance ceramics proved that both colours were
made using similar raw materials.
A B
Fig. 2 Measured Raman spectra of glazes: A - yellow grains in the green glaze of technical
bowl and B - yellow glaze of large-format tile
References
[1] TAYLOR, J.R. and A.C. BULL. Ceramics Glaze Technology. Oxford: Pergamon Press,
1986. ISBN 0-08-033466-0.
[2] HANYKÝŘ, V. and J. KUTZENDÖRFER. Technologie keramiky. 2nd. Praha: Silikátový
svaz, 2010. ISBN 978-80-86821-48-1.
[3] CAGGIANI, A.C. a P. COLOMBAN. Raman microspectroscopy for Cultural Heritage
studies. Physical Sciences Reviews. 2018, 3(11), 1-18. DOI: https://doi.org/10.1515/psr-
2018-0007.
[4] BURGIO, L. a R.J.H. CLARK. Library of FT-Raman spectra of pigments, minerals,
pigment media and varnishes, and supplement to existing library of Raman spectra of
pigments with visible excitation. Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy. 2001, 57(7), 1491-1521.
[5] KLOUŽKOVÁ, A., M. KAVANOVÁ, M. KOHOUTKOVÁ, K. KLÁPŠŤOVÁ, P. DVOŘÁKOVÁ
a A. MICHALCOVÁ. Archaeometric study of ancient Maya figurines from the collection of
the National Museum. Journal Ceramics-Silikáty. 2018, 62(4), 418-431. DOI:
10.13168/cs.2018.0039.
[6] CHU, P.K. a L. LI. Characterization of amorphous and nanocrystalline carbon films.
Materials Chemistry and Physics. 2006, 96, 253–277. DOI:
10.1016/j.matchemphys.2005.07.048.
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Miroslav Hnatko, Michal Hičák, Jaroslav Sedláček, Pavol Šajgalík

Institute of Inorganic Chemistry, Slovak Academy of Science, Dúbravská cesta 9,
842 36 Bratislava, Slovakia
e-mail: uachmiho@savba.sk, michal.hicak@savba.sk, uachjase@savba.sk,
uachsajg@savba.sk
Silicon nitride-based ceramics with SiO2, CaO and Ca3(PO4)2 as sintering additives, have
been prepared in order to investigate of substrate surface structure and composition after
flame thermal treatment. Dense ceramic bodies were oxidized by an oxyacetylene torch at
approx. 1475 °C, for 60 seconds. After oxidation, two concurrent processes occurred on the
ceramic body surface: (i) the formation of a thin glassy layer with a composition close to that
of the ceramic body grain boundary, and (ii) decomposition of silicon nitride. The latter one
resulted in the formation of gasses (N2 and SiO), which formed bubbles in the soft surface
viscous glassy phase formed by diffusion of the grain boundary oxide phases.
Keywords: silicon nitride, surface modification, acetylene-oxygen flame oxidation,
Introduction
Silicon nitride-based ceramics are characterized by high chemical resistance and a
superior combination of fracture toughness, strength, hardness, and tribological and
thermomechanical properties. These features are not only important for engineering
applications, but they are also attractive for medical applications such as implants in
the human body. A survey of the literature shows a wide range of applications [1-4]
for which these materials’ bioinertness and biocompatibility have made them
suitable. However, the majority of biological applications require not only
biocompatibility but also the additional property of bioactivity, so as to enable
stronger bonding to the host tissue. The mechanical properties of a biomaterial are
mainly governed by the bulk of the material; implant bioactivity, on the other hand, is
determined by the surface properties (as the host tissues interact with the surface of
the implant). This means that enhancement of the bioactivity of a bioinert material
like silicon nitride requires modifications of the surface to enable the host tissue to
cooperate with the implant. Bio-coatings are applied by a variety of surface
engineering techniques. High temperature oxidation can also be used for surface
modification of non-oxide ceramic instead of coating. Si3N4 is thermodynamically
unstable at high temperatures, especially in an oxidizing atmosphere. Oxidation of
Si3N4 grains causes formation of a silica layer. This intergranular glassy phase,
when molten, serves as a path for outward diffusion of cations (such as cations
deriving from sintering aids or impurities) and inward diffusion of oxygen [5]. The
surface is covered by this protective layer of silica and grain boundary species,
which can form either amorphous or crystalline phases adjacent to the silicon nitride
bulk [6]. The same processes occur in a very short timeframe during ablation and
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M. Hnatko, M.Hičák, J. Sedláček, P. Šajgalík
oxidation tests of ultrahigh temperature ceramics by oxyacetylene torch with a flame

temperature of about 3000 °C [7].
This paper deals with the preparation, using an oxyacetylene torch flame, of an
oxidized surface layer on silicon nitride-based ceramics sintered with bioactive
sintering additives. The chemistry of the surface layer is controlled by the
composition of the sintering additives. The surface layer phase composition,
thickness and porosity are controlled by the flame temperature and exposure time.
Preparation of dense Si3N4 substrates
Substrates were prepared using commercial Si3N4 powder (grade SN-E10, Ube
2 -1
Industries Ltd., Japan) and SiO2 (Aerosil OX-50, Degusa, Germany, 50 m .g ),
together with a bioactive phase acting also as a sintering aid, either CaO (Lachema,
Czech Republic, p.a. quality) or Ca3(PO4)2 (Lachema, p.a. quality). The chemical
compositions of the initial powder mixtures are given in Table 1.
Table 1 Chemical composition of the initial powder mixture

Si3N4 SiO2 CaO Ca3(PO4)2 Sintering T m
samples
[wt.%] [wt.% ] [wt.% ] [wt.%] [°C] [wt.%]
SNSi 90 10 - - 1750 5.24
SNSiCa 90 6.4 3.6 - 1600 3.8
SNCaP 90 - - 10 1630 6.8
Samples were prepared by hot pressing at temperatures between 1600 and 1750°C
(Table 1) at 30 MPa for 60 min under nitrogen (N 2) atmosphere. The microstructures
were examined by scanning electron microscopy (EVO 40HV, Carl Zeiss SMT,
Germany). An oxyacetylene torch was used for thermo-oxidative treatment of
substrate surfaces, ground and polished to 1µm by diamond suspension, using a
constant O2: C2H2 = 1:1.1 ratio and dwell time of 60 sec. The surface temperature
was kept at approx. 1475°C, measured with an optical pyrometer, and controlled by
changing the distance between the nozzle tip of the burner and the surface.
Microstructure and the chemical composition of the surface and cross sections, and
phase composition of the tested samples were characterized by scanning electron
microscopy attached with x-ray spectrometers (JEOL JSM-7600
F/EDS/WDS/EBSD) and X-ray diffraction analysis (Bruker AXS D8 Discover),
respectively.
Microstructure and phase composition of Si3N4 substrates
The microstructure of all three prepared substrates consists of elongated β-Si3N4
grains and grain boundary phases (Fig. 1). Weight loss, density and phase
composition of all samples are listed in Table 2.
The existence of Ca-containing phases in the SNSiCa substrate was proved by EDX
analysis (Tab. 3). The detection of 1.9 wt.% of calcium in the SNSiCa substrate
confirms that a certain amount of CaO or CaSiO3 is present in the sample.
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L 16
Fig. 1 The microstructures of the prepared

substrates with SiO2 (A),
SiO2 and CaO (B), and
Ca3(PO4)2 (C) as sintering additives
Table 2 Density and phase composition of the prepared Si 3N4 substrates

SNSi SNSiCa SNCaP
m [wt.%] 5.24 3.80 6.8
-3
density [g.cm ] 3.05 3.07 3.11
Density / Theoretical density [%] 97.13 97.15 97.49
XRD phase analysis Si3N4, Si2N2O, SiO2, Si3N4, SiO2 Si3N4, SiO2, CaO
Substrate SNCaP was fabricated with the aim of introducing bioactive calcium
phosphate into the system, for which reason 10 wt.% of Ca3(PO4)2 was added to the
starting powder (Tab. 1). However, XRD analysis did not indicate the presence of
calcium phosphate. This had probably decomposed at the sintering temperature to
calcium and phosphorus oxides; however, only CaO was detected by XRD (Tab. 2).
On the other hand, EDX analysis confirmed the presence of both Ca and P (Tab. 3).
Table 3 Chemical composition (EDX analyses) of the substrates (wt %)
Substrate N O Si Ca P
SNSi 37.0 16.0 47.0 0.0 0.0
SNSiCa 28.4 14.9 54.8 1.9 0.0
SNCaP 14.6 8.2 68.3 4.2 4.7
Substrate surfaces after thermal treatment with acetylene-oxygen flame

The substrate surfaces after thermal treatment with acetylene-oxygen flame are
shown in Fig. 2A-C. The front faces of the substrates were covered by a strongly
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bonded oxide layer. The substrate surfaces have a porous structure and are visibly
eroded (Fig. 2A-C). Less of an effect was observed in the SNSi system. This was
expected because this system contains SiO2, whose melting point of 1660°C
exceeds the flame temperature, as well as Si2N2O, which has good resistance
against oxidation up to 1600°C (see Tab. 2).
Fig. 2 Structures of substrate surfaces after

thermal treatment with flame (1475 °C
± 25°C;
O2 : C2H2 ratio = 1 : 1.1;
dwell time 60s)
The surface of the SNSiCa sample looks different to that of SNSi after the thermal
treatment, and has evidently eroded in a different manner. The image magnification
of Fig. 2A is 10× higher than Fig. 2B, as the surface damage to the substrate SNSi
was not sufficiently visible and higher magnification was needed. The surface
topology of sample SNCaP (Fig. 2C) is similar to that of SNSiCa: large
interconnected droplets and the porous nature of the surface are clearly visible.
All three substrates were cut and polished in order to measure the thickness of the
formed layers and their chemical and phase compositions. Micrographs of the cross-
sections are given in Fig. 3 and their phase compositions are listed in Table 4.
It is visible from Fig. 3 that the different sintering additives have led to significant
differences in thickness (varying from almost 20 m to 100 m) and pore structure of
the sample surfaces. Their phase composition is also dependent on the chemistry of
sintering additives (Tab. 4). Rapid evolution of gases, such as nitrogen and/or SiO,
leads to interconnected, irregularly-shaped pores with a wide size distribution.
Nitrogen evolves from bulk silicon nitride ceramics on decomposition by
oxyacetylene flame treatment, and SiO is formed as a result of reactions between
the sintering additives and Si3N4.
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L 16
A damaged surface layer was created in the SNSi substrate (Fig. 3A). The thickness
of this surface layer was uneven, with an average thickness of approx. 14 m but
maximum thickness of about 20 m (Fig. 3A). Under the oxidized surface layer is a
layer of Si3N4 characterized by increased porosity compared to the denser bulk Si 3N4
substrate laying beneath (Fig. 3A).
Porouslayer
Fig. 3 Cross-sections of the substrates

after thermal treatment
In the case of SNSiCa, the substrate’s upper surface seems to be a solidified melt
(probably SiO2). The surface is characterized by a high porosity, with pore sizes of
about 10 to 30 m, and an average layer thickness of 70 m. Pores located under
this layer are smaller and spherical. These pores are probably interconnected and
form a channel structure terminating in the compact upper layer (see arrow in Fig.
3B). The thickness of the surface damage in the SNCaP sample is partway between
that of the SNSi and SNSiCa substrates, being about 30 m on average (Fig. 3C).
The phase composition of this layer is listed in Table 4.
Composition of substrate surfaces after flame thermal treatment
The phase composition of the surface layers was measured by the low angle
grazing incidence X-ray diffraction technique at  = 6° in order to get the diffractions
from the sample surface. The results are summarized in Table 4. In the case of
SNSi, the phase composition did not change compared to the reference state. In the
case of the SNSiCa substrate, the phase composition of the thick surface layer
contains a Ca5Si2N6 phase in addition to the SiO2 and Si2N2O phases.
Unfortunately, formation of the bioactive calcium silicate (CaSiO 3) could not be
confirmed. The surface layer of the SNCaP sample contains Si 12P5 and Si (see Tab.
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4), in addition to the starting materials, Si3N4, SiO2 and CaO, (see Tab. 2). In this
case, too, the bioactive calcium phosphate Ca3(PO4)2 was not formed. The calcium
phosphate Ca3(PO4)2 introduced into the starting mixture probably dissociates under
the oxyacetylene flame treatment to CaO and P2O5. CaO remains stable at the
treatment temperature, but P2O5 starts to react with SiO2. Phases in the P2O5-SiO2
binary system have a rather low melting temperature, e.g. SiP 2O7 has a melting
temperature of 1250 °C. At the temperature of the acetylene-oxygen flame, which
was 1475 °C ± 25 °C, such phases would have been melted and probably reduced
by the carbon contained in acetylene, resulting in the formation of the non-oxide
phase Si12P5 and elemental Si by carbothermal reduction of the silica and
phosphorus oxides.
Table 4 Phase composition of substrate surfaces after thermal treatment, measured by the
grazing incidence X-ray diffraction technique ( = 6°)
SNSi SNSiCa SNCaP
Si3N4, Si2N2O, Si3N4, Si2N2O, Si3N4, Si12P5, Si, SiO2,
composition
SiO2 SiO2,Ca5Si2N6 CaO
During the flame thermal treatment, three processes occur in parallel: i.) melting of
oxide phases, resulting in viscous flow or diffusion of cations (from the sintering
aids) located at the grain boundaries of Si3N4, ii.) reduction of these phases by
carbon, and iii.) oxidation/ dissociation of Si3N4 and/or Si2N2O, with formation of
gaseous products and pore formation in surface layer.
In this experiment the O2:C2H2 ratio in the flame was chosen to have more
acetylene than oxygen, and was thus in carbon-rich mode. Contamination of the
surfaces of all three samples by carbon (in amounts of 6 - 8 wt.%) confirms its
presence and thus potential reduction of oxide phases (Table 5).
Table 5 Chemical composition (EDX analyses) of substrate surfaces after dynamic oxidation
[wt.%]
Layer C O Si Ca P
SNSi 7.9 51.2 40.9 X x
SNSiCa 6.0 51.1 37.2 5.7 x
SNCaP 8.2 52.9 10.6 14.6 13.7
On the other hand, the conditions of flame treatment performed in air lead to the
oxidation of Si3N4 (or Si2N2O in the SNSi system), by the following reactions:
2Si3N4(s) + 3O2(g) = 6SiO (g) + 4N2 (g);
Si2N2O(s) + 3/2O2(g) = 2SiO2 (s) + N2 (g).
Dissociation of Si3N4 at the temperature of the flame treatment is also a potential
source of gaseous species:
Si3N4(s) = 3Si (l) + 2N2 (g).
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The nature of the porous surface layers prepared in this way is significantly different
to that of layers prepared by traditional techniques such as PVD, CVD, dip-counting,
etc. The bonding of the prepared surface layer is visibly stronger, without any
spallation.
Conclusion
Dense silicon nitride materials with different sintering additives of SiO 2, SiO2 and
CaO, and Ca3(PO4)2 were prepared by the hot-pressing method. The surfaces of the
substrates after thermal treatment by acetylene-oxygen flame were covered by
oxide phases and pores. The thickness of the flame-treated surface ranges from 10
to 100 m, depending on the sintering additive. The wide size distribution,
interconnectivity, and irregular shapes of the pores are a result of the rapid evolution
of gaseous products related to the decomposition of phases of the substrate matrix.
Acknowledgement: This work was supported by the Slovak Grant Agency VEGA Project No.
2/0152/18, APVV-0540-15 and MVTS - CERANEA project (in the framework of FLAG ERA II).
This publication is also the result of the project implementation: Effective control of production
and consumption of energy from renewable sources (ITMS code 26240220093) supported by
the Research & Development Operational Programme funded by the ERDF.
References
[1] M.Akazawa, K.Kato, Wear properties of Si3N4 in rolling-sliding contact, Wear 124 (1988)
123-132. https://doi.org/10.1016/0043-1648(88)90239-6
[2] A.Neumann, C. Unkel, C. Werry, C.U. Herborn, H.R. Maier, C. Ragoss, K. Jahnke,
Prototype of a Silicon Nitride Ceramic-Based Miniplate Osteofixation System for the
Midface, Otolaryngol. Head Neck Surg. 134 (2006) 923-930.
https://doi.org/10.1016/j.otohns.2006.01.022
[3] D.A. La Van, T. Mcguire, R. Langer, Small-scale systems for in vivo-drug delivery, Nat.
Biotechnol. 21 (10) (2003)1184-1191. https://doi.org/10.1038/nbt876
[4] C.C. Sorrell, P.H. Hardcastle, R.K. Druitt, E.R. McCartney, In: A. Ravaglioli, A Krajewski
(Eds.), Proceedings 5th Meeting and Seminar on: Implants for Spine. Ceramics, Cells
and Tissues annual conferences, ISTEC-CNR edn, Faenza (Italy), 1999. p. 47.
[5] V. Medri, M. Bracisiewicz, K. Krnel, F. Winterhalter, A. Bellosi. Degradation of
mechanical and electrical properties after long-term oxidation and corrosion of non-oxide
structural ceramic composites, J Eur Ceram Soc. 25 (10) (2005) 1723-1731.
https://doi.org/10.1016/j.jeurceramsoc.2004.12.002
[6] X. Pan, Atomistic structure of silicon nitride/silicate glass interfaces, J Am Ceram Soc.
79 (11) (1996) 2975-2979. https://doi.org/10.1111/j.1151-2916.1996.tb08737.x
[7] X. H. Hou, H. J. Li, Y. Chen,K. Z. Li, Modelling of chemical vapor infiltration process for
fabrication of carbon–carbon composites by finite difference methods, Carbon. 37 (4)
(1999) 669-677. https://doi.org/10.1016/S0008-6223(98)00243-7
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L 17
SINTERING BEHAVIOUR AND MICROSTRUCTURAL EVOLUTION

OF SILICON NITRIDE COMPOSITES WITH BORON NITRIDE
PLATELETS
1 1 2 3
Monika Tatarková , Peter Tatarko , Ivo Dlouhý , Ján Dusza
1
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9,
2
Institute of Physics of Materials, Academy of Sciences of the Czech Republic,
Žižkova 22, 616 62 Brno, Czech Republic
3
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47,
040 01 Košice, Slovak Republic
e-mail: monika.tatarkova@savba.sk
Silicon nitride with the addition of hexagonal boron nitride platelets were prepared using spark
plasma sintering. The effect of the presence of BN platelets, their amount and size, on the
microstructure evolution and the  transformation was investigated in the present work.
Keywords: silicon nitride, boron nitride platelets, spark plasma sintering, microstructure
Introduction
Silicon nitride (Si3N4)/ hexagonal boron nitride (h-BN) is a widely used ceramic
composite that utilizes high strength of Si3N4 and good lubricating properties of h-BN
[1,2]. Therefore, such a composite material is mainly used for the applications that
require high hardness, fracture toughness, strength and good wear resistance.
During the last decades, the development of nanomaterials offers a new alternative
for the reinforcing ceramics. The synthesis of new nano-phases, such as boron
nitride nanoplatelets and nanotubes, combined with the use of spark plasma
sintering (SPS), has opened up the possibility of developing new ceramic
nanocomposite materials with potentially improved mechanical and functional
properties [3,4].
In the present work, the boron nitride nanoplatelets (BNNPs) with different lateral
sizes and thicknesses were produced using the liquid phase exfoliation process,
followed by the controlled centrifugation. High purity of the BNNPs is granted by a
high purity of initial h-BN powder. Two different sizes of the nanoplatelets were than
selected to reinforce the Si3N4 matrix.
The aim of this work was to study the effect of different contents and lateral sizes of
BN platelets on the microstructural evolution – grain size and ratio of α/β Si3N4
grains in the Si3N4 / h-BN ceramic composite system. The paper aims to answer the
question how different loading and size of BNNPs would influence the Si3N4 grain
evolution and their transformation.
Experimental Materials and Procedure
The Si3N4-BNNP composites were prepared using SPS with loading of 1 wt.% or
2wt.% of BNNPs and 5 wt.% of Y2O3 and 2 wt.% Al2O3 as sintering additives. The
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SINTERING BEHAVIOUR AND MICROSTRUCTURAL EVOLUTION OF SILICON NITRIDE COMPOSITES
WITH BORON NITRIDE PLATELETS M. Tatarková, P. Tatarko, I. Dlouhý, J. Dusza
high-energy sonic probe was used to exfoliate BN nanoplatelets from highly pure h-
BN powder with the mean particles size of 35-60 µm dispersed in ethanol. Two
batches of platelets at 1000 rpm and at 3000 rpm were collected. The composites
were sintered in vacuum at 1750 °C using the pressure of 50 MPa and the sintering
time of 7 min. To obtain the same α/β ratio of Si3N4 grains as for the composites,
different sintering temperatures from 1600 °C to 1750 °C were applied during the
SPS process to prepare monolithic Si3N4. Relative densities of all samples
measured by the mercury immersion method were higher than 98.7 % of theoretical
density. The as-prepared BNNPs were characterised using SEM. After sintering of
the specimens, X-ray diffraction and Rietveld analysis were used to identify
crystalline phases and determine the ratio of α/β Si3N4 phases.
The boron nitride nanoplatelets studied by SEM in STEM mode are shown in Fig.1.
The statistical analysis in Fig. 2 revealed that BNNPs collected by centrifugation at
3000 rpm are much smaller than the ones collected by centrifugation at 1000 rpm.
The most frequent lateral size of BNNPs collected at 3000 rpm are ~ 0.3 µm while it
was ~ 1.1 µm for the BNNPs collected by centrifugation at 1000 rpm
a.) b.)
Fig.1 BN nanoplatelets collected by centrifugation at 1000 rpm (a) and 3000 rpm (b)
45 45
Relative Frequency
40 a.) b.)
Relative Frequency
40
35 35
30 30
25 25
20 20
15 15
10 10
5 5
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
lateral size [m] lateral size [m]
Fig. 2 Lateral size distribution of BNNPs collected by centrifugation at 1000 rpm (a)
and3000rpm (b)
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Fig. 3 shows the results of Rietveld structure refinement of all sintered specimens:
the monoliths sintered at the temperature range of 1600 – 1750 °C and the Si3N4-
BNNPs composites with 1 and 2 wt.% of BN nanoplatelets collected by
centrifugation at 1000 and 3000 rpm, sintered at 1750 °C. It is obvious that the
amount of -phase of Si3N4 increased with the increasing of sintering temperature:
only ~ 18 % of -Si3N4 grains were transformed to -Si3N4 at the temperature of
1600°C, while 52 % of the grains were -Si3N4 after sintering at 1700 °C. When the
sintering temperature of 1750 °C was applied, all of the grains of -Si3N4 were
transformed to -Si3N4. In the case of composites, all the materials contained similar
amount of -phase (~ 70 %), regardless the size or amount of BN nanoplatelets.
This confirmed that the presence of BNNPs suppressed the transformation of 
silicon nitride, when compared to the monolithic Si3N4 sintered at the same
temperature. However, the investigated different quantities and lateral sizes of
BNNPs did not have a significant effect on the phase transformation of silicon nitride
grains.
100
The amout of -Si3N4 [%]
90
80
70
60
50
40
30
20
10
0
1600 1650 1700 1750 1-1000 1-3000 2-1000 2-3000
Fig. 3 Effect of sintering temperature and the presence of BN platelets on the quantity
ofβSi3N4 grains in the microstructure
Conclusions
In this work, silicon nitride with the addition of liquid phase exfoliated hexagonal
boron nitride nanoplatelets were prepared using spark plasma sintering. It was
observed that the BNNPs significantly affected the sintering behaviour and α to β
Si3N4 phase transformation, when compared to the Si3N4 monolith sintered at the
same temperature. On the other hand, no significant influence of the lateral size of
BNNPs or their quantity on the microstructure evolution was observed.
Acknowledgement: Authors gratefully acknowledge the financial support of the Scientific

Grant Agency of the Slovak Republic under the grant No. VEGA 2/0152/18, Slovak Research
and Development Agency under the grant No.: APVV-18-542 and Joint Mobility Project within
Czech-Slovak scheme for the period 2018–2020 under the ASCR-SAS agreement.
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SINTERING BEHAVIOUR AND MICROSTRUCTURAL EVOLUTION OF SILICON NITRIDE COMPOSITES
WITH BORON NITRIDE PLATELETS M. Tatarková, P. Tatarko, I. Dlouhý, J. Dusza
References
[1] H.Y. Liu, S.M. Hsu, Fracture behavior of multilayer silicon nitride/boron nitride ceramics,
Journal of the American Ceramic Society 79 (1996) 2452-2457
[2] A. Kovalčíková, J. Balko, Cs. Balázsi, P. Hvizdoš, Influence of hBN content on mechanical
and tribological properties of Si3N4/BN ceramic composites, Journal of the European
Ceramic Society 34 (2014) 3319-3328
[3] T. Li, Y. Chen, W. Li, J. Li, L. Luo, T. Yang, L. Liu, G. Wu, Fabrication and mechanical
properties of boron nitride nanotube reinforced silicon nitride ceramics, Ceramics
International 44 (2018) 6456–6460
[4] C.G. Yue, W.W. Liu, L. Zhang, T.H. Zhang, Y. Chen, Fracture toughness and toughening
mechanisms in a (ZrB2-SiC) composite reinforced with boron nitride nanotubes and boron
nitride nanoplatelets, Scripta Materialia 68 (2013) 579–582
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HYDROXYAPATITE BASED MATERIALS FOR FDC 3D PRINTING

FILAMENTS APPLICABLE IN TISSUE SCAFFOLDS DEVELOPMENT
1,3 1 1 1
Marián Janek , Tatiana Gabošová , Roman Fialka , Zora Hajdúchová ,
1 1,2 2 2
Peter Veteška , Katarína Tomanová , Jozef Feranc , Roderik Plavec ,
1 4 1 2
Vladimír Kovár , Peter Peciar Ľuboš Bača and Pavel Alexy
1
Slovak University of Technology, Faculty of Chemical and Food Technology,
Department of Inorganic Materials, Radlinského 9,
2
Slovak University of Technology, Faculty of Chemical and Food Technology,
Department of Plastics, Rubber and Fibbers, Radlinského 9,
3
Comenius University, Faculty of Natural Sciences, Department of Physical and
Theoretical Chemistry, Ilkovičova 6, Mlynská dolina,
4
Slovak University of Technology, Faculty of Mechanical Engineering,
Institute of Process Engineering, Nám. slobody 17, 812 31 Bratislava, Slovakia
e-mail: marian.janek@stuba.sk
Commercial hydroxyapatite was used for preparation of filaments suitable for fused deposition
of ceramics. The solid content was at the level of 50 % of prepared polymer/HAp composite
and in the comparative material 10 % of HAp used was replaced with SiO2 based bioactive
glass components. The bioactive glass was supposed to be formed in situ during filament
material firing at 1200 °C for 1 hour. The morphology of primary microcrystalline HAp particles
changed during firing and SEM images showed increased interparticle neck connections and
merged material areas with preserved porosity. The powder x-ray diffraction and infrared
analysis proved the dehydroxylation reaction and new phases formation. The effect of
chemical composition and amount of SiO2 based bioactive glass for reasonable bioactivity of
produced HAp scaffolds will be essential for their application for production of 3D printed
bioactive tissues.
Keywords: hydroxyapatite, 3D printing, FDC, bioactive glass, SEM , PXRD, infrared
Introduction
The development of novel bone tissue replacements in recent years is intensified in
the areas of the most compatible biomaterials, including principal substance found in
natural hard tissues, the hydroxyapatite (HAp). However, synthetic HAp does not
reach the same bioactivity as bone HAp. New engineering approaches are emerging
for reparation of human bone tissues and include utilisation of more bioactive
phosphate compounds such as calcium phosphates, because the bioactivity and
rate of biodegradation in body environment depend on the Ca/P ratio. The novel
bioengineering approaches recognise the fact that bone remodelling is an active
lifetime process that includes bone resorption, bone tissue withdrawing and the
ossification - the new bone tissue growth. These mechanisms involve the activities
of specialised cells for the bone growth, the osteoblasts and the bone resorption, the
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HYDROXYAPATITE BASED MATERIALS FOR FDC 3D PRINTING FILAMENTS APPLICABLE IN TISSUE
SCAFFOLDS DEVELOPMENT M. Janek, et al.
osteoclasts as responsible for the successful ingrowths of man-made hard tissue

®
replacements such as the bioactive glasses e.g. Bioglass [1–3].
The fact that bone is one of the tissues which is the most frequently transplanted
and can be successfully replaced by other biocompatible and/or bioactive materials
using the phosphate based scaffolds (which could mimic well the behaviour of
natural bone), motivate the effort of many researchers. The challenges are of the
micro-structural design, bioactivity and mechanical properties of bone tissue
replacements, which require further optimization to achieve desired properties.
These are supposed to fit various applications such as bone reconstruction, coating
of orthopaedic implants, dental applications and novel drug delivery systems for
various biomedical devices required in the treatment of bone-related diseases.
Herewith, several types of the man-made materials including composites of calcium
phosphate combined with metals or polymers were used to developed scaffolds with
biological response. In general the composite materials which include inorganic-
organic or inorganic-inorganic materials are the most acceptable for achieving of
specific implant bioactivity and mechanical properties [4–7].
The recent advances in 3D printing technology created new technology frontiers and
possibilities leading to breakthroughs in several distinct and multidisciplinary
sciences including bone tissue engineering [8]. Vaezi and S. Yang [9] reported
several additive manufacturing (AM) technologies applicable for production of bone
tissue replacements and/or scaffolds production. Nevertheless, each of the AM
technology requires its own production conditions optimisation, including
development of material workable on respective 3D printer and important biological
response required. Recently, Elsayed et al. [10] reported that 3D scaffolds produced
by direct ink writing after thermal treatment of silicone polymers containing
micro‐sized oxide fillers, may at the 60 % porosity achieve high compressive
strength e.g. ~7 MPa. To ensure high bioactivity of produced scaffolds, the
®
Biosilicate glass‐ceramics was used in above mentioned work. From these
reasons, the main aim of our work was to verify the preparation of HAp based
materials with bioactive glass components applicable for fused filament fabrication
3D printing technology and hard tissue scaffolds production.
Commercially available parent HAp powder used as received with spherical primary
particles having diameters ranging from ~ 1 up 200 µm with d50 ≤ 35 µm (Figure 1)
The filament test composition was modified with components able to form SiO 2
based bioactive glass in situ during the filament firing in air at 1200 °C for 1 hour.
The composition of test filaments is indicated in Table 1.
The HAp powder was homogenised with thermoplastic polymer (alternatively with
bioactive glass components) and filament with diameter of 1.75 mm was prepared
by extrusion of inorganic/organic composite material using single screw extruder and
printability tests of fused deposition of ceramics (FDC) were performed using
commercial 3D printer Leapfrog Creatr™ (Leapfrog 3D printers, Netherlands).
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Table 1 Composition of HAp based filaments prepared for 3D print testing in weight %
Component / Hydroxyapatite Thermoplastic polymer Bioactive glass

Sample (mass %) [%] [%] [%]
HAp-A 50 50 -
HAp-B 40 50 10
The surface of prepared filaments was inspected prior and after filament firing in air
at 1200 °C using optical microscope Zeiss Stemi 508 coupled with camera module
Axiocam 105 (Carl Zeiss AG, Germany). The inspection of mesopores of the
sintered material was performed by SEM using a JEOL 7500 F (JEOL Ltd., Tokyo,
Japan) with an accelerating voltage of 15 kV. The changes of the material structure
induced by filament firing were investigated by powder X-ray diffraction (PXRD)
analysis using Brag-Bretano geometry of Stoe Thetha-Thetha goniometer equipped
with linear position sensitive detector. The cobalt lamp radiation CoK(1) with
wavelength of 0.1788965 nm and measuring range of 20-70 2θ° with 0.2 step and
integration time of 10 s were used. The chemical changes of the material induced by
filament firing were examined by infrared spectroscopy measured by ATR module
PIKE MIRacle™ with ZnSe crystal using FTIR spectrometer Nicolet 6700 and DTGS
–1
detector. The spectra were measured in the range of 4000-400 cm and averaging
–1
64 spectral scans with resolution of 4 cm . The background signal was measured
®
prior each measurement and spectra were evaluated by Omnic ver. 7.1 software
(Thermo Electron Corporation).
Fig. 1 SEM images of used HAp powder at different magnification: – left 250x – right 15000x

The majority of HAp particles as can be seen on SEM images in the Figure 1 have
spherical shape - including irregular pieces of HAp with size ranging from about
100 µm down to a less than few µm. These larger particles are aggregates of
primary microcrystalline HAp particles of about 100 nm size as can be seen in the
Figure 1 - right. The filament was debinded during firing process up to temperature
1200 °C and resulting material was inspected by optical and SEM microscopy as
shown in the Figure 2. The filament surface morphology was irregular with rough
surface originating from largest HAp particles which slipped along the filament
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surface during material extrusion through extruder head calibre-hole. No principal

morphology differences could be observed for HAp-A or HAp-B surfaces (Figure 2).
Filaments with certain surface roughness are still machinable on the FDM 3D
printers. However, to achieve smoother filament surface, fraction of smaller HAp
particles has to be used for filament preparation (data not shown).
Fig. 2 Filament surface morphology comparison OM (left) SEM (right) after filaments firing
at 1200 °C; HAp-A (top) and HAp-B (bottom)
As can be seen in the Figure 3, the microstructure of primary microcrystalline HAp

particles changed after the sintering of the filaments at 1200 °C. The development of
local necks interconnections between HAp grains can be observed. Much more
intense development of local necks interconnections and merged material areas with
porosity preservation was observed for the sample containing bioactive glass
components.
Another important question arising for future filament application is the adjustment of
the bioactivity of glass and apatite substances present in biological fluids, after their
common reactions induced by heat treatment. The chemical changes induced by
thermal treatment are documented in the literature [11,12]. Pure HAp substance
may undergo several decomposition reactions depending on the conditions of
decomposition during thermal heating including dehydroxylation reaction ( =
structural vacancy):
Ca10(PO4)6(OH)2  Ca10(PO4)6(OH)2–2xOxx + xH2O (1)
Ca10(PO4)6(OH)2  2Ca3(PO4)2 + Ca3(P2O8) + CaO + H2O (2)
Ca10(PO4)6(OH)2  2-Ca3(PO4)2 + Ca4P2O9 + H2O (3)
Ca10(PO4)6(OH)2  3-Ca3(PO4)2 + CaO + H2O (4)
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-Ca3(PO4)2  -Ca3(PO4)2 (5)

While according to literature data the reaction (1) takes place below temperatures
800-1150 °C, the reaction (2) can be observed in temperature range 1150-1350 °C
or above. The progress of both reactions should be affected by the presence of
other reactive components, such as those required for glass formation.
Fig. 3 Comparison of filament surface microstructure; left - HAp-A, right - HAp-B,

afterfilaments firing at 1200 °C
The progress of the HAp reactions and effect of heat treatment can be investigated
by several techniques such as PXRD and FTIR. The effect of thermal treatment on
structure of HAp-A and HAp-B samples is shown in the Figure 4.
PXRD patterns show changes in HAp structure after thermal treatment of pure HAp
sample and Hap-B (with addition of bioactive glass components). The HAp improves
its crystal order after heating at 1200 °C (HAp-A) as denoted by (*) diffractions and
reacted further with glass components (HAp-B) added to HAp particles clearly
identified by new diffractions (x). These changes indicate transformation of HAp
structure induced by SiO2 bioglass and removal of hydroxyl groups, resulting in
production of new phosphate components created by chemical reactions (1 – 4).
Similarly, the effect of thermal treatment on HAp-A and HAp-B samples was proved
by FTIR spectroscopy (Figure 5). The FTIR spectrum of pure HAp before and after
firing at 1200 °C is in agreement with the literature data. The vibrations of triply
degenerated antisymetric stretching 3 of P–O bonds at 1090, 1047(1056) and
–1 –1
1030 cm , non-degenerated symmetric stretching of P–O bonds at 961 cm and
–1
OH vibration at 631 cm were observed. The heat treatment significantly improved
the peaks resolution, hence the decrease in Full Width at Half Maximum (FWHM)
values.
–1
Additionally, new small intensity peaks can be observed at 946, 676 and 649 cm in
HAp-A sample spectra. These peaks are associated with the dehydroxylation
reaction and formation of new phases as indicated in the reactions (1-4). However,
the band intensities indicate that the changes should be minor and sample
preserves hydroxyapatite structure that is in agreement with the results of PXRD
(Figure 4). Intense changes were observed after addition of 20 mass % (with respect
to final inorganic phase content) of SiO2 bioactive glass components.
Jahodná, Slovakia
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25 -27 June, 2019 119
Fig. 4 PXRD patterns a) used parent HAp and fired b) HAp-A and c) HAp-B samples
at1200 °C
Fig. 5 FTIR spectra a) used parent HAp, b) fired HAp-A and c) HAp-B samples at 1200 °C
–1
Interestingly, the antisymmetric stretching 3 of P–O bonds at 1090 cm
–1
disappeared completely, while the vibration main band component at 1047 cm
–1
remained preserved and the band at 1009 cm may include the Si–O stretching
vibration. In the literature data reported fundamental fused silica vibrations were at
–1
1126, 809, 452 cm [13,14]. The exact attribution of strong bands at 941, 905 and
–1 –1
887 cm and the weak bands at 647, 617 and 606 cm is less straightforward. The
question is whether these bands may be connected to Si–O–P structural units.
® 31 17
According to molecular dynamics model of Bioglass 45S5 , the P and O NMR,
phosphorus is present in an orthophosphate environment with charge balanced by
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sodium and/or calcium [2]. Nevertheless, the presence of Si–O–P structural units in
HAp biomaterial would be essential for further material development and interesting
for assessment of its biological activity.
Conclusions
Presented study showed that HAp based filaments can be produced for FDC 3D
printing technology and production of porous fired ceramic scaffolds. As
demonstrated in this preliminary study, specific reactivity of used HAp and bioactive
glass components play an important role for products achieved during material high
temperature treatments and later scaffold bioactivity. In addition, several other
crucial parameters are to be optimised for an easy usability of produced filaments
using commercial 3D printers, mainly mechanical properties of produced
filaments/fired scaffolds. Effect of chemical composition/amount of SiO 2 based
bioactive glass must also to be optimized for reasonable bioactivity of produced HAp
scaffolds. The FDC technology using HAp based filaments may be an efficient tool
for production of small dimension implants e.g. for dental and specific bone
replacements.
Acknowledgements: The financial support of the Slovak Grant Agency for Science VEGA
grant No. 1/0906/17 and Slovak Research and Development Agency APVV-16-0341 are
greatly appreciated. The assistance of Dr. Karol Lušpai from Department of Physical
Chemistry Faculty of Chemical and Food Technology STU, during FTIR measurements is as
well greatly appreciated. This work is based on the results of the project Center for Applied
Research of New Materials and Technology Transfer, ITMS 26240220088, supported by the
Science and Research Operational Program by the European Regional Development Fund.
References
[1] S.M. Rabiee, N. Nazparvar, M. Azizian, D. Vashaee and L. Tayebi, Effect of ion
substitution on properties of bioactive glasses: A review, Ceramics International 41
(2015) 7241–7251.
[2] J.R. Jones, Review of bioactive glass: From Hench to hybrids. Acta Biomaterialia 9
(2013) 4457–4486.
[3] A.M. Deliormanlı and M. Yıldırım, Sol-gel synthesis of 13-93 bioactive glass powders
containing therapeutic agents.Journal of the Australian Ceramic Society52(2016)9–19.
[4] M. Alizadeh-Osgouei, Y. Li and C. Wen, A comprehensive review of biodegradable
synthetic polymer-ceramic composites and their manufacture for biomedical
applications. Bioactive Materials 4 (2019) 22–36.
[5] W. Habraken, P. Habibovic, M. Epple and M. Bohner, Calcium phosphates in biomedical
applications: materials for the future? Materials Today 19 (2016) 69–87.
[6] S. Bose and S. Tarafder, Calcium phosphate ceramic systems in growth factor and drug
delivery for bone tissue engineering: A review. Acta Biomaterialia 8 (2012) 1401–1421.
[7] E. Verron, I. Khairoun, J. Guicheux and J.-M. Bouler, Calcium phosphate biomaterials as
bone drug delivery systems: a review. Drug Discovery Today 15, (2010) 547–552.
[8] R. Narayan (editor) Rapid prototyping of biomaterials - Principles and applications.
Woodhead Publishing Series in Biomaterials: No. 70, Cambridge (2014) 323pp.
[9] M. Vaezi and S. Yang , Freeform fabrication of nanobiomaterials using 3D printing. In R.
Narayan (editor) Rapid prototyping of biomaterials - Principles and applications.
Woodhead Publishing Series in Biomaterials: No. 70, Cambridge (2014) 16–74.
[10] H. Elsayed, P. Rebesan, M.C. Crovace, E.D. Zanotto, P. Colombo, E. Bernardo,
®
Biosilicate scaffolds produced by 3D‐printing and direct foaming using preceramic
polymers. Journal of American Ceramic Society 102 (2019) 1010–1020.
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[11] S.-F. Ou, S.-Y. Chiou, K.-L. Ou, Phase transformation on hydroxyapatite decomposition.
Ceramics International 39 (2013) 3809–3816.
[12] H. Nishikawa, Thermal behavior of hydroxyapatite in structural and spectrophotometric
characteristics. Materials Letters 50 (2001) 364–370.
[13] R. Hanna, Infrared absorption spectrum of silicon dioxide. Journal of the American
Ceramic Society 48 (1965) 595–599.
[14] M. Criado, A. Fernández-Jiménez and A. Palomo, Alkali activation of fly ash: Effect of
the SiO2/Na2O ratio Part I: FTIR study. Microporous and Mesoporous Materials 106
(2007) 180–191.
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MEASUREMENT OF BIOACTIVITY AND ANTIBACTERIAL EFFECT

OF TITANIA BASED COATINGS WITH Ag, Ca, P
Kristýna Švagrová, Diana Horkavcová, Aleš Helebrant

Department of Glass and Ceramics, Faculty of Chemical Technology, University
ofChemistry and Technology Prague, Technická 5, 166 28 Prague, Czech Republic
e-mail: svagrovk@vscht.cz
The aim of this work was to prepare antibacterial and bioactive coatings using sol-
gel method and dip-coating technique on titanium substrate. The treated titanium
samples were coated in the sol based on tetra-n-butyl-orthotitanate with the addition
of silver, calcium, and phosphorus. After drying and firing part of the samples were
treated in the solution of sodium hydroxide and, in the end, all samples were tested
by static in-vitro test and against bacteria Escherichia coli.
Keywords: sol-gel, titania coating, silver, calcium-phosphate, dip-coating, bioactivity,
antibacterial effect
Introduction
Metallic materials are widely used as biomaterials for implantation into the human
body, primarily for hard tissue replacement due to its superior properties [1]. The
most commonly used is titanium and its alloys such as Ti-6Al-4V, however, they are
biologically inert materials. Surface modification of these metallic implants can
improve their existing properties like tissue tolerance, osseointegration or corrosion
resistance [2]. Many methods were developed to modify implants surface and one
of the easiest is coating preparation. Common coatings technique is atomic layer
deposition, magnetron sputtering, plasma spraying, spin or dip technique. The last
three are used for the sol-gel method [3]. This method starts by mixing of sol, colloid
solution consisting of metal alkoxides, hydrolysis agent, alcohol as solvent and acid
or base as a catalyst. Alkoxides undergo hydrolysis and polycondensation according
to reactions 1-3.
Reactions Mechanism
Hydrolysis M(OR)4 + H2O → M(OR)3OH + ROH (1)

Alkoxolacion (OR)3M - OR + HO - M(OR)3 → (OR)3M - O M(OR)3 + ROH
(2)
Oxolacion (OR)3M - OH + HO - M(OR)3 → (OR)3M - O - M(OR)3 + H2O
(3)
These reactions cause particles connection, solidifying the sol into a wet gel. Final
products are usually shaped during the sol-gel transformation. The vaporisation of
water and solvents produced dried gel and its heating or firing produces dense,
homogenous materials. At acidic pH, longer linear chains are formed, at pH > 7,
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MEASUREMENT OF BIOACTIVITY AND ANTIBACTERIAL EFFECT OF TITANIA BASED COATINGS WITH
Ag, Ca, P K. Švagrová, D. Horkavcová, A. Helebrant
branched short chains are formed which create clusters [4]. Dip-coating technique
belongs into the oldest, cheapest and fastest way for coating preparation and it is
based on withdrawn vertically from the sol at a constant speed. Withdrawn speed is
crucial for final thickness of coatings [5]. One of the most important coating's
properties is bioactivity and antibacterial effect. Incorporation of other elements into
the sol can enrich its abilities. Silver in the different forms (Ag, AgNO3, Ag3PO4) is
known as an antimicrobial agent against gram-negative and gram-positive bacteria.
Addition of the Ca-P precursors (especially hydroxyapatite) can improve the
bioactivity of the coatings. The apatite-forming ability is the sight of bioactivity and is
commonly tested by in vitro test [3, 6, 7].
This work is focused on the preparation of titania-based coatings with the addition of
silver, calcium and phosphorous from chosen precursors to reach homogenous,
bioactive and antibacterial coatings on pure titanium, which could be used in clinical
medicine and to avoid in this way often implants failure after implantation.
Experimental and results
In the present work, three types of coatings were prepared on the basis of tetra-n-
butyl-orthotitanate with the addition of silver, calcium and phosphorous. Titanium
slides sized 10 x 30 x 1 mm were ground and cleaned in an ultrasonic bath with
acetone and ethanol. The treated titanium substrates were coated using the dip-
coating technique in titania sol (T) with composition: tetra-n-butyl-orthotitanate,
acetylacetonate, triton, ethanol and nitric acid. Than in TA sol with the addition of
silver nitrate and in TACP sol with silver nitrate, calcium nitrate tetrahydrate and
-1
triethyl phosphate. Chosen speed of dipping was 20 cm∙min , dwell time 30 s and
-1
withdrawal speed 6 cm.min . After drying (laboratory temperature) and firing (at 400
°C for 2 hours) part of samples was exposed in 10 M solution of sodium hydroxide at
the temperature of 60 °C for 24 hours (TN, TAN, TACPN coatings). All coatings
were investigated by electron microscopy and tested on chosen properties.
Antibacterial test of fired coatings without exposing in sodium hydroxide was
performed against gram-negative bacteria Escherichia coli (E. coli: DBM 3138). The
coated substrate was dipped into a suspension of E. coli in a physiological solution
4 −1
with concentration 10 CFU (colony forming unit). ml for 24 hours. Afterwards, the
substrate was removed and 100 μl of the suspension was spread on a Petri dish
with LB(Luria Bertami) agar. After the incubation, the Petri dish was photographed
and the quantity of colonies of surviving bacteria was counted. Bioactivity of all
coatings was tested by in vitro test in accordance with ISO 23317 in simulated body
fluid (SBF). SBF was prepared by the gradual dissolution of reagents at the
temperature of 36.5 ±1.5 °C during stirring. Two samples of the same coatings type
were immersed in the plastic bottle with SBF. The resulting ratio of the tested
samples surface and the SBF volume (S/V) was 0.1. After 14 days of interaction in a
thermostat at 36.5 °C samples were removed from SBF, washed demineralized
water and left to dry in the air at room temperature. The samples were,
subsequently, characterized by a scanning electron microscope (Hitachi S4700) and
X-Ray diffraction. All types of coatings copied relief of the substrate and contained
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cracks on the entire surface. White circle particles of silver were located on the
coating's surface but its distribution was inhomogeneous. In the case of TACP
coating, the silver particles were determined mainly in the cracks. Coatings after 24
hours exposition in sodium hydroxide solution had a porous structure with more
incorporated small - sized cracks. This structure is the most distinctive by TACP
coating. After antibacterial test coatings contained silver proved 100 % antibacterial
effect against E. Coli because no colonies of surviving bacteria were found after
incubation on Petri dish. The number of colonies of surviving bacteria in the case of
referent was on average 600 and on the dish after contact with basic T coating was
counted on average 240 surviving colonies. Thus, the titania coating had a partial
antibacterial effect around 60 % (Fig. 1 a-d).
a) Ref b) T
c) TA d) TACP
Fig. 1 Petri dish after 24 hours long antibacterial test
Test of bioactivity in SBF did not provide the bioactive ability of coatings after firing
and after exposition in NaOH solution either (Fig. 2 a-f). On the coating surfaces
after firing the newly precipitated phase was detected which looked like some pre-
phase of hydroxyapatite, but its amount was too small and the structure was not
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MEASUREMENT OF BIOACTIVITY AND ANTIBACTERIAL EFFECT OF TITANIA BASED COATINGS WITH
Ag, Ca, P K. Švagrová, D. Horkavcová, A. Helebrant
crystalline and so X-Ray diffraction did not confirm it. Coating surface of TN, TAN
and TACPN was more porous.
a) T b) TA
c) TACP d) TN
e) TAN f) TACPN
Fig. 2 Coatings after static in vitro test in SBF
Conclusion
In this work we reached preparation of titania coatings with addition of calcium,
phosphorous and silver. Antibacterial effect of these coatings against E. coli was
100 % in the case of silver contained coatings. Bioactivity wasn’t confirmed but
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coatings contained small non-crystalline Ca-P phases. In the further testing we will
consider our research on gaining bioactive properties and higher homogeneity of
coatings.
Acknowledgement: This work was supported from specific university research MSMT No 21-
SVV/2019.
References
[1] Sidane D., Rammal H, Beljebbar, A., Gangloff S., Chicot D., Velard F., Khireddine H.,
Montagne A., Kerdjoud, H. (2016). Biocompatibility of sol-gel hydroxyapatite-titania
composite and bilayer coatings. Materials Science and Engineering C. 72. 650-658.
10.1016/j.msec.2016.11.129.
[2] Catauro M, Bollino F., Giovanard, R., Veronesi P. (2016). Modification of Ti6Al4V implant
surfaces by biocompatible TiO2/PCL hybrid layers prepared via sol-gel dip coating:
Structural characterization, mechanical and corrosion behavior. Materials Science and
Engineering: C. 74. 10.1016/j.msec.2016.12.046.
[3] Horkavcova D., Novak P., Fialova I., Cerny, M., Jablonska E,Lipov J.,Ruml T.,Helebrant,
A. (2017). Titania sol-gel coatings containing silver on newly developed TiSi alloys and
their antibacterial effect. Materials Science and Engineering C. 76. 25-30.
[4] Sakka S. (2013). Sol–Gel Process and Applications. 10.1016/B978-0-12-385469-8.00048-
4.
[5] Brinker Ch., Hurd A. (1994). Fundamentals of Sol–Gel Dip-Coating. Journal de Physique
III. 4. 1231-1242. 10.1051/jp3:1994198.
[6] Kim Hae-Won, Koh Young-Hag, Li Longhao, Lee Sook, Kim, H.-J. (2004). Hydroxyapatite
Coating on Titanium Substrate with Titania Buffer Layer Processed by Sol–Gel Method.
Biomaterials. 25. 2533-8. 10.1016/j.biomaterials.2003.09.041.
[7] ISO 23317:2014. Implants for surgery -- In vitro evaluation for apatite-forming ability of
implant materials. Berlin: DIN Deutsches Institut für Normung e.V., 2014. 13 p.
Jahodná, Slovakia
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SYNTHESIS OF CUBIC/TETRAGONAL LEUCITE BY CONTROLLED ION

EXCHANGE
1 1 2
Alexandra Kloužková , Pavla Dvořáková , Martina Kohoutková
1
Department of Glass and Ceramics, University of Chemistry and
Technology Prague, Technická 5, 166 28 Prague, Czech Republic;
2
Central Laboratories, University of Chemistry and Technology Prague,
Technická 5, 166 28 Prague,
e-mail:alexandra.klouzkova@vscht.cz
This paper is focused on the synthesis of fully and partially stabilized cubic leucite. X-ray
powder diffraction analysis was used to determine quantitatively the amount of cubic and
tetragonal forms of hydrothermally prepared Cs ion-exchanged leucite. It was proved that the
hydrothermally synthesised Cs - leucite is formed by spherolites having particle size of
c.10μm and consisting of crystallites in tens of nm scale using SEM analysis.
Keywords: cubic leucite, tetragonal leucite, phase transformation, X-ray powder diffraction,
SEM
Introduction
Leucite (KAlSi2O6) is the dominating crystalline phase in most feldspathic dental
porcelains used for dental restorations [1]. It was found that addition of the 15 –
30% of leucite increased the thermal expansion coefficient of the base glass from
-6 -6
10.7 × 10 /°C to 13 - 15 × 10 /°C and it also approximately two times increased
the flexural strength of a feldspathic porcelain [2, 3]. The mineral leucite can be
incorporated into a dental porcelain either from the incongruent melting of feldspar
or it can be added as a synthetic powder. Leucite crystallises at high temperatures in
the cubic form. On cooling below approximately 625 °C, there is a phase transition
to a tetragonal form. Conversion of cubic leucite into the tetragonal modification
involves deformation of the six-fold rings, i.e. the channels distortion is accompanied
+
by slight movements of the K ions. Martensitic temperature Ms is not constant, for
example in the case of hydrothermally prepared leucite it is 550 °C [4].
The aim of this study is the hydrothermal synthesis of partially stabilized cubic
leucite by controlled ion exchange. Particle size and morphology analyses were
completed by scanning electron microscopy (SEM).
Experimental
Synthesis of partially stabilized cubic leucite
Preparation of leucite powders proceeded in two steps, both in hydrothermal
conditions: 1) synthesis of analcime (NaAlSi2O6·H2O), and 2) preparation of Cs -
leucite performed by ion exchange of analcime. Analcime was synthesised in
hydrothermal conditions at 200 °C for 2 h in a Teflon lined stainless steel autoclave.
Starting sols were prepared from a fine-ground amorphous silica powder (SiO2, Lach
- Ner, s.r.o.), sodium hydroxide solution (NaOH, Lach - Ner, s.r.o.) and an aluminium
th
SYNTHESIS OF CUBIC/TETRAGONAL LEUCITE BY CONTROLLED ION EXCHANGE
A. Kloužková, P. Dvořáková, M. Kohoutková
powder (Alfa Aesar GmbH & Co KG). After this hydrothermal treatment, the content
of the autoclave was washed with boiling distilled water, vacuum filtered and dried in
+
an oven at 100 °C. K-leucite was prepared by ion exchange of analcime (Na ions
+ -3
for K ions) from 4 M(mol.dm ) solution of KCl (Penta, s.r.o.) in an autoclave at
200°C for 4 hours [6]. Cs - leucites were prepared by dual ion exchange of
analcime. The synthesis was performed in hydrothermal conditions at 200 °C. First
ion exchange proceeded in 4 M CsNO3 (Sigma – Aldrich, s.r.o.) for 4h. For second
ion exchange a 4 M KCl solution was used. The reaction time was modified to obtain
the desired amount of the cubic form in the final product. After the hydrothermal
treatment, the content of the autoclave was washed, vacuum filtered and dried at
100°C.
X-ray fluorescence, powder diffraction and scanning electron microscopy
analyses
An Performix (Thermo ARL, Switzerland) sequential WD-XRF spectrometer was
used to perform the XRF measurements. The powders to be analyzed were pressed
into pellets about 5 mm thick and diameter of 40 mm without any binding agent and
covered with a supporting 4 mm polypropylene film. The time of measurement was
about 15 min. The data were evaluated with the standardless software Uniquant 5.
3
Powder XRD data were collected at room temperature with a PANalytical X'Pert
Powder θ-θ powder diffractometer using CuKα radiation (λ = 1.5418 Å, U = 40 kV,
I= 30 mA) in parafocusing Bragg-Brentano geometry. Data were scanned with an
ultrafast 1D detector PIXCEL detector over the angular range 5 - 80°(2θ) with a step
size of 0.0167°(2θ) and a counting time of 120s step-1. Mass fractions of the cubic
and tetragonal leucite forms were estimated using the scale factor and the RIR
(Reference Intensity Ratio) values from the ICDD database by HighScore Plus 4.8.
Software. Raman spectroscopy was used for the identification of transformation of
analcim to pollucite (RS-Spectrometer DXR, Thermo Scientific). A diode Nd: YAG
laser with a wavelength of 532 nm and an input power of 10 mW was used as the
excitation source. Samples were measured at 8 mW, 10 sec measurement time and
10 spectrum accumulations. A grid of 900 scratches/ mm and an aperture of 25 µm
pinhole was used. A multichannel thermoelectrically cooled CCD camera was used
as a detector. The OMNIC 5.0 program was used for evaluation.
The morphology and particle size analysis of the synthesised samples were
determined using SEM (Hitachi S-4700). The images were scanned at different
magnifications to demonstrate the homogeneity and particle size distribution in the
whole sample and to show the morphology of the single grains.
Results
Partially stabilised cubic leucite powders were prepared by dual ion exchange of the
synthesised analcime powders with particle size 10-15 μm. The reaction time of the
second ion exchange Na  Cs was modified to obtain the desired amount of the
+ +
cubic form in the final leucite product: sample B - 2h (1 wt.% cubic form), C - 24h
(14 wt.% cubic form) and D - 48h (21 wt.% cubic form). Sample LS representing
tetragonal K – leucite was prepared by single ion exchange of analcime. Chemical
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and phase compositions of the products prepared by the above mentioned synthesis
procedures are shown in Table1 resp. Table 3. Raman band positions of analcime
and pollucite are presented in Table 2.
Fig. 1 XRD synthetized products - tetragonal leucite (LS) and partialy stabilized cubic leucites
(SL-S-2; SL-S-24 and SL-S-48 )
Table 1 Chemical compositions of products – analcime, pollucite

chemical composition mineralogical composition
sample/signification/ [wt.%] [wt.%]
time of synthesis
Na2O Al2O3 SiO2 Cs2O analcime pollucite
A, A4-S, analcime 16 27 57 0 100 -
B, P4-S-2, pollucite/ 2 h 2,77 15,34 80,17 1,72 98 2
C, P4-S-24, pollucite /24 h 2,39 14,30 72,65 10,65 93 7
D, P4-S-48, polucit /48 h 2,22 13,73 69,02 15,03 90 10
Table 2 Raman band positions of analcime and pollucite

mineral analcim pollucite
sample A4-S P4-S-2 P4-S-24 P4-S-48
-1
band position [cm ] 484,5 483,9 483,4 482,6
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SYNTHESIS OF CUBIC/TETRAGONAL LEUCITE BY CONTROLLED ION EXCHANGE
A. Kloužková, P. Dvořáková, M. Kohoutková
Fig. 2 Detail of Raman spectra of syntetized products of partially stabilized cubic leucite
Table 3 Mineralogical compositions of products - t - leucite, partially stabilized c - leucite

mineralogical
chemical composition
sample/signification/ composition
[wt.%]
time of synthesis [wt.%]
Cs2O / T– C–
Na2O Al2O3 SiO2
*K2O leucite leucite
LS, leucit, from A4-S 0,3 25,4 52,5 0/21,7 100 -
LS-S-2, leucite, from P4-S-2 0,3 25 52,6 1,1/ 21 97 1
LS-S-24, leucite, from P4-S-24 0,3 24,4 50,7 5,7/18,8 88 14
LS-S-48, leucite, from P4-S-48 0,2 24,1 50,1 7,9/17,6 85 21
Fig. 3 SEM images of the syntetized products of partially stabilized cubic leucite
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L 20
Prepared samples were in form of homogenous powders with a uniform particle size
~ 10 μm and shape (Fig. 3). SEM images revealed that these particles are
spherolites composed by much smaller particles.
Conclusions
XRD analysis showed that partially stabilized Cs - leucite powders prepared by dual
ion exchange of analcime correspond to crystalline Cs - leucite in both tetragonal
and cubic forms. XRF analysis was used to estimate the degree of ion - exchanges
+ +
(K , Cs ) in the samples. The method is fast and reliable in the stage of
optimalization of the synthesis procedure. SEM was used to study the grain
morphology and size distribution. The final products are spherolites of about 10 μm
large consisting of particles of tens nm scale.
References
[1] ŠATAVA, V., KLOUŽKOVÁ, A., LEŽAL, D. & NOVOTNÁ, M., 2002, Ceramics –
Silikáty,46, 37.
[2] DENRY, I.L., MACKERT, J.R., HOLLOWAY, J. & ROSESTIEL, S., 1996, J. Dent.
Res.,75(12), 1928.
[3] RASMISSEN, S.T, MC LAREN, C.I. & O`BRIEN, W.J., 2004, J. Biomed. Mater. Res.B, 69,
195.
[4] NOVOTNÁ, M. & MAIXNER, J., 2006, Z. Kristallogr. Suppl., 23, 455.
[5] MAIXNER, J., KLOUŽKOVÁ, A., MRÁZOVÁ, M., KOVOTNÁ, M. Z. Kristallogr.,26, 531-
536, 2007.
[6] Vysoká škola chemicko-technologická v Praze. Leucit pro výrobu kovo-keramických či
celo-keramických zubních náhrad, synteticky získaný v hydrotermálních podmínkách.
Vynálezci: KOHOUTKOVÁ, M., KLOUŽKOVÁ, A., ŠATAVA, V., MRÁZOVÁ, M. Česká
republika. Patent CZ 303284 B6. 30. 5. 2012. a Užitný vzor CZ 22403 U1. 2
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Ce3+ DOPED YTTRIA NANOPOWDERS FOR TRANSPARENT YTTRIA

CERAMICS PREPARED BY PRECIPITATION METHOD
1 2 1
Nibu Putenpurayil Govindan , Monika Michálková , Dušan Galusek
1
FunGlass - Centre for functional and surface functionalized glass, TnUAD, Trenčín,
Slovakia
2
Vitrum Laugaricio – Joint Glass Center of the IIC SAS, TnUAD, and FChPT STU,
Trenčín, Slovakia
e-mail:nibu.puthenpurayil@tnuni.sk
3+
Cerium doped yttrium oxide (Y2O3:Ce ) nanopowders have been synthesized using
precipitation method. Ammonium hydroxide was used as a precipitation agent. Partly
agglomerated powders with the primary size of Y2O3 nanoparticles ~ 55 nm and cubic crystal
structure were prepared. A slurry in isopropanol was then ultrasonicated to deagglomerate
the nanopowder. Polyethylene glycol was used as a dispersant to improve the rheological
properties of the alcoholic slurries. The green compacts were prepared by vacuum-pressure
filtration of prepared alcoholic suspension and the green bodies with relative density > 43 %
were prepared. In order to eliminate porosity, the green bodies were sintered at 1550 °C for
-1 3+
3h at a heating rate of 10 °C.min . The density of sintered Ce doped yttria samples was in
all cases close to 98 %. All sintered ceria doped samples displayed dense microstructure with
closed porosity and monomodal grain size distribution.
Keywords: Y2O3, Transparent ceramics, Precipitation.
Introduction
Transparent polycrystalline ceramics are attractive optical materials that offer many
advantages over single crystals, including greater shape control, higher
homogeneity of the dopant, and faster and lower cost fabrication methods. The
interest in transparent ceramics is dated back to 1960's when translucent Al2O3 for
lighting applications was developed [1–3], and slowly expanded into other areas
including transparent armour [4], infrared windows [4], lasers [5,6], and scintillators
[7]. To date, various transparent ceramics with high purity and high density have
been prepared, including simple oxides such as MgO, Y2O3, and ZnO, composite or
complex oxides such as ZrO2–Y2O3, Y3Al5O12, spinel (MgAl2O4), ferroelectric PLZT
((PbLa)(ZrTi)O3), SBN (SrxBa1-xNb2O6), Gd2O2S:Pr, and (YGd)O3:Eu, and even non-
oxides such as AlON and AlN, for applications in solid-state lasers, electro-optical
devices, X-ray scintillators, and thermally conductive components [8–10]. Among
transparent ceramic materials yttria ceramics has been developed for applications in
e.g. solid state lasers. Y2O3 transparent ceramics are also very efficient NIR-visible
up-converters, and can be used as materials for X-ray scintillator applications [11].
Present paper deals with the preparation of Y2O3 nanopowders by precipitation
method using ammonium hydroxide as precipitation agent. The green compacts
were successfully prepared by vacuum-pressure filtration of alcoholic suspension
stabilized with polyethylene glycol.
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Ce3+ DOPED YTTRIA NANOPOWDERS FOR TRANSPARENT YTTRIA CERAMICS PREPARED BY
PRECIPITATION METHOD N. Putenpurayil Govindan, M. Michálková, D. Galusek
Experimental part
-3
The 0.1 M(mol.dm ) aqueous yttrium (III) nitrate solution was prepared by
dissolving yttria powders (99.99 %) in nitric acid (HNO 3) under stirring and heating,
and dilution in deionized water. The 0.1 M cerium (III) nitrate solution was prepared
by dissolving of salt (99.99 %) in deionized water. The metal nitrate solution is mixed
-1
together and added dropwise with the use of a peristaltic pump at 5.0 ml.min , into a
0.5 M ammonium hydroxide solution,under continuous rapid stirring, ensuring there
was sufficiently high excess of ammonia to eliminate any pH fluctuations throughout
the process. The reaction was completed in 24 h and the clear solution turned to
opaque white slurry. After 12 h aging the slurry was vacuum filtrated and the white
precipitate washed with distilled water. The washed precipitate was dried overnight
in air at 100°C. The dried precipitate was crushed and ground in an agate mortar
-1
and pestle, and calcined in air for 3 h at 700 °C (heating rate 5°C.min ).
Crystallization temperatures of the pre-calcined powders were determined by
differential scanning calorimetry combined with thermogravimetry (Netzsch STA 449
F1 Jupiter TG / DTA / DSC). Powder X-ray diffraction (XRD) patterns were acquired
using powder X-ray diffractometer (Panalytical Empyrean DY1098). The Scherrer
equation was used to determine the size of coherently diffracting domains, which
can be, in an ideal case, identified as the primary size of individual particles. Particle
size and morphology of prepared particles were examined by scanning electron
microscopy (JEOL JSM-7600 F / EDS / WDS / EBSD).
3+
The precipitation method led to severe agglomeration of Ce doped yttria powder.
The powder had to be subjected to efficient deagglomeration before it could be used
for preparation of green compacts. This was carried out by ultrasonication with high
acoustic power, using calculated amounts of Y2O3 powder and isopropyl alcohol and
adding polyethylene glycol (Vanderbilt Minerals, Germany) as a dispersant. After
sonication, particle size distribution was determined as a function of sonication time
using particle size analyser (Brookhaven 90Plus BI-Zeta).
Green compacts were prepared by vacuum - pressure filtration of the ultrasonically
deagglomerated yttria suspension. The vacuum - pressure filtration was performed
in a special die with the diameter of 15 mm. The suspension (20 wt.% solid loading)
was poured into the die and after closing the mould, a pressure of 20 bar was
applied by a hydraulic press. The water from the suspension was drained through
massive perforated metal bottom with a polymeric membrane (pore size 0.2 µm).
The density of green samples was determined by calculating volume of the green
compact and weight of the sample was measured. In order to eliminate porosity, the
-1
green bodies were sintered at 1550 °C for 3 h, at a heating rate of 10 °C.min .
Relative density of sintered samples was determined by Archimedes principle in
water.
Figure 1 presents the results of DTA and related TG analysis of prepared
[Y(NO3)3·xY(OH)3·yH2O] precipitate. TGA curve shows a weight loss of sample in
five steps. The first and second stages in the DTA curve correspond to the absorbed
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L 21
and bonding water, which relate to weak endothermic peaks at 104°C and 232°C ,
respectively. The exothermic peaks at 330 °C and 530 °C (steps 3 and 4) are
caused by decomposition of yttrium hydroxide precursor and crystallization of yttria.
Dehydration of chemisorbed and combined water from Y(OH)3 and α-Y(OH)3 is
represented by the endothermic effect at 394 °C. Due to the presence of HNO3
during dissolution of yttria, basic yttrium hydroxy-nitrate complex
[Y2(NO3)3·xY(OH)3·yH2O] is formed. Decomposition of such complexes takes place
approximately at 530 °C. This temperature is also related to the onset of
crystallization of the yttrium oxide [12-15] Consequently, as confirmed by the TG/
DTA record, decomposition of prepared yttria precursor is completed at 600 °C. No
more exo- or endothermic effects were detected at higher temperatures. The
calcination of Y2O3 powder prepared by precipitation was therefore carried out at
700 °C.
105 0.5
Exothermic
530°C
100
330°C
0.4
95
90
0.3
weight(%)
Endothermic
DTA(v/mg
85
80 0.2
75
0.1
70 104°C 232°C
65 394°C 0.0
60
0 200 400 600 800 1000
Temperature (C)
Fig. 1 DTA/TGA data for the precipitated hydroxide precursor
3+
Figure 2 shows the powder diffraction patterns of Ce doped Y2O3 powder calcined
at 700 °C. The pure cubic Y2O3 phase was obtained with good crystallinity. The
primary particle size of prepared nanopowder, as determined from the Scherrer
3+
equation, was approximately 50 nm. Due to the very low concentration of Ce in
doped yttria powder no change or shift of peak positions in the XRD pattern was
observed. Hence, the change of the crystal lattice is so small that it could not be
detected by XRD, which is in agreement with the literature [16].
Microstructure analysis and particle size distribution of yttria powders
3+
Figure 3 shows the SEM micrographs of synthesized Ce doped Y2O3 powders. The
powders are agglomerated with the primary particle size of approximately 55 nm,
3+
which is in accord with the X-ray diffraction data. All Ce doped samples show the
same particle size and all powders are agglomerated. Doping of yttria powder by
Jahodná, Slovakia
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25 -27 June, 2019 135
cerium(III) ions did not have any significant effect on particle size and distribution.

PDF no 89-5591  Y2O3
0.01%Ce 
 
   
0.005%Ce   
   
0.001%Ce 
  
  
10 20 30 40 50 60 70 80
2/°
3+
Fig. 2 XRD pattern of prepared Ce doped Y2O3 powder calcined at 700 °C
Fig. 3 SEM micrograph of the synthesised

3+
Ce doped Y2O3 powder,
A) 0.001 % Ce,
B) 0.005 % Ce,
C) 0.01 % Ce
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L 21
3+
Figure 4 summarizes the changes in particle size of 0.01 % Ce doped yttria with
the sonication time. Extension of the ultrasonication time results in significant
reduction of both the mean particle size and the width of the particle size distribution.
The best results were achieved after 32 minutes of sonication. Both the SEM
examination and the results of X-ray powder diffraction indicate the primary particle
size around 55 nm. However, ultrasonication of alcoholic yttria suspension leds to an
average particle size of 200 nm. This clearly shows that the powder was not
completely deagglomerated down to primary particles, and hard agglomerates with
the diameter of about 200 nm were still present. Green compacts were prepared by
vacuum-pressure filtration of yttria alcoholic suspension. The relative density
reached 43 %.
3+
Figure 5 shows the fracture surfaces of sintered Ce doped yttria ceramics. SEM
3+
analysis of all Ce doped samples displayed microstructure closed porosity, which
could be used as a starting material for hot isostatic pressing. Table 1 summarizes
3+
the relative densities of all Ce doped yttria samples after sintering at 1550 °C.
2000
1800
1600
1400
particle size(nm)
1200
1000
800
600
400
200
0
0 5 10 15 20 25 30 35
Time(min)
3+
Fig. 4 The change of particle size distribution of the 0.01 % Ce doped yttria powder
withthe sonication time
3+
Table 1 Relative density of Ce doped yttria ceramic prepared by pressure filtration method,
sintered at 1550 °C for 3 h
3+
Ce doped yttria Relative density
3+
0.001 Ce 97.88 %
3+
0.005 Ce 98.38 %
3+
0.01 Ce 98.57 %
Conclusion
Ce-doped Y2O3 nanopowders with various content of doping were synthesized by
precipitation method using ammonium hydroxide as the precipitation agent. Partly
agglomerated powders with the primary size of Y2O3 nanoparticles 55 nm and cubic
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25 -27 June, 2019 137
crystal structure were prepared by calcination of precipitates at 700 °C. The relative
density of green compacts prepared by vacuum-pressure filtration of isopropanol-
3+
based suspensions was ~ 43 %. The relative density of sintered Ce doped yttria
samples was in all cases close to 98 %.
3+
Fig. 5 Fracture surfaces of sintered Ce
doped Y2O3 powder,
A) 0.001 % Ce,
B) 0.005 % Ce,
C) 0.01 % Ce
Acknowledgment: This paper is a part of dissemination activities of the project FunGlass.

This project has received funding from the European Union´s Horizon 2020 research and
innovation programme under grant agreement No 739566. Financial support of this work by
the grants VEGA 2/0026/17, and SAS-MOST 2015-06 is gratefully acknowledged.
Reference
[1] R.L. Coble. Transparent Alumina, US Patent 3,026,210. Mar. 20; (1962)
[2] R.L. Coble. J. Appl. Phys. 32, 787. (1961)
[3] G.C. Wei. J. Phys. D. Appl. Phys. 38, 3057.(2005)
[4] P.J. Patel, G.A. Gilde, P.G. Dehmer, J.W. McCauley. Proc. Soc. Photo-Opt. Instrum.
Eng. 4102. (2000)
[5] V. Lupei, A. Lupei, A. Ikesue. Opt. Mater. 30, 1781. (2008)
[6] J. Li, Y. Pan, Y. Zeng, W. Liu, B. Jiang, J. Guo. Int. J. Refract. Metals Hard Mater. 39,
44. (2013)
[7] C. Greskovich, S. Duclos, Annu. Rev. Mater. Sci. 27, 69. (1997)
th
L 21
[8] A.Ikesue,T.Kinoshita ,K.Kamata. J. American Ceramic Society. 78, 1033. (1995).

[9] G.D .Miles, R.A.J. Sambell, J .Rutherfo, G.W. Stephens j. British Ceramic Society.
66,319 (1967)
[10] R.W.Rice, J. of the American Ceramic Society. 54,205. (1971)
[11] C.Greskovich, M.J. Curran, C.R.Oclair J. American Ceramic Society. 55,324.(1972)
[12] H. Gong, T. Ding-Yuan, H. Hui, Z. Tian-Shu, M. Jan. Effect Mater. Chem. Phys. 112,
4234(2008)
[13] M.Khajelakzay,R.S.Razavi, M. Barekat, M. Naderi . Int. J. Appl. Ceram. Technol. 13, 209
(2016)
[14] R. Srinivasan, N. R. Yogamalar, J. Elanchezhiyan, R. J. Joseyphus, A. C. Bose.Journal
of Alloys and Compounds. 496, 477.(2010)
[15] L. Muresan, E. J. Popovici, R. Grecu, L. B. Tudoran.Journal of Alloys and Compounds.2,
421, (2009.)
[16] S. Singhal, A. Chawla, R. Chandr. Journal of Nanoscale Research Letters.1, 321.
(2009).
Jahodná, Slovakia
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25 -27 June, 2019 139
L 22
THE EFFECT OF CALCIUM FLUORIDE ON MINERAL PHASES

ANDPROPERTIES OF LIGHTWEIGHT EXPANDED CLAY AGGREGATES
Mohamed Abdelfattah*, István Kocserha, Robert Géber

Institute of Ceramic and Polymer Engineering, University of Miskolc, Miskolc,
Hungary
e-mail: madatow@yahoo.com
This work is focused on studying the effect of calcium fluoride (CaF2) on physico-mechanical,
and expansion properties and mineral phases of expanded clay minerals. Samples were
collected from Mályi quarry Miskolc, Hungary. They were characterized by XRF, XRD, SEM
microscopy and heating microscope. Physico-mechanical properties of specimens were
measured according to relating standards. Results showed that, CaF2 decreased the bulk
density of the lightweight aggregates. In addition to, sintering temperature decreased by
approximately 125 °C lower than the temperature used by the LWA manufacturing sector.
Keywords: expanded clay, CaF2, lightweight aggregates
Introduction
Additive materials are the solutions to enhance the physical, mechanical and
expansion properties of lightweight expanded clay aggregates (LECA) or to change
the plasticity of raw clays [1,2]. There are lots of different materials that are in use
usually added to the lightweight aggregates to improve the compressive strength,
expansion or decrease density. Among them the most important additive is calcium-
fluoride [3] as it has a positive effect on sintering temperature. In other industrial
branch CaF2 is also has positive effect on technology. CaF 2 can be used in different
industrial application such as additive material into lightweight aggregates and
cement and concrete technology. CaF2 was affected on the sintering temperature,
clinkering temperature and compressive strength of the solid material. In lightweight
aggregates (LWA) manufacturing for concrete industry, partially replacing river
sediment formed from with 10–20 % of CaF2 can effectively manufacture LWAs via
sintering at 1050–1100 °C for 10 min [3]. According to studies in the field of cement
and concrete production, adding 10–20 % of CaF2 to a mortar, compressive strength
of it was increased by 25–35 % after curing for 7–90 days [4]. In contrast, Kim and
Qureshi made different mixtures of CaF2 sludge, portland cement, and white
portland cement to solidify/stabilize. They observed the compressive strength of the
solidified substance reduced with increasing CaF 2 content. Clinkerization
temperature was decreased by 220 °C by addition of CaF 2 (1–2 %) to cement raw
materials [5,6]. A mixture of 60 % sludge and 40 % waste glass could be
successfully co-melted at 1163°C to fine aggregates for construction and
engineering application [7]. Fathi et al [8] was investigated the effect of CaF 2 on the
solubility of apatite-mullite. The general formula used for forming glass was 4.5SiO2
-3Al2O3-3CaO-1.5P2O5-xCaF2, where x = 0.5–3. They concluded that fluoride
facilitated crystallization because it incurred phase separation by rearranging the
Jahodná, Slovakia
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25 -27 June, 2019 141
THE EFFECT OF CALCIUM FLUORIDE ON MINERAL PHASES AND PROPERTIES OF LIGHTWEIGHT
EXPANDED CLAY AGGREGATES M. Abdelfattah, I. Kocserha, R. Géber
glass network through replacement of O 2 by F [9]. Present study aims to analyse the
effect of addition of CaF2 on different expandable clays.
Material and method
Three types of expanded clay samples were collected from Mályi quarry, Miskolc,
Hungary. Clays were named as follows: grey clay: G, blue clay: B and Yellow clay:
Y. Samples were dried at 105 °C for 24 h in an air circulating electric drying
chamber. They were readily ground for a few seconds to reduce particle
agglomeration and milled to pass through an opening sieve 150 µm for further
measuring. Chemical composition of the samples was determined by X-ray
fluorescence spectrometer (Rigaku Supermini 200 WDXRF), in addition the results
of the chemical composition after calcined basis were plotted in the Riley diagrams
[10]. Mineral phases were analyzed by X-ray diffraction (Rigaku Miniflex II, Cu Kα,
2θ range from 3 to 90°). Microstructure of LECAs was observed with an
environmental scanning electron microscope (ESEM) under high vacuum mode
(Carl Zeiss EVO MA10). The expansion of clay samples was measured and
observed by heating microscope (Camar Elettronica). The three types of clay are
mixed with 10 % and 20 % of CaF2. Green pellets (five each) were produced by
hand-rolling. Pellets were dried 105 °C in a drying chamber. Dried pellets were
sintered at five different temperatures. For air atmosphere sintering an electrical
furnace was used. Temperature values were set to 1000 °C, 1050 °C and 1100 °C
respectively. Sintering time was ten minutes at maximal temperature. Lastly, after
the heating process at 1050 – 1100 °C, sintered products were naturally cooled in
the atmosphere, and their physical and mechanical properties were analysed.
Uniaxial compressive strength and bulk density were measured according to UNE-
EN-13055-1 European standards.
The bulk density was measured using the Archimedes method after the LECAs were
placed in water for 24 h. The bulk density was calculated using equation [1]
–3
Bulk density = W D/ (W S –W I) [g.cm ] [1]
where W D: dry weight of the LECA, W S: 24 h saturated surface-dry weight, W I:
immersed weight in water [11].
The compressive strength was measured by an INSTRON 5556 universal tester with
-1
a cross-head speed of 0.1 mm.s . The compressive strength of the LECA was
calculated according to equation [2]
Compressive strength = F/A [MPa] [2]
where F: load belongs to fracture, A: area of the LECA [12].
Results
Expansion, Mineral and Chemical composition
From chemical analysis, the three Mályi clay samples were bloated according to the
Riley diagram [10]. The five patches of expanded clay were located in the bloating
area (Fig 1a.), which means that the five batches can be expanded upon firing below
1300 °C [13]. Analysis of images obtained from heating microscope revealed the
characteristic temperatures (T) and height expansion (H) of the samples, (Fig. 1b).
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Results show that the blue clay sample had the highest expansion of 38 % at
1265°C, while melting point of this sample was 1325 °C (Fig. 2a). After adding 20 %
of CaF2 to the blue clay, sintering temperature of it decreased to 1110 °C and reach
the maximum expansion of 10 % at 1140 °C and the melting point of it lower to
1160°C (Fig. 2b). Grey clay sample expanded by 9 % extent with 20 % of CaF2
addition at 1150 °C, whilst, the yellow clay sample didn’t expand. On the other side,
10 % of CaF2 addition caused no expansion on aggregates.
Fig. 1 a) Chemical composition of the technological sample as plotted on Riley's diagram

(1951). b) The relation between height expansion of clay samples with the temperature
Fig. 2 a) Heating microscope measurement of sample of blue clay samples with 0 % of CaF 2,
b) Heating microscope measurement of sample of blue clay samples with 20 % CaF 2
Lightweight aggregate characterization

The physical and mechanical parameters of the expanded Mályi clay with CaF 2 were
measured according to the requirements specified in the UNE-EN-13055-1
European standards. Results were summarized in Table 1. The bulk densities of the
–3
aggregates in this study were lower than 1.6 g.cm . According to European Union
–3
regulation EN-13055-1, particle bulk density between 0.8 and 2.0 g.cm can be
used as lightweight aggregates. Bulk density range of the Mályi clay samples with
–3
20 % of CaF2 was (1.2–1.49) g.cm at 1100 °C. By addition of 10 % of CaF2 to
Jahodná, Slovakia
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25 -27 June, 2019 143
Mályi clay samples, the bulk densities of the fired samples were between 1.39-
–3
1.6g.cm at 1100 °C. Whilst, the compressive strength range of these aggregates
at 1100°C was (1.35–4) MPa, and this range is higher than 1 MPa. So these values
are acceptable according to Liao and Huang [14, 15].
Table 1 Bulk density and compressive strength of expanded clay aggregates with CaF 2
additive at different temperature
Bulk density, g.cm-3 Compressive strength, MPa
Samples CaF2 0% CaF2 10% CaF2 20% CaF2 10% CaF2 20%
1050 1100 1050 1100 1050 1100 1050 1100 1050 1100
°C °C °C °C °C °C °C °C °C °C
B 1.82 1.8 1.77 1.39 1.77 1.2 16 9.31 4.50 3
Y 2.05 2 2 1.52 2 1.37 23 10.89 6.00 4.00
B+G (50-50) 1.97 1.95 1.9 1.43 1.9 1.38 18 10.34 5.50 1.34
B+Y (50-50) 1.95 1.93 1.95 1.60 1.95 1.49 12 4.93 5.12 3.80
G 1.99 1.98 1.92 1.39 1.92 1.25 15 5.196 4.90 3.77
Discussion
The mineral phases after firing temperatures at 1100 °C and 1225 °C were studied
by XRD (Fig. 3a). The mineral phases formed at 1225 °C were quite different from
the pre-firing stages. The mineral phases of blue clay sample were quartz (pdf no.
01-079-1910), hematite (pdf no. 01-073-0603), and anorthite (pdf no. 01-073-0265),
whilst the mineral phases of yellow were quartz, hematite (pdf no. 01-073-0603),
anorthite and mullite mineral (pdf no. 01-083-1881). (Fig. 3a). On the other hand, the
CaF2 had great effect on the mineral phases of the lightweight aggregates (Fig.3b).
After adding CaF2, mineral phases of aggregates were fluorite (pdf no. 01-077-
2093), hematite, quartz low (pdf no. 01-085-0335), cristobalite (pdf no. 01-071-
0785), and anorthite.
Fig. 3 a) XRD patters of lightweight expanded clay aggregates at 1225 °C b) XRD patters of
lightweight expanded clay aggregates with CaF 2 at 1100 °C
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L 22
Therefore, after studying the expansion, physical and mechanical properties of the
clay sample it can be shown, the blue Mályi clay samples can be used as lightweight
aggregates with add 20 % of CaF2.
From previous measurement, the blue clay sample with 20 % of CaF 2 had bloated,
–3
in addition, the density was the lowest at the 1100 °C (10 % and 1.2 g.cm ),
respectively. The compressive strength of the samples with 20 % of CaF 2 was lower
than the compressive strength of the samples with 10 % of CaF 2, due to, the some
of CaF2 didn’t react with the clay and didn’t transformed to other mineral phases.
Mohs hardness of fluorite is 4, so the compressive strength of the aggregates
decreased with increasing the percentage of CaF 2. The microstructure of the Mályi
clay aggregates was determined using a scanning electron microscope. The cross-
section of the aggregate pellet was revealed that the material was composed of two
layers. The SEM micrograph was showed that the inner layer had large pores,
whilst, the pores in outer layer were not only small but also more irregular (Fig. 4a).
The large pores can affect on the properties of this aggregate, in addition, the high
percentage of porosity had great effect on the compressive strength of this
aggregate.
Fig. 4 SEM micrograph of a) Blue clay aggregate at 1225 °C; b) Blue clay aggregate with
20% of CaF2 at 1100 °C; c) Yellow clay aggregate with 20 % of CaF2 at 1100 °C;
d)Yellow clay aggregate with 10 % of CaF2 at 1100 °C
On the other hand, adding CaF2 had crucial effect on the shape of pores in
aggregates. 20 % of CaF2 addition, the roundness of pores was increased (Fig. 4b,
Jahodná, Slovakia
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25 -27 June, 2019 145
4c), whilst, pores in aggregates with 10 % of CaF 2 were angular (Fig. 4d). Besides,
in aggregates with 20 % of CaF2, small pores were closed and they contained only
the large. In addition, the surface of the aggregates was also smoother
Conclusion
Addition of CaF2 to the clay samples has great effect on the density, sintering and
melting point of the lightweight expanded clay aggregates. CaF 2 can be used for
decreasing the bulk density of the lightweight aggregates. This additive caused the
decreasing the sintering temperature approximately by 125 °C lower than the
temperature used by the LWA manufacturing sector. Melting point was also
decreased by 165 °C. This replacement may help in decreasing the sintering
temperature and cost of furnace maintenance.
Acknowledgement: This research was supported by the European Union and the Hungarian
State, co-financed by the European Regional Development Fund in the framework of the
GINOP-2.3.4-15-2016-00004 project, aimed to promote the cooperation between the higher
education and the industry.
Reference
[1] I. Kocserha, L.A.Gömze: Friction properties of clay compounds, Appl.Clay.Sci.48(2010)425-430
[2] I. Kocserha, A. Hamza, R. Géber: The effects of red mud on clay compounds, Mater. Sci.
Eng. (2018) 426.
[3] Y.Wei, S.Weng, X.Xie: Reduction of sintering energy by application of calcium fluoride as flux
in lightweight aggregate sintering, Construction and Building Materials.190(2018) 765–772.
[4] T. C. Lee, F. J. Liu: Recovery of hazardous semiconductor-industry sludge as a useful
resource, J. Hazard. Mater. 165 (2009) 359–365.
[5] Y. J. Kim, T. I. Qureshi: Recycling of calcium fluoride sludge as additive in the solidification–
stabilization of fly ash, J. Environ. Eng. Sci. 5 (2006) 377–381.
[6] K. Raina, L.K. Janakiraman: Use of mineralizer in black meal process for improved
clinkerization and conservation of energy, Cem. Concr. Res. 28 (1998) 1093–1099.
[7] W. T. Liu, K. C. Li: Application of reutilization technology to calcium fluoride sludge from
semiconductor manufacturers, J. Air Waste Manage. Assoc. 61. (2011) 85–91.
[8] H. Fathi, A. Johnson, R. van Noort, J.M. Ward, I.M. Brook: The effect of calcium fluoride
(CaF2) on the chemical solubility of an apatite–mullite glass–ceramic material, Dent. Mater.
21 (2005) 551–556.
[9] A.Clifford, R.G.Hill: Apatite–mullite glass–ceramics, J.Non-Cryst. Solids 196(1996) 346–351.
[10] C.M. Riley: Relationship of chemical properties to bloating of clays. J. Am. Ceram. Soc. 34.
(1951)121–128.
[11] A. M. Neville.: Properties of Concrete, 4th ed. Prentice Hall. 1995.
[12] Y. Li, D. Wu, J. Zhang, L. Chang, Z. Fang, Y. Shi.: Measurement and statistics of single pellet
mechanical strength of differently shaped catalysts, Powder Technol. 113 (2000) 176–184.
[13] T. Kavas, A. Christogerou, Y. Pontikes, G. N. Angelopoulos.: Valorisation of different types of
boron-containing wastes for the production of lightweight aggregates. J Hazard Mater. 185.
(2011)1381–1389.
[14] Y. Liao, C. Huang.: Effects of heat treatment on the physical properties of lightweight
aggregate from water reservoir sediment, CERAM INT. 37 (2011) 3723–3730.
[15] K. Piszcz-Karaśa, M. Kleinb, J. Hupkaa, J. Łuczaka.: Utilization of shale cuttings in
production of lightweight aggregates. J ENVIRON MANAGE. 231 (2019) 232–240.
th
L 23
NEW ZEOLITE-ALUMINA COMPOSITE MATERIALS - DEVELOPMENT

AND INVESTIGATION
1,2 1 1,3,4
Jamal F. M. Ibrahim , Emese Kurovics , László A. Gömze
1
Institute of Ceramics and Polymer Engineering, University of Miskolc, Hungary.
2
Department of Materials Technology, University of Bahri, Khartoum, Sudan.
3
IGREX Engineering Service LTD, Hungary.
4
Tomsk State University, Russian Federation.
e-mail: jamalfadoul@gmail.com
In this work, zeolite-alumina ceramic composite materials were developed by the authors
on the basis of natural zeolite from Tokaj region (Hungary) and MOTIM Al 2O3 powder using
mechanical activation and reactive sintering methods. The structure, morphology and
characteristics of the complex composite structured were investigated using different
characterization techniques including, scanning electron microscopy (SEM) and X-ray
diffraction (XRD). The X-ray investigating of the natural zeolite from Tokaj region has
shown many phases with different contents of minerals like montmorillonite, quartz,
cristobalite, clinoptilolite, and calcite. Meanwhile, after mechanical activation, compaction
and sintering of the zeolite-alumina samples, new compositions of the ceramic composite
were achieved. In their presentation, the authors would like to introduce th is new ceramic
composite materials and their properties.
Keywords: zeolite, composite, reactive sintering.
Introduction
High attention and tremendous interest have been lately paid to study ceramic
reinforced ceramic composites due to their fascinating properties such as high
hardness, good compressive strength, resistance to aggressive media, refractory
properties and good fracture toughness [1-7]. All these properties make Ceramic
matrix composites (CMCs) a popular candidate for many practical applications
including electronic substrate, bio-ceramics, wear resistance materials, refractories,
catalyst, cutting tools and armour [8-9]. The main reason beyond synthesizing
ceramic composite materials is to reduce their brittle nature which highly diminishes
their properties and restricts their applications [10]. Reinforcing a ceramic matrix with
a secondary ceramic phase in different forms like fibres, whiskers or particulates is
considered as the most effective methods toward enhancing the different properties
[11], The major challenge is the elimination of agglomeration through the
homogeneous distribution of the reinforcement. Many research works have been
done concerning the synthesis of ceramic reinforced CMCs [12-15]. Among ceramic
materials zeolites have been largely used in various applications, thanking for their
appealing characteristics, for instance, their high ions exchange capacity, their large
surface area, good adsorption efficiency and their capability to host a secondary
phase in their structure [16-17]. Great enhancement of different behaviours of
Zeolite- based ceramic composite have been achieved [18-20]. Yasumori A., et al.
Jahodná, Slovakia
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25 -27 June, 2019 147
NEW ZEOLITE-ALUMINA COMPOSITE MATERIALS - DEVELOPMENT AND INVESTIGATION
J. F. M. Ibrahim, E. Kurovics,, L. A. Gömze
[21] demonstrated that titania reinforced zeolite composite can effectively adsorb
polar molecules. Moreover, an improvement in mechanical properties in zeolite
reinforced ceramic composites had been revealed in many research works [22-23].
In this work, zeolite-reinforced alumina composite materials were prepared using
mechanical activation and reactive sintering method. The morphology and
microstructure of the raw materials and the final product have been examined using
X-ray diffraction (XRD) and scanning electron microscopy (SEM). Furthermore, the
correlation of the composition, firing temperature to the density and water absorption
was investigated. These ceramic products which produced from relatively cheap raw
material could be used in many applications.
Materials and experiments
Zeolite reinforced alumina composite ceramic materials were synthesized using
mechanical activation and reactive sintering techniques. The starting raw materials
include zeolite powders from Tokaj region (Hungary) and Al2O3 powder of MOTIM
with purity 98 %. An adequate proportion of the raw materials were accurately
weighted mixed then milled in Retsch PM 400 planetary ball mill for 15 minutes in
150 rpm using silica balls. The milled powders then uniaxially compacted at 500
MPa pressures to produce cylindrical disc specimens with diameters of 25 mm,
meanwhile, the filling weights of specimens were 10 grams in each case. After
compacting, the prepared specimens were sintered in normal (oxidation)
atmosphere at temperatures of 1100°C and 1200°C in a programmable furnace for
3 h, with a heating rate of 60 °C/h.
Results and discussions
The sintering temperatures had influenced very strongly on colours and the
shrinkages of the ceramics samples (Fig. 1) thanking to the physicochemical
reactions during firing.
Fig. 1 Influence of composition and sintering temperature on colour and shrinkage
X-ray diffractogram of zeolite reveals the existence of many minerals with different
percentages, including montmorillonite, quartz, cristobalite, clinoptilolite, and calcite
which shown in Figure 2 and Table 1.
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Fig. 2 XRD diffractogram of the natural zeolite
Table 1 Mineralogical constituent, chemical composition and loss of ignition (LOI) of the
natural zeolite in wt.%, obtained from XRD analysis
Quartz Cristobalite Montmorillonite Calcite Clinoptilolit Total

wt.% 8.00 50.00 30.00 2.00 10.00 100
CaO 1.12 1.12
SiO2 8.00 50.00 19.13 5.79 82.92
Al2O3 4.06 1.89 5.95
MgO 3.21 3.21
Na2O 0.74 0.57 1.31
CO2 0. 88 0.88
H2O 2.87 1.60 4.47
LOI 0.00 0.00 2.87 0.88 1.75 5.50
Fig. 3 Structure of 90 % zeolite-10 % alumina sintered a) at 1100 °C, b) at 1200 °C
Jahodná, Slovakia
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25 -27 June, 2019 149
During the sintering and after drying, removal of the crystalline waters from zeolite
structure at about 450 °C occurred. Further heating to 1200 °C leads to the
formation of mullite crystal phases and free SiO 2 components. Due to the sintering
process and new phase formation, a remarkable reduction in the density has been
achieved as shown in Figure 3. Figures 4 exhibits the weight loss and density of the
sintered samples respectively. The weight loss of the two type specimens was
almost the same and it is highly increased with increasing the zeolite composition.
while the density is highly increasing with increasing the sintering temperature and
decreasing with increasing the zeolite composition.
Fig. 4 The correlation between a) weight loss and b) density of zeolite based on composition
of the samples sintered at different temperatures
Conclusion
Through the processing technique proposed, zeolite-based alumina composites
were successfully produced. The properties of the final products are highly affected
by the composition percentages and sintering temperatures, a remarkable change is
observed in density, weight loss and colour of the produced specimens, this change
in the characteristics of the different samples can be assigned to the
physicochemical reactions which take place at high temperature.
Acknowledgements: “The described study was carried out as part of the EFOP-3.6.1-16-
2016-00011 “Younger and Renewing University – Innovative Knowledge City – institutional
development of the University of Miskolc aiming at intelligent specialisation” project
implemented in the framework of the Szechenyi 2020 program. The realization of this project
is supported by the European Union, co-financed by the European Social Fund.”
References
[1] Gömze, László A., and Ludmila N. Gömze. "Alumina-based hetero-modulus ceramic
composites with extreme dynamic strength–phase transformation of Si3N4 during high-
speed collision with metallic bodies." 2009 Építöanyag –JSBCM 61 (2) 38.
http://dx.doi.org/10.14382/epitoanyag-jsbcm.2009.7
[2] Gömze, L. A., and L. N. Gömze. "Ceramic-based lightweight composites with extreme
dynamic strength." 2013 IOP Conf. Ser.: Mater. Sci. Eng. 47 012033
https://doi.org/10.1088/1757-899X/47/1/012033
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[3] Gömze, Laszlo A., and Liudmila N. Gömze. "Hetero-modulus alumina matrix
nanoceramics and CMCs with extreme dynamic strength." 2011 IOP Conf. Ser.: Mater.
Sci. Eng. 18 082001 http://dx.doi.org/1757-899X/18/8/082001
[4] Gömze, L. A., et al. "methods and equipment for the investigation of rheological
properties of complex materials like conventional brick clays and ceramic-reinforced
composites." 2015 Építöanyag-JSBCM 67 (4) 143
[5] Savchenko, Nickolai, et al. "The influence of porosity on the elasticity and strength of
alumina and zirconia ceramics." 2014 AIP Conference Proceedings. 1623 (1)
http://dx.doi.org/10.1063/1.4899003
[6] Gömze, L. A., and L. N. Gömze. "Mechanical stress relaxation in hetero-viscous
complex ceramic materials." 2010 Építöanyag –JSBCM 62 (4) 98
[7] Gömze, L. A., and L. N. Gömze. "Rheological principles of development hetero-modulus
and hetero-viscous complex materials with extreme dynamic strength." 2017 IOP Conf.
Ser.: Mater. Sci. Eng. 175 012001 http://dx.doi.org/1757-899X/175/1/012001
[8] Maitra, Saikat, and Jagannath Roy. "Nanoceramic matrix composites: Types,
processing, and applications." 2018 Advances in Ceramic Matrix Composites.
Woodhead Publishing, 27.
[9] Kumar, A. Senthil, A. Raja Durai, and T. Sornakumar. "Development of alumina–ceria
ceramic composite cutting tool." 2004 International Journal of Refractory Metals and
Hard Materials 22 (1) 17 http://dx.doi.org/10.1016/j.ijrmhm.2003.10.005
[10] Marshall, David B., Joseph J. Ratto, and Fred F. Lange. "Enhanced fracture toughness
in layered microcomposites of Ce‐ZrO2 and Al2O3." 1991 Journal of the American
Ceramic Society 74.(12) 2979 https://doi.org/10.1111/j.1151-2916.1991.tb04290.x
[11] Thomson, K. E., et al. "Characterization and mechanical testing of alumina-based
nanocomposites reinforced with niobium and/or carbon nanotubes fabricated by spark
plasma sintering." 2012 Acta Materialia 60 (2) 622
https://doi.org/10.1016/j.actamat.2011.10.002
[12] Apkaryan, Afanasy S., Sergey N. Kulkov, and László A. Gömze. "Foam glass-ceramics
as composite granulated heat-insulating material." 2014 Építöanyag-JSBCM 66 (2) 38
[13] Perez-Rigueiro, J., et al. "Revisiting the mechanical behaviour of alumina/silicon carbide
nanocomposites." 1998 Acta materialia 46.(15 ) 5399
[14] Wu, H. Z., et al. "The strength of Al2O3/SiC nanocomposites after grinding and
annealing." 1998 Acta materialia 46.(11) 3839
[15] Zhao, Junhong, et al. "Mechanical Behavior of Alumina-Silicon Carbide
„Nanocomposites”.1993 Journal of the American Ceramic Society 76 (2) 503
http://dx.doi.org/10.1111/j.1151-2916.1993.tb03814.x
[16] Xu, Ruren, et al. Chemistry of zeolites and related porous materials: synthesis and
structure. 2009 John Wiley & Sons
[17] Buzimov, A. Y., et al. "Effect of Mechanical Treatment on the Structure and Properties of
Natural Zeolite." 2018 Inorg. Mater. Appl. Res. 9 910.
https://doi.org/10.1134/S2075113318050040
[18] Buzimov, Alexandr Y., et al. "effect of mechanical treatment on properties of Si-Al-o
zeolites." 2018 Építöanyag –JSBCM 70 (1) 23
https://doi.org/10.14382/epitoanyag-jsbcm.2018.5
Jahodná, Slovakia
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25 -27 June, 2019 151
[19] Buzimov, A. Y., et al. "Effect of mechanical treatment on properties of zeolites with
chabazite structure." 2017 J. Phys.: Conf. Ser. 790 012004
http://iopscience.iop.org/1742-6596/790/1/012004
[20] Buzimov, A. Y., et al. "Effect of mechanical treatment on properties of zeolites with
chabazite structure." Journal of Physics: Conference Series. Vol. 790. No. 1. IOP
Publishing, 2017.
[21] Yasumori, Atsuo, Sayaka Yanagida, and Jun Sawada. "Preparation of a titania/X-
zeolite/porous glass composite photocatalyst using hydrothermal and drop coating
processes." 2015 Molecules 20 (2) 2349 https://doi.org10.3390/molecules20022349
[22] Naji, Ghassan Abdul-Hamid, et al. "Sodalite zeolite as an alternative all-ceramic
infiltrating material for alumina and zirconia toughened alumina frameworks."
2016 Ceramics International 42 (10) 12253
https://doi.org/10.1016/j.ceramint.2016.04.171
[23] Iqbal, Nida, et al. "Nano-hydroxyapatite reinforced zeolite ZSM composites: A
comprehensive study on the structural and in vitro biological properties." 2016 Ceramics
International 42 (6) 7175 https://doi.org/10.1016/j.ceramint.2016.01.107
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INFLUENCE OF COMPOSITION ON PROPERTIES OF A CALCIUM

CERAMIC BODY
1 2 1
Pavla Dvořáková , František Oujiří , Alexandra Kloužková ,
1 3
Mária Kavanová , Martina Kohoutková
1
Prague, Technická 5, 166 28 Prague, Czech Republic;
2
LASSELSBERGER, s. r. o., Adelova 2549/1, 320 00 Plzeň, Czech Republic;
3
Technická 5, 166 28 Prague, Czech Republic;
e-mail: dvorakap@vscht.cz
The paper is focused on the study of ceramic bodies used in the manufacture of large format
single-fired wall tiles with required properties of tile bodies which are directly related to the
selection of suitable glazes. The main aim of this work was to study the influence of
compositions of ceramic mixtures made from natural raw materials on final properties of wall
tile ceramic bodies.
Keywords: Ca-rich ceramic body, large-format wall tiles, phase transformation, X-ray powder
diffraction, SEM
Introduction
Production of traditional ceramic tiles used in interior and exterior have recently
undergone significant changes. Rapid technological development has allowed the
development of the production of new tile formats. These large format tiles have
become the current trend in a ceramic production. Large format tiles are frequently
used by interior designers for optical enlargement of space. Nowadays, large format
tiles of extreme dimensions (3 × 1 m, 3.5 mm thick) are often presented at trade
fairs.
A problem with the production of large format tiles is primarily to meet the exact
dimensions of the tiles and to prevent formation of planarity defects. The presented
work deals with this issue. The production process usually consists of ceramic body
preparation, tile shaping mostly by dry pressing or another forming process like
extrusion, tile drying, glazing and fast cycles firing with maximum firing temperatures
ranging from 1000 °C to 1250 °C to obtain final properties. Firing time ranges from
40 min for porous tiles to 60 - 70 min for sintered tiles. [1-4]
Two basic processes take place during firing of a ceramic tile:
a. dehydroxylation of clay minerals (up to approx. 500 °C) followed by mullite
formation (approx. 1000 °C):
Al2O32SiO22H2O  Al2O32SiO2 + 2H2O;
3(2Al2O33SiO2)  3 Al2O32SiO2 + 5SiO2,
b. calcite decomposition (approx. 700 - 800 °C) followed by products reaction i.e. the
reaction of calcium dioxide with metakaolinite to gehlenite:
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INFLUENCE OF COMPOSITION ON PROPERTIES OF A CALCIUM CERAMIC BODY
P. Dvořáková, F. Oujiří, A. Kloužková, ,M. Kavanová, M. Kohoutková
2CaO + Al2O3.2SiO2 → 2CaO.Al2O3.SiO2 + SiO2.

A thermodynamically unstable crystalline phase gehlenite reacts to a stable
crystalline phase anorthite:
2CaO.Al2O3.SiO2 + Al2O3.2SiO2 + SiO2 → 2(CaO. Al2O3.2SiO2).
Presence of anorthite has a main influence on final properties of a product,
especially its strength and shrinkage. The ratio of CaO, Al2O3 and SiO2, which is
expressed by ternary diagram, influences the formation of an anorthite phase
(Figure 2 right).
Experimental part
Nine model systems were produced from raw materials – six types of clays, kaolin,
calcite and feldspar.
Characterization of parameters of ceramic bodies
Parameters of ceramic bodies especially bulk density, weight absorption, apparent
porosity and apparent density were evaluated according to a standardized method
ČSN ISO 10545-3 [5].
Evaluation of chemical composition – X-ray fluorescence (XRF)
Chemical compositions were evaluated using fully automatic sequential XRF
spectrometer ARL 9400 XP (Thermo ARL, Switzerland). The X-ray fluorescence
method was used for semi-quantitative and qualitative element analysis up to 83
elements of periodic table (B-C O-U) in the range from ppm to 100 %. The
spectrometer is suitable for measurement of solid materials, powders, thin films and
fluids and is equipped with Rh tube, 4kW generator, 4 collimators, 6 crystals (AX 20,
TLAP, PET, Ge 111, LiF 200, LiF 220), 2 detectors – proportional and scintillation.
Obtained data were evaluated by software Uniquant 4.
Evaluation of mineralogical composition – X-ray diffraction (XRD)
Mineralogical compositions were measured by X-ray diffractometer PANanalytical
X´Pert PRO (PANanalytical, Holland) equipped with Cu tube and 1D detector
PIXCEL. Measured data were evaluated by software X´Pert HighScore Plus 3.0 with
reference sample database. [6]
Measurement of thermal expansions
Thermal expansions of ceramic bodies were measured by dilatometry.
Measurements were carried out on samples before and after hydrothermal treatment
by LINSEIS L75 HS 1600C PT dilatometer. The heating rate was 5 °C/min up to 25
– 700 °C with 8 min dwell at final temperature. Obtained data were evaluated by
software Linseis Platinum Evaluation V1.0.90.
Hydrothermal treatment (HT)
Fired compact samples of ceramic bodies were exposed to hydrothermal treatment
in a laboratory autoclave A/650/20 (Ceramic Instruments, Italy). The autoclave is
built according to PED standards with a maximum pressure of 20.0 bar (2000 kPa),
a manometer with a range of 0.25 bar (2.5 MPa) and an operating temperature of
218 °C. The internal capacity of the autoclave is 300 l.
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Simultaneous thermal analyses (STA)

Measurement of powder samples of ceramic bodies was carried out using STA PT
1600/1750 °C HiRes (Linseis, Germany) in mode TG-DTA at a temperature range
25 °C - 1200 °C with a heating rate 10 °C/min in a helium flow. The measured
sample was placed in a platinum crucible. The released gasses mainly CO 2 a H2O
were analysed by ThermoStarTM GSD320 (Pfeiffer Vacuum, Austria) mass
spectrometer. Evaluation of measured data was performed using Linseis Evaluation
software.
Results
Chemical composition of raw materials and model ceramic mixtures is presented in
the form of PCA biplot (Fig. 1). One of the basic required parameters of ceramic
bodies for the ceramic production is shrinkage. The shrinkage Ss of nine prepared
mixtures was determined after pressing/drying and after firing. Further evaluation
was carried out on samples with the lowest shrinkage (0.91 %). Mineralogical
composition of three selected mixtures (H0, H1 and H2) is presented in Figure 2.
These three ceramic mixtures correspond well to the desired properties of ceramic
body of large-format tiles.
Fig. 1 The principal component biplot of the XRF data of raw materials with active variable
guidelines (left hand side) and of prepared ceramic bodies (right hand side)
Processes that take place in the ceramic body during thermal load in the
temperature range 25 - 1200 °C caused changes of relative expansions of moldings
(Fig. 3, right). Expansions of ceramic bodies at a temperature range of 700 - 850 °C
were observed. These expansions were caused by the formation of a new phase
anorthite which increased in volume during formation. The calcite particles
decompose above 800 °C and carbon dioxide releases, which results in material
shrinkage. However, if there is a sufficient content of anorthite in a ceramic body, the
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INFLUENCE OF COMPOSITION ON PROPERTIES OF A CALCIUM CERAMIC BODY
P. Dvořáková, F. Oujiří, A. Kloužková, ,M. Kavanová, M. Kohoutková
shrinkage will be interrupted within a certain temperature range. The shrinkage

delay may be advantageous. The dimensional accuracy of the product and thus
possibility of producing large format tiles is enabled.
3
Fig. 2 Mineralogical composition of ceramic mixtures H0, H1, H2 (left hand side),
ternary phase diagram CaO - Al2O3 - SiO2 (right hand side) [1]
0,8
quartz
anorthite
H1
Rel. Exp. [%]
0,6
mullite
0,4
4
H0
0,2 H2
Position [°2Theta] (Copper (Cu)) 200 400 600 800 1000
Temperature [°C]
Fig. 3 Detail of X-ray patterns of ceramic bodies of the set H (left hand side),
relative expansion curves of compact samples of the set H
Conclusions
The aim of the work was to form new ceramic body with defined porosity for the
manufacture of large format wall tiles. The basic properties influencing the final
planarity of the product were evaluated, e.g. shrinkage, coefficients of thermal
expansion, moisture expansion. Finally, the characteristic parameters of the
selected ceramic body (bulk density, weight absorption, apparent porosity and
apparent absorption) were determined. The results of all tests and measurements
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confirmed the suitability of the produced ceramic mixture for the production of large
format wall tiles.
Acknowledgment: This work has been financially supported from Specific University
Research (No. 107 088 1906).
References
[1] HANYKÝŘ, V.; KUTZENDÖRFER, J. Technologie keramiky. Praha: Vega, s.r.o., 2000.
ISBN 80-900860-6-3.
[2] SVOBODA, L. a kolektiv. Stavební hmoty. Praha: Jaga Group, s.r.o, 2004. 978-80-260-
4972-2.
[3] HLAVÁČ, J. Základy technologie silikátů. Praha: Nakladatelství technické literatury, 1981.
[4] FERRER, S.; MEZQUITA, A.; GOMEZ-TENA, M. P.; MACHI, C.; MONFORT E. C.;
MONFORT, E. Estimation of the heat of reaction in traditional ceramic compositions.
Applied Clay Science, 2015, vol. 108, p. 28–39.
[5] ČSN EN ISO 10545–3. Keramické obkladové prvky – Část 3: Stanovení nasákavosti,
zdánlivé pórovitosti, zdánlivé hustoty a objemové hmotnosti. Praha: Český normalizační
institut, 1998.
[6] KLOUŽKOVÁ, A.; ZEMENOVÁ, P.; KLOUŽEK, J.; PABST, W. Termická analýza. Praha,
2012.
Jahodná, Slovakia
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25 -27 June, 2019 157
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CHARACTERIZATION OF CERAMIC BODIES AND GLAZES

OF FAIENCES FROM HRADČANY PALACES
1 1 1
Alexandra Kloužková , Pavla Dvořáková , Mária Kavanová ,
2 1
Martina Kohoutková , Veronika Pulcová
1
Prague, Technická 5, 166 28 Prague 6, Czech Republic
2
Technická 5, 166 28 Prague 6, Czech Republic
e-mail: alexandra.klouzkova@vscht.cz
Several fragments of glazed ceramics, which were found during archaeological researches of
Hradčany Palaces, were submitted to analyses of ceramic bodies and glazes. X-ray
fluorescence and X-ray diffraction analyses were performed in order to characterise chemical
and mineralogical composition of ceramic bodies and glazes of fragments of five faience
objects. The analyses confirmed that the objects were from the same production centre and
the marks on two of them indicate that they come from the Bayreuth manufactory from the
time of the owner of Johann George Knöller [1]. The analyses of polychrome lead-tin glazes
showed that the amount of lead and tin oxide varied in a wide range. Results of the blue
pigments proved the presence of Co and Fe. The results of XRF were statistically processed
to reveal similarities in compositions of pigments, ceramic bodies and glazes.
Keywords: Faience ceramics, X-ray fluorescence, X-ray diffraction, lead-tin glazes, pigments,
Hradčany Palaces
Introduction
The coloration of ceramics has played an important role since the ancient ceramic
production and it is based on the traditional experience of potters from Egypt,
Mesopotamia and Persia. Faience (from French faïence, Italian Faenza) arrived in
Europe through two routes in Renaissance period, when the Mediterranean became
an important trade centre. Faience is the name for fine lead-tin glazed pottery with
blue, yellow or orange decors. Glazed ceramics with colourful decorations was firstly
produced in Faenza (hence the name faience) then the production expanded to
th th
Urbino and Florence. In the 17 and 18 century, the production came from
Mediterranean region to France and the Netherlands. The Dutch blue-white faience
which was produced at that time in Delft was successful in the world. From the
Netherland, the development of faience ceramics further expanded to Germany and
England. Each production centre had a distinctive character of the site. Bayreuth
faience production centre, whose mark is painted on the two objects found during
the archaeological excavations of Hradčany Palaces, was founded in 1716 by
Margrave George Wilhelm in St. Georgen am See and Johann Peter Demleutner.
[1-4]
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158 REPARATION OF CERAMIC MATERIALS
CHARACTERIZATION OF CERAMIC BODIES AND GLAZES OF FAIENCES FROM HRADČANY PALACES
A. Kloužková, P. Dvořáková, M. Kavanová, M. Kohoutková, V. Pulcová
Faience is a light-coloured pottery manufactured from CaO-rich clays exposed to

several firing steps from a bisque firing (firing of a green ceramic body) to a glaze
firing (firing of a tin glaze with inglaze decoration applied prior to firing) or to a third
firing (firing after further decorations by overglaze enamel pigments). A green
ceramic body was fired in a kiln at relatively low temperatures of 900 - 1000 °C, and
then was glazed by a glaze slurry. After drying, a glaze could be decorated by
inglaze colours which are absorbed to a white glaze powder. The glazed object was
then fired at temperatures approximately 950 - 1050 °C. Applied pigment decors
remained as insoluble crystalline phases or precipitated as colloidal phases and only
metal oxides which provided blue, yellow, green or black colours were used. The
last painted surface decors called overglaze colours were fired at lower
temperatures (600 - 800 °C) in muffle kilns. [4-6]
Experimental part
The samples of five ceramic objects which were found during archaeological
research of Hradčany Palaces were subjected to several analyses:
 The chemical composition of powdered samples of ceramic bodies and glazes
were analysed using an ARL Performix (Thermo ARL, The Netherlands) fully
automatic sequential WD-XRF spectrometer equipped with RD anode X-ray tube.
Measured spectra were evaluated using Uniquant software.
 The mineralogical composition was determined by powder X-ray diffraction.
3
Powder XRD data were collected at room temperature with a PANalytical X'Pert
Powder θ-θ powder diffractometer using CuKα radiation (λ = 1.5418 Å, U = 40
kV, I = 30 mA) in parafocusing Bragg-Brentano geometry. Data were scanned
with an ultrafast 1D detector PIXCEL detector over the angular range 5 - 80°(2θ)
with a step size of 0.0167°(2θ) and a counting time of 120s step-1. Identification
of the individual crystalline phases was performed using the PANanalytical High
Score Plus 4.8 software package and a reference samples database.
 Glaze colouring was evaluated by a spectrophotometer KONICA MINOLTA CM-
700d to interpret the effect of colouring oxides. The spectrophotometric
measurement was also performed to ceramic bodies to identify the effect of
colouring agents (mainly Fe and Ti compounds) and of firing temperature. The
measured data were evaluated in the SpectraMagic NX software and are
presented in the CIE colour space.
 Parameters of ceramic bodies especially bulk density, weight absorption,
apparent porosity and apparent density were evaluated by a weighting method
according to a standardized method.
 Optical microscopy was used for the study of the microstructure of ceramic
bodies, defects within glazed surfaces and used overglaze or inglaze decors.
Microscopic observations were performed using an Olympus BX60 polarizing
optical microscope (Olympus Europa Holding GmbH, Germany) with a Canon
1000D digital SLR camera and a Olympus stereomicroscope SZX9 (Olympus
Europa Holding GmbH, Germany) with a Canon 1100D digital SLR camera. The
images were processed in QuickPhoto Industrial 3.1 software.
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The data obtained from X-ray fluorescence were evaluated using the statistical
factor analysis – principal component analysis PC by XLStat software.
The results of chemical composition of ceramic bodies confirmed the high content of
CaO and MgO. However, they showed also different presence of alkali oxides.
Chemical composition presented in Figure 1 was introduced in the form of PCA
analysis which was performed with data of 20 variables as determined by XRF.
The ceramic bodies were divided into three areas mainly according to the higher
content of MgO in samples 587 and 591 and the lower content of CaO in samples
600 and 608 (15 and 16 wt.%). The result of ceramic bodies 600 and 608 were also
affected by slightly higher content of SiO2. The ceramic body 588 was separated
from others due to a higher content of alkali oxides.
The data obtained by XRF analysis were supported by mineralogical compositions
of samples obtained by XRD. The comparison of XRD patterns showed that
samples 587 and 591 with a significantly higher content of MgO contained gehlenite
(Ca2Mg0.35Al1.3Si1.35O7). The presence of this type of gehlenite in the samples
indicates the use of MgO-rich raw materials.
Fig. 1 The principal component biplot of the XRF data of ceramic bodies with the active
variable guidelines
Other identified crystalline phases were quartz and pyroxene. In mineralogical

compositions of samples 588, 600 and 608 the presence of crystalline phase
anorthite was also detected.
The analyses of glazes proved the presence of SnO 2 within the wide range of 1 -
13wt.%, which was identified as a crystalline phase cassiterite added as an
opacifier. The analyses of blue painted areas of glazes showed the presence of
Co3O4, NiO and As2O3 and higher content of Fe2O3 and CaO in comparison to white
glazes. It could be concluded that these components were used to produce the blue
pigment. However, no crystalline phase except cassiterite was found, the raw
material of blue pigment was not identified. Blue decors were usually produced by
ground cobalt glass or frits. Prepared cobalt frits contained apart from cobalt other
elements such as iron, nickel or arsenic [7].
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CHARACTERIZATION OF CERAMIC BODIES AND GLAZES OF FAIENCES FROM HRADČANY PALACES
A. Kloužková, P. Dvořáková, M. Kavanová, M. Kohoutková, V. Pulcová
Microscopic evaluations of surfaces of glazes showed that they were cracked due to
long-term deposition in the environment of waste pits. Corrosion products have
grown in the area of the damaged surface (cracks). The composition of corrosion
products was not identified by X-ray diffraction; however the presence of P2O5, SO3
and Cl was detected by XRF. Several parts of fragments were degraded by
specking originated from a production process.
Fig.2 Microscopic evaluation

ofdegraded parts of the glaze
of the sample 588
Conclusion
The paper presents a unique set of faience ceramic imports which was found in
waste pits of Hradčany Palaces. The analyses of ceramic bodies proved similarities
in chemical and mineralogical compositions. The presence of anorthite was proved
in three samples, which was probably due to a slightly different composition of raw
materials or also by different conditions of a firing process. The glazes were
decorated by blue cobalt based painted decors. The only crystalline phase in white
and blue glazes was cassiterite. The surfaces of glazes were severely degraded due
to conditions of long-term deposition in a soil and due to impurities or contaminants
which caused specking during a production process.
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References
[1] HOFMANN, F.H. Geschichte der Bayreuther Fayencefabrik St. Georgen am See; Benno
Filser Verlag G. m. b. H.: Augsburg, 1928, p. 41.
[2] WEIß, G. Keramika umění z hlíny. 1. Praha: Grada Publishing, 2007. ISBN 80-247-
1954-1.
[3] GUILHERME, A., S. PESSANHA, M.L. CARVALHO, J.M.F. DOS SANTOS a J.
CORORADO. Micro energy dispersive X-ray fluorescence analysis of polychrome lead-
glazed Portuguese faiences. Spectrochimica Acta Part B. 2010, 65, 328-333. DOI:
10.1016/j.sab.2009.12.010.
[4] MAGGETTI, M., V. SERNEELS a G. STASCH. Composition and technology of 18th
century high magnesia faïences from Fulda. Journal of Archaeological Science: Reports.
2015, 2, 40-50. DOI: http://dx.doi.org/10.1016/j.jasrep.2014.12.004.
[5] ZEH, E. Hanauer Fayence. Ein Beitrag zur geschichte der deutschen keramik, 1.st ed.;
Ludwigs-Universität: Giessen, 1913; p. 195-203, 208.
[6] RADA, P. Techniky keramiky, 2.nd ed.; Aventinum nakladatelství, s. r. o.: Nikoly
Vapcarova, Praha 4, 1996. ISBN 80-85277-88-3.
[7] SMRČEK, A. Složení a kmeny českého skla v historickém vývoji. In: Drahotová, O.(ed)
Historie sklářské výroby v českých zemích, Praha, 443.
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L 26
USE OF HYDROTHERMAL CONDITIONS IN THE FIELD OF SPECIAL

CERAMIC MATERIALS
1 2
Alexandra Kloužková , Martina Kohoutková
1
Prague, Technická 5, 166 28 Prague, Czech Republic
2
Technická5, 166 28 Prague, Czech Republic
e-mail: alexandra.klouzkova@vscht.cz
Hydrothermal conditions can be used both in the synthesis of ceramic raw materials and in
evaluation of the stability prediction of ceramic materials. Three examples are given:
hydrothermal synthesis of leucite precursors, accelerated aging of clay ceramics and low
temperature aging of zirconia toughened ceramics including prediction of their stability.
Keywords: hydrothermal condition, leucite, moisture expansion, aging, ZTC, LTD
Introduction
The use of hydrothermal conditions in the synthesis of minerals has occurred in the
Earth's crust since the Earth's origins long before the beginning of human existence.
Typical products of hydrothermal processes are hydrothermal veins containing e.g.
quartz, carbonates, barite, fluorite, sulphide minerals etc. The primacy of the
purposeful use of steam in a closed vessel in chemical processes has been
attributed by ancient authors to the "mother of the laboratory technic" Mary Hebrew
(ca. 1 st century) and her “kerotakis” (a closed vessel bonded with clay binder called
"wisdom mud"). Many years later, the vessel was significantly improved by the
French scientist Denis Papin (1647–1712), who in 1679 patented a pressure cooker
which was used first in the laboratory, later in industry, and in gastronomy as late as
in the 20th century.
The influence of hydrothermal conditions on the crystallization of substances was
studied by geologists and mineralogists from the beginning of the 20th century.
Pioneers in research of the hydrothermal mineral production were George W. Morey
at the Carnegie Institution and later Percy W. Bridgman at Harvard University.
Nowadays hydrothermal synthesis is used to produce rubies, emeralds, alexandrites
and other minerals. The term hydrothermal process can very often be perceived in
the context of so-called hydrothermal carbonization (HTC). It was first described in
1913 by Frederick Bergie, and in 1931 he was awarded the Nobel Prize for
Chemistry. The Web of Science contains about a hundred thousand publications
with the key word hydrothermal, of which almost 3,000 are works from the ceramic
field.
An interesting application is the use of hydrothermal conditions to study degradation
processes and to predict material durability. In the field of technical ceramics, it
concerns mainly zirconia-based composites and bio-ceramic applications. In the
Jahodná, Slovakia
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USE OF HYDROTHERMAL CONDITIONS IN THE FIELD OF SPECIAL CERAMIC MATERIALS
A. Kloužková, M. Kohoutková
field of classical ceramic products it includes tiles and brick products. The aim of the
paper is to present two research areas from the ceramic field, in which hydrothermal
conditions were applied:
 synthesis of leucite dental raw materials under hydrothermal conditions,
 aging of "clay" ceramics,
 degradation of the ZTC (Zirconia Toughened Ceramics) in hydrothermal
conditions,
 prediction of durability of ceramic materials.
Experimental
Synthesis of leucite dental raw materials under hydrothermal conditions
The glass-ceramics used in dentistry are produced from highly viscous alkali
aluminosilicate glasses. Conventionally, leucite crystallises incongruently from a
precursor containing potassium, aluminium, silica and other components like alkali
fluxes, nucleating agents etc.. The volume crystallisation of leucite was described for
example in the US Patent No. 4,455,383 [1] or in the US Patent No. 4,798,536 [2].
Our team [30] firstly synthesised highly pure tetragonal leucite using the
hydrothermal method in a two-step process at the lowest temperature ever.
Homogeneous leucite powders were prepared by an ion exchange of hydrothermally
synthesised analcime at 200 °C. The reaction occurred in a solution of KCl in a
teflon-lined stainless steel autoclave [3], see Figure 1. Later, we hydrothermally
synthesised leucite from an amorphous precursor, followed by a subsequent high
temperature treatment at 1000°C [4]. The scheme of both syntheses is shown in
Figure 1. Table 1 summarizes the raw materials used, the individual processes and
the overall time demands of the both syntheses.
Ion Exchange
of analcime
Calcination
of precursor
Fig. 1 Scheme of the leucite syntheses, right particle size distribution of products
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L 26
Table 1 Overview of raw materials, individual processes and overall time demands of the
both methods
Method 1. step 2. step Laboratory work Device initialization Chemicals

preparation of NaOH
autoclave, autoclave,
solutions, drying oven Al
ion exchange 200 °C 200 °C
cooling, washing, 1,5 hour SiO2
2 hour 4 hour
drying 5hour KCl
preparation of
calcination autoclave, drying oven – 1 hour KOH
1000 °C solutions, cooling,
ofamorphous 150 °C furnace – 2 hour Al
3 hour washing, drying
precursor 1,5 hour mill – 0,5 hour SiO2
6hour
Ageing of fired-clay ceramics, identification of moisture expansion value by

contraction dilation method
Kaolinite Al2Si2O5(OH)4 is a clay mineral which is used for a ceramics fabrication
from its very beginnings. When kaolinite is heated, it loses any physically absorbed
water between 100 °C and 200 °C, i.e. dehydration occurs. Kaolinite transforms to
an unstable non-crystalline product, metakaolinite (Al2Si2O7), after calcination at
450–600 °C, by loss of chemically bound water, i.e. dehydroxylation occurs. The
process of dehydroxylation is accompanied by a mass loss of approximately
14wt.%. The unstablemeta-clay (metakaolinite) fired at temperatures below 950 °C
can partially rehydroxylate to the structures close to that of the original clay
(kaolinite). The processes of rehydration and rehydroxylation are called ageing.
Natural ageing of a ceramic object can be simulated in a laboratory by using
hydrothermal conditions in an autoclave by standardized test methods — e.g.
according to the French standard method (NF P 13–302, 1983) and its
modifications. Ageing lead to moisture expansion of a ceramic body and it is
affected by chemical composition, firing temperature and also by the surrounding
temperature.
During the research of the aging of ceramic bodies [5], it has been shown that
moisture expansion can also be determined by a contraction dilation method that is
not as demanding for sample preparation as a standardized method. The
dilatometric method utilises a thermal dilatometer with the precise displacement
measurement by LVDT transducer. The usual length of a specimen is 35-25 mm.
The proposed testing method consists of several stages (Fig. 2), which are
described below:
1. measurement of a nature aged sample,
2. measurement on the same sample,
3. measurement on the sample subjected to an accelerating test by high pressure
steaming at 180 °C.
The strain-temperature relationships in Fig. 2 are plotted in such a way that the end
points at 685 °C are identical, because the same temperature and the same degree
of rehydroxylation occur at this moment. The difference between the first and
Jahodná, Slovakia
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25 -27 June, 2019 165
second annealing in the dilatometer is due to the release of OH - hydroxyl groups

from the ceramic body, and is equal to the nature irreversible moisture expansion of
the sample. Similarly, the difference between the third measurement and the second
measurement is equal to the irreversible expansion due to the accelerating test.
6000
5000
4000
strain e [1E-6]
Expansion of fired
3
clay subject to
3000
high pressure
steaming
2000
Nature expansion of
1 historical sample
1000 2
Thermal expansion
0
0 100 200 300 400 500 600 700 800
temperature T [°C]
Fig. 2 Strain-temperature relationships measured using a dilatometer on a sample from
Prague-pantile
Low-temperature degradation of the ZTC

The application of ZTC (zirconia toughened ceramics) in various technical and
medical fields is due to their excellent mechanical properties and biocompatibility.
For all types of ZTC, ZrO2 in the ceramic matrix must be in the metastable tetragonal
phase using a stabilizer (usually Y2O3, MgO, CaO, Ce2O3) in order to toughen and
reinforce the composite. It was proved that t- ZrO2, especially in Y-TZP, undergoes
unusual spontaneous t → m transformation in the temperature range of 70 - 400 °C
in the presence of water vapor. This phenomenon is called low temperature
degradation (LTD) of ZrO2 – composites and its kinetics is described by the Mehl-
n
Avrami-Johnsonon equation: f=1-exp.(-bt) , where f is the transformed t-phase
fraction to the m-phase, t is time, b and n are constants. Three basic mechanisms
are assumed in LTD:
1) corrosion – interaction of water and ZrO2 to form Zr-OH bonds,
2) destabilization – consists in the reaction of OH- with Y2O3 to form Y(OH)3 or
Y(O)OH and consequently destabilization of the t-grains and their transition to
the m-form occurs,
3) voltage-induced transformation – the nucleation of the m-phase is induced by
-
the stress that is generated by diffusion of the OH and expansion of the lattice.
When evaluating the LTD behavior of the different microstructural types of ZTA,
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L 26
TZP and ATZ [6], hydrothermal loads (HL) are used to simulate their aging in a
humid environment (it is reported that 1h at 134°C corresponds to c. 3–4 years
in vivo [6]). An example is the use of isothermal degradation in a water vapor
environment at 150°C (4–40 days), see Fig. 3. From the comparison of different
types of ZTC materials [6,8] in terms of long-term aging, it was evident that in the
case of ZTA materials (preparation of powders by coprecipitation, fabrication by
CIP with subsequent sintering under controlled formation of different
microstructural types) the rate of degradation depended on environmental
conditions (temperature and humidity) and especially on the microstructural type
and and on the preparation method of composite precursors and their
subsequent processing. From the amount of transformed m - phase fraction of
composites with the same microstructure and different Y2O3 content, it was clear
that the degree of degradation increased with the content of Y2O3. The process
of aging was significantly slower in composites with a lower stabilizer content
(confirming the assumption that the LTD process involves the formation of a new
phase of Y(OH)3 or Y(O)OH).
Fig. 3 XRD patterns of LTD composites of ATZ including SEM images; A after firing (100%
tetragonal phase), B -150°C/4 days HL (54 % tetragonal phase), C – 150 °C/7 days
(65 % tetragonal phase), D -150 °C/10 days (73 % tetragonal phase), E – TZP
150°C/40 days, F - ATZ 150 °C/40 days
Conclusion
The paper presents "ceramic" investigations which were realized using hydrothermal
conditions. At the beginning of the research, these topics seemed to be diverse,
Jahodná, Slovakia
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25 -27 June, 2019 167
solved individually side by side or subsequently. However, at some stage of the

research, they have interconnected. Nowadays, the hydrothermally synthesized
leucite precursors are being studied in combination with ZTC composites for the
preparation of dental restorations, especially for all-ceramic veneers.
References
[1] PANZERA, C.: US Patent No. 4,455,383 (1984).
[2] KATZ, B.: US Patent No. 4,798,536 (1989).
[3] KOHOUTKOVÁ, M., KLOUŽKOVÁ, A., ŠATAVA, V., MRÁZOVÁ, M. Česká republika.
Patent CZ 303284 B6. 30. 5. 2012. a Užitný vzor CZ 22403 U1. 2
[4] NOVOTNÁ M., ŠATAVA, V., KOSTKA, P., LEŽAL, D., MAIXNER, J., KLOUŽKOVÁ, A.:
Glass Technol. 45, 105 (2004).
[5] VOKÁČ, M., KLOUŽKOVÁ, A., HANYKÝŘ, V., BOUŠKA, P.: Ceramics-Silikáty, 53, 4, p.
303-309 (2009).
[6] Chevalier, J. Low Temperature Aging of Y-TZP Ceramics. J. Am. Ceram. Soc., 1999,
82(8), 2150-54.
[7] KLOUŽKOVÁ, A.: Ph.D. Dissertation, VŠCHT Praha, 1993.
[8] ŠPRINGER, J. Degradace ZTC kompozitů. Thesis, vedoucí práce Kloužková, VŠCHT
Praha, 1995.
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L 27
SEASONAL VARIABILITY IN COMPOSITION AND PROPERTIES

OF ASHES FROM COMBUSTION OF WOODCHIPS
Beatrice Plešingerová, Pavol Vadász, Gustav Jablonský, Dávid Medveď,

Róbert Dzurňák, Ľuboš Popovič
Letná 9, 042 00, Slovakia
e-mail: beatrice.plesingerova@tuke.sk
The aim of the work is to show the differences in combustion of woodchips in the grate boiler
depending on season and the impact on character of slag and ashes. The analyses point to
the fact that the composition of dendromass is independent on seasonal timber harvesting
and combustion (winter / summer). The chemical composition, alkalinity, specific surface,
softening temperature and fusibility of slags and ashes were measured. Except the higher
part of residual carbon in slag and ashes in winter season not observed were the larger
seasonal differences. The composition of slag and ash from smoke outlet 4/5 and from
cyclone are comparable from point of their chemistry and phases. Only the dust-ash caught
on the cloth filter is significantly different. This ash-deposit contains less of SiO2 and more
K2SO4 and CaCO3. The fusibility temperature increases with the decreasing SiO2 content.
Because the ashes contain high content of alkaline compounds the alkalinity of primary
leachates is very high.
Keywords combustion, dendromass, dust – ash waste
Introduction
The utilization of fossil fuels for the energetic purposes is for their wide application in
the chemical, pharmaceutical and paper industry rather unsuitable. The source of
fossil fuels is diminishing however the power consumption has progressive
tendency. Nowadays one of priorities of Europe Union states (EU) is the utilization of
renewable energy sources (RES). The program is focused on ecology and general
economy, and reduction of fossil fuels import [1].
The most frequent RES is biomass, thence dendromass represents 70 %. The
biomass for energy utilization can be divided into the following categories [1]:
 biomass (dendromass, resp. wood wastes from different industrial production
plants)
 biomass from plants grown for the energetic purposes
 waste from the agriculture production (harvest, plant processing)
 waste from the food industry and from household
 organic industrial waste.
The most simple and fast form of biomass transformation to energy is a combustion.
The energetic utilization of biomass has also some disadvantages, among them the
most important are the low softening temperature, high content of alkalis, and the
dependence on the combustion effectiveness, also the fuels humidity.
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SEASONAL VARIABILITY IN COMPOSITION AND PROPERTIES OF ASHES FROM COMBUSTION
OFWOODCHIPS B. Plešingerová, P. Vadász, G. Jablonský, D. Medveď, R. Dzurňák, Ľ.Popovič
The presented work characterises the slag and ashes caught in the dust-collecting
plant (cyclone extractor, fabric filter) of grate boiler for woodchips combustion. The
slags and ashes were sampled in winter and summer months. The aim was to
determine the seasonal differences in combustion technology and the character of
slag and ash wastes. Despite of the small amount of slag and ash wastes need is to
know character of these wastes, the ecological, as well as economical aspects, and
consider the possibility their subsequent disposal.
Experimental part
The samples of wood chips (W), slags from primary chamber and outlet 2/3 (S),
ashes from outlet 4/5 (T45), cyclone (C) and light ashes from cloth filter (F) of grate
boiler for the steam production (Fig.1) were taken from the dumping boxes in
summer and winter months (July-2018/ marked- 1, January -2019/marked- 2). The
hot slag and ashes are cooled by water and sequentially stored in open boxes. The
agglomerates of slag are therefore fragile.
Fig. 1 Scheme of plant on combustion of woodchips and production of steam
The woodchips (W) were dried and very slowly smoulder. Subsequently, the ashes
were annealed at temperature of 500 °C in conveyer furnace.
The slags and ashes (S, T45, C a F) were dried, annealed at 500 °C and ignited at
1000 °C, subsequently, and in the steps were analysed. The chemical composition
was determined by AAS (Perkin-Elmer 3100). The phase analyses (S, T45, C, F)
were carried out on diffractometer RIGAKU MiniFlex600 with CuK lamp and the
patterns were evaluated using PDXL 2 software. The Netzsch Proteus TA version
6.1 software was used to thermal analyses. The measurements were carried out in
Pt –crucible in air atmosphere up to temperature of 1400 °C. The heating rate was
10 °C/ min. The fusibility of samples (S, T45, C, F) was determined according to
norm STN ISO 540 [2] by the high-temperature microscope (Leitz-Wetzlar,
Germany) with heating up to 1500 °C. The size analyse was realized (sieve with
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L 27
mesh of 0,4; 0,1; 0.04 mm). The specific surface area with adsorption of N2 was
measured by NOVA 1000e (fy. Quantachrome Instruments) and the results were
evaluated with BET method.
The W, S, T45, C and F samples from July were leached in distilled water in two
parallel series. Sample of 1 g was leached in 100 ml water during 1 hour at
temperature of 25 °C. After 1 hour the solution was replaced with 100 ml of fresh
distilled water. This procedure was carried in the 5 cycles of water exchange. Before
and after leaching test the pH and concentration elements in solutions were
measured. The obtained results are presented in Tables 1-7 and Fig. 2.
Results
Chemical analyses and character of ashes from woodchips
The chemical analyses of ashes in laboratory burned woodchips W-1 (offtake in
July-2018) and W-2 (offtake in Janurary-2019) are shown in Table 1. Only little
differences in the chemical analyses of ashes from the seasonal woodchips were
2 -1
found. The specific surfaces area of ashes was 14 – 16 m .g .
Table 1 Chemical analysis of ashes from woodchips sampled in July (1) and January (2)
Al2O3 SiO2 CaO MgO Fe2O3 MnO Na2O K2O LOI** Ash content *
Sample [wt. %]
W-1 3.5 9.7 40.9 4.1 3.7 0.9 0.1 8.3 28.7  0.75
W-2 3.2 10.7 43.6 5.2 2.1 1.3 0.2 9.1 24.5  0,60
* Ash content from woodchips dried at 105 °C and annealed at 500 °C
**Loss on ignition
Evaluation of slags and ashes

The dried samples (slags /S, ashes from outlet 4 and 5 /T45, cyclone /C and filter /F)
were subsequently annealed at 500 °C and then at 1000 °C as shown in Table 2.
The differences in granularity and the specific surface area are presented in Table 3.
The effect of wet weather and dumping in open boxes is evident in the amount of
free and physically bounded water of stored slag and ashes, too. The residual
carbon was burnt and hydrates and hydroxides decomposed when annealed at 500
°C. Hydroxides and hydrates could be formed in reaction with water in boxes. Loss
in ignition at 1000 °C is the indicator of carbonates and sulphates presence.
The loss of annealing at 500 °C cannot be compared between seasonal samples (S,
T45 and C). The cause of this difference is the humidity of burned woodchips and
intense operation in winter months. The carbon content in winter season slag (S-2),
ash from outlet (T45-2) and ash from cyclone (C-2) form up to 65 wt.%, 27 % and
10%, respectively. The carbonized particles of woodchips are light and are drifted
by hot burnt gas into cyclone. The results of ignition loss at 1000 °C of samples from
winter and summer seasons are comparable. The specific surface of the
decarbonised slags and ashes (at 500 °C) is low (Tab.3). The very fine ash, soft
agglomerates under tenths micrometre), coughed on filter (F) has a bit higher
specific surface area. This fine fraction (F) has the significantly higher loss of ignition
Jahodná, Slovakia
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25 -27 June, 2019 171
at 1000 °C. It corresponds to the assumption that the alkaline sulphates and
carbonates are present, they were formed at interaction of the alkaline oxide
particles with CO2 a SO2 during the gas cooling.
Table 2 Loss on weight of samples during the drying and annealing; (July /1 and January /2)
Weight loss [wt. %]
Sample
Drying at 105 °C Annealing at 500 °C Annealing at 1000 °C/ 2h
S -1 (26,3) 3.9 7.6
S -2 75 65 10.2
T45 -1 0-0.4 0.7 6.6
T45 -2 0,9 -1,1 27 4.8
C -1 0-0.5 0.75 7.6
C- 2 0.4-0.5 10 6.5
F -1 0-0.5 1.75 18.3
F- 2 0.4-0.5 2 19.6
Table 3 Comparison of granularity and specific surface area of slags and ashes
2 -1
Sample after annealing at 500 °C Specific surface area [m .g ]
Sample Size analyse [mm] Summer dose
Winter dose after
after drying at 105
annealing at 500 °C
 0.4 0.1 -0.4 0.04-0.1 0-0.04 °C
S -1 33 31 16 20 7 -
S -2 27 24 17 32 - 1.5
T45 -1 1 31 43 25 3 -
T45 -2 3 26 51 20 - 2
C -1 0 8 61 31 5 -
C -2 0 1 39 60 1.8
F -1 0 0 adhesion of 7 -
F -2 0 1 particles - 5
Chemical and phase composition after complete burn-out of residual carbon

The qualified chemical and phase analyses of slag and ashes required the burn-up
of residual carbon, i.e. annealing at 500 °C. As it can be seen in Table 4 the greater
differences between seasonal samples of the same type are only in SiO 2 : CaO
ratio. Important differences among slag (S) and ashes (T45, C) were not evident.
The low content of SiO2, Al2O3 and two times higher content of K (potassium) was
detected in the ashes from filter. The rising ignition loss can be explained by the
decomposition of sulphates and carbonates, which are here probably in prevalence.
The results of X–ray diffraction analyses confirmed that observation.
The evaluation of X–ray diffraction patterns slag and ashes is in Table 5 and pattern
of thermogravimetric and differential thermal analyses (TG, DTA) are in Fig. 2. The
X-ray diffraction analyses confirm that CaO is in slag partially bounded into form of
alumino-silicates and partially into carbonates. The SiO2 is also eminently presented
in S, T45 and C samples.
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L 27
The majority content of CaCO3 and K2SO4 was confirmed in the ash form filter. The
patterns of TA (Fig. 2) show on conformity between T45 and C samples.
Table 4 Comparison of chemical composition of slags and light ashes from winter and
summer period
Chemical composition [wt.%]

-
Sample Al2O3 SiO2 CaO MgO Fe2O3 MnO Na2O K2O Cl SO3 LOI
S -1 8.5 38.6 29.6 4.3 5.0 0.8 0.2 5.4 0.0 0.1 7.6
S -2 6.1 26.3 43.4 3.5 3.6 0.6 0.4 5.6 0.2 - 10.2
T45 -1 8.1 38.4 31.2 4.2 4.1 1.1 0.3 4.9 0.2 0.9 6.6
T45 -2 7.1 33.1 42.1 4.0 3.9 0.7 0.4 3.8 0.1 0.0 4.8
C -1 8.9 36.3 30.8 4.4 3.6 1.2 0.3 6.2 0.2 0.5 7.6
C -2 6.8 20.6 52.6 5.1 3.7 0.9 0.3 3.3 0.3 - 6.5
F -1 2.2 7.7 44.8 4.7 2.7 0.8 0.2 12.1 1.2 - 18.3
F -2 1.4 3.9 50.5 5.4 2.1 0.8 0.3 13.1 1.9 - 19.6
LOI. – loss on ignition
Table 5 Results of X-ray diffraction analyses of slag and ashes after annealing at 500 °C
Sample
Major phase
S T45 C F
CaCO3 ++ + - +++
K2SO4 - - - ++
(Ca-Mg-Fe)CO3 K2Ca(CO3)2 - + (+) -
silicate and alumino-silicate
SiO2 ++ +++ +++ +
2CaO.SiO2 (+) + -
CaO.Al2O3.2SiO2 ++ - - -
K2O.Al2O3.6SiO2 - - + -
The endothermic peaks on DTA curves correspond with loss weight on TG curves.
Probably, the major loss weight at 50-150 °C of sample F is due to the removal of
adsorbed water by fine particles The endo-peaks around temperature of 420 °C and
700 °C are an expression of decomposition of hydrates and/or carbonates
(CaSO4.2H2O, Ca(OH)2 ,Fe-MgCO3, CaCO3). In case of F sample, the gradual
decrease can be assigned to slow evaporation of K–compounds. The sharp endo-
peaks at 1200-1320 °C are the result of melting process.
Fusibility temperatures
The measured fusibility temperatures of slag and ashes are in Table 5. Despite of
high content of K2O and low content of Al2O3 and fine-grained of F sample from filter,
this F sample shows the highest fusibility temperature, and that is 1466 – 1467 °C.
Very low content of SiO2, which forms base of silicate melts is probably the reason.
Leaching components
As it can be seen in Tables 6 the alkalinity of solution is high. As results in Table 7
show the large portion of alkaline compounds in slag and ashes is easily soluble in
water.
Jahodná, Slovakia
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25 -27 June, 2019 173
Fig. 2 Thermal analyse patterns (TG, DTA ) of ashes: samples T45-1, C-1 a F-1
Table 5 Fusibility of ashes by norm of STN ISO 540 [2]

-1
Fusibility of sample in air atmosphere on corundum plate, heating rate: 10 °C.min
ST HT
DT FT –
Sample spherolite hemisphere 𝐴𝐹 =
deformation flowing 4 𝐷𝑇 + 𝐻𝑇
shape shape
temperature temperature
[°C]
temperature temperature
[°C] 5
[°C] [°C]
S-1 1220 1228 1230 1245 1222
S-2 1200 1207 1210 1220 1201
T45-1 1230 1238 1242 1270 1232
T45-2 1228 1230 1232 1240 1228
C-1 1205 1220 1223 1236 1209
C-2 1261 1266 1268 1275 1262
F-1 1375 1465 1466 1467 1393
F-2 1355 1410 1450 1450 1377
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Table 6 pH value of leach after cycle leaching test of 1 g sample in 100 ml water at
temperature of 25 °C; every cycle took 1 hour; distilled water was changed after
each 1 hour of leaching
pH Weigh change of
of distil. 1. cycle 2. cycle 3. cycle 4. cycle 5. cycle sample at leaching
Sample water [%|*
S 11.37 10.98 10.63 10.55 10.55 17.8
T45 12.71 12.10 11.40 10.98 10.92 14.5
5,75
C 12.75 11.96 11.40 11.00 11.00 15.7
F 12.9 12.16 11.50 11.30 11.10 46,6
* Hydration of same component increases the mass of rest l of leached sample.
rt
Table 7a Concentration of major components in leach after 1 cycle of leaching slag and
ashes ((1g / 100 ml water)
1.Leach Al Si Ca Mg Fe Mn K Na
-1
Sample [mg.l ]
S 0.8 16.9 92.7 1.4 0.6 0.3 164.4 6.1
T45 0.3 1.3 395.2 0.2 0.3 0.0 65.8 2.0
C 0.33 1.33 362.9 0.23 0.13 0.05 128.76 3.25
F 1.0 1.7 407.3 0.5 0.2 0.1 1175.0 14.3
Table 7b Average concentration of major components in leach of 2-5 cycle of leaching test
(400 ml)
(2.-5.) leach Al Si Ca Mg Fe Mn K Na
-1
Sample [mg.l ]
S 0 3.11 41.66 0.43 0.57 0.007 14.86 0.56
T45 0.16 1.77 68.75 0.58 0.13 0.05 3.59 0.56
C 0.32 3.11 54 0.31 0.78 0.01 3.4 0.2
F 0.49 3.11 58.33 0.5 2.36 0.007 14.25 0.4
Discussion
The obtained results need to be consider from more views: - efficiency of
combustion, - vapour generation, - character of wastes.
Combustion
The woodchips on grate in boiler pass before combustion through zones: i) the
evaporation of water (drying); ii) the release, ignition and combustion of volatile
combustible components, iii) after-combustion of solid carbon [3,4]. The higher fuel
humidity broadens the drying zone and other zones are shifted. The last zone
(combustion of solid carbon) is shortened; therefore the residual carbon content in
winter slag increases. As shown in Table 1 the seasonal woodchips quality is
comparable. Input woodchips humidity in boiler was not checked. The great amount
Jahodná, Slovakia
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25 -27 June, 2019 175
of non-combusted carbon in slag and ashes clearly shows the difference condition in
the seasonal combustion (Table 2). The carbonised chips are light and therefore the
small pieces of carbon are drifted by hot air up-to cyclone. The ratio of carbon in
slags is significantly increased in winter, and probably in wet months (from 4 % to
2 -1
65%). The specific surface of carbonised woodchips is large (150 – 200 m .g ). The
fine carbon particles are caught in cyclone and therefore the carbon content in filter
is negligible.
It means that approximately the 2.5 – 3 % of woodchip batch under-burns at higher
steam production in winter months.
Evaluation of slag and ashes
The seasonal differences in chemical and phases composition of slag and ashes are
not significant (Table 4). The composition of slag (S) and ashes (T45) and cyclone
(C) are similar. The main components are CaO and SiO 2 which form with other the
SiO2-CaO-Al2O3 – (MgO-Fe2O3) the more complex compounds. The carbonates and
sulphates are here in minor quantity.
The fine ashes from filter are different from point of their chemistry and phase
composition. There are major phases CaCO3 and K2SO4, which decompose at
1000°C (loss in ignition 18 -20 wt. %). The K2SO4 is very well soluble in water.
The fusibility temperature of slag and ashes (S, T45, C) are lower (below 1250 °C)
than of ash from filter (around 1400 °C). The low softening temperatures of ashes
are cause of ash sticking and formation of accretion and together with aggressive
hot gas damage the inner-surface of boiler and heat-exchanger.
Alkalinity of slag and ashes
rst
The reason of high alkalinity of leachates in 1 cycle of leaching of slag and ashes
is the presence of well soluble K2SO4 and fine particles of CaCO3 (Table 4, 6). The
most markedly it is at F sample, because the F sample contains more of K 2SO4 and
CaCO3. Potassium salts strongly increase the pH value of primary leachates. The
rst
leachate from 1 cycle is strong alkaline (converges to 13). The pH value decreases
+ 4+
with every exchange of the water, the K concentration decrease but Si
concentration moderately increases. The alkaline medium is aggressive toward the
4+
alumino-silicates and decomposes them. Therefore the Si content in leachates
increases.
Conclusion
Nowadays trends of utilization of “carbon-free fuels“, resp. the fuels of renewable
energy sources, motivate the energy producers to transform the energetic facilities,
to transfer on “the green fuels”. The dendromass is a potential source of fuels and
the composition and properties of ashes from dendromass will be a limited factor for
the replacement of already existing boilers on the coal combustion.
The work has shown the following seasonal variance in the dendromass, slag and
ash composition:
- The differences in the dendromass (wood) composition were minimal. However,
the humidity of combusted woodchips in plant was probably very different.
th
L 27
- The dendromass humidity and high steam production in winter months have
negative effect on increase of residual carbon in slag and ashes from cyclone.
- After the complete combustion of residual carbon from slags (S), ashes from
outlet (T45) and cyclone (C) seasonal differences are not so marked. The
composition and properties of these wastes are comparable. The dominant
components are CaO and SiO2. The fusibility temperature is around 1200 °C.
- In case of fine ashes caught on filter, the seasonal differences are minimal. The
ash is formed mainly of K2SO4 and CaCO3. Despite of high alkaline content their
fusibility temperatures are high, above 1350 °C.
- The alkaline content in form of K2SO4 and CaCO3 in form fine particles, which
generate strong alkali leaches (pH = 12.7 – 12.9) in the first stage of leaching.
The analyses of seasonal slags and ashes assist at the problems solving with
selection of the suitable linings of boilers. The results point on problems of the
effective dendromass combustion during high output of boilers in winter months.
Acknowledgement: This study was financially supported by project APVV-17-0483

professional cooperation with ŽP VVC, s.r.o. Podbrezová and Žiaromat, a.s, Kalinovo and the
Slovak Grant Agencies through “VEGA – MŠVVaŠ SR a SAV” project No.1/0015/18.
References
[1] http://www.forestportal.sk/odborna-sekcia/podpory-a-dotacie/biomasa/Stranky/
rozdelenie biomasy.aspx
[2] STN ISO 540 – Stanovenie taviteľnosti popola. SÚTN, 2010
[3] NOSKIEVIČ, P.: Biomasa a její energetické využití. Praha: Ministerstvo životního
prostředí, 1996, 68 s. ISBN 80-707-8367-2.
[4] Vilga, F.: Vliv teploty sekundárního vzduchu na spalování biomasy, bakalárska práca.
VUČT v Brne, Fakulta strojního inženýrství, Energetický ústav, Brno 2015
Jahodná, Slovakia
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25 -27 June, 2019 177
AND RECYCLING
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research and education on the needs of practice and requirements of companies.
The faculty cooperates with leading companies from the industry; students of the
faculty study in top laboratories and have the opportunity to study and work abroad.
One of the benefits for university students is also working with companies during
their studies at the University. The faculty focuses on the formation of chemical
substance, structures and final properties of materials, their production and
processing by metallurgical processes, their recycling and the use of raw materials.
The main mission of FMMR is to provide a broad and balanced three-level higher
education in an environment that promotes learning pleasure, strong motivation and
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and students, the public, city, region and our partners will enable our students to
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th
POSTERS

XIII t h International Conference
Jahodná, Slovakia
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25 -27 June, 2019 179
P1
THERMO-ANALYTICAL ANALYSIS OF KAOLIN AND BIO-ADDITIVE

MIXTURES USING A DERIVATOGRAPH AND HEATING MICROSCOPE
1 1,2
Emese Kurovics , László A. Gömze
1
Institute of Ceramic and Polymer Engineering, University of Miskolc, Hungary
2
GREX Engineering Service LTD, Hungary.
e-mail: fememese@uni-miskolc.hu
Keywords: derivatograph, kaolin, sawdust, thermo-analysis
The bio-original additives are playing important role in development of properties of

ceramic materials [1-3]. In this research the authors have examined how their
powder mixtures based on kaolin and bio-materials (sawdust), behave under heating
with permanent temperature gradient. To test the powder mixtures MOM
Derivatograph-C and Camar Elettronica heating microscope were used to get the
TG, DTG, DTA curves and understand the thermochemical processes during their
sintering. The geometric deformations of the tested samples under heating in the
tube furnace were observed using heating microscope. During the experiment the
change in the height of the sample was investigated and the sintering temperature
was recorded. The data obtained by the two test methods are shown on a common
diagram, showing that the derivatograph and the heating microscopy complement
each other.
In this research Zettlitz Sedlecky ml kaolin and fine grain oak sawdust (additive)
were used as starting raw materials. For the thermo-analytical tests, a mixture of
kaolin and 10 % sawdust was milled in Retsch PM 400 planetary ball mill for 20 min
at 150 rpm.
The most characteristic three states of our material mixtures under their heating are
shown in Figure 1.
Fig. 1 Images taken by the heating microscope
The results of the thermo-analytical test of the kaolin - sawdust mixture are shown in
Figure 2 and Table 1. The distinguish between drying, burning of biological additive
(leaving volatiles), thermal degradation of kaolin (conversion to metakaolin),
formation of mullite and sintering point (where the height of the sample compared to
the original is 95 %) are well seen from the achieved TG, DTG, DTA curves.
th
THERMO-ANALYTICAL ANALYSIS OF KAOLIN AND BIO-ADDITIVE MIXTURES USING A DERIVATOGRAPH
AND HEATING MICROSCOPE E. Kurovics, L. A. Gömze
Fig. 2 Thermo-analytical curves of C mixture (10 m% sawdust)
Table 1 Typical points on the thermo-analytical diagram for the C mixture

Marked Temperature TG DTA DTG Height
point [°C] [w.%] [°C] [w.%/min] [%]
1 69,25 -0,101 0,084 -0,115 100
2 348,04 -3,160 4,260 -0,344 100
3 375,94 -3,636 3,383 -0,154 101
4 460,58 -4,880 1,632 -0,167 104
5 545,53 -7,385 -2,503 -0,581 103
6 947,48 -10,181 -2,285 -0,012 100
7 1038,20 -10,199 -2,375 -0,004 97
8 1198,50 -10,211 -2,539 0,007 92
Acknowledgements: “The described study was carried out as part of the EFOP-3.6.1-16-
2016-00011 project implemented in the framework of the Szechenyi 2020 program. The
realization of this project is supported by the European Union, co-financed by the European
Social Fund.”
References
[1] E. Kurovics, A. Y. Buzimov, L. A. Gömze 2016 IOP Conf. Ser.: Mater. Sci.
Eng. 123 012058 https://doi.org/10.1088/1757-899X/123/1/012058
[2] E. Kurovics, A. Shmakova, B. Kanev and L. A.0 Gömze 2017 IOP Conf. Ser.: Mater. Sci.
Eng. 175 012013 https://doi.org/10.1088/1757-899X/175/1/012013
[3] E. Kurovics, S. N. Kulkov, L. A. Gömze 2018 Építőanyag-JSBCM 70 (1) 3
https://doi.org/10.14382/epitoanyag-jsbcm.2018.1
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P2
COLOUR PROPERTIES OF PEROVSKITE SrSn1-xMnxO3 PREPARED

BY CERAMIC METHOD
Jan Hroch, Žaneta Dohnalová

Department of Inorganic Technology, Faculty of Chemical Technology, University
ofPardubice, Studentská 95, 532 10 Pardubice, Czech Republic
e-mail: jan.hroch@student.upce.cz
Keywords: ceramic pigments, perovskite, colour properties, particle size distribution
In recent years, perovskites are widely studied among others as cool pigments. The
cool pigments have high reflectivity in the near infrared region, therefore don´t heat
walls of buildings and roof surfaces as much as common pigments [1]. Perovskites
based on SrSnO3 doped by manganese cations are a valuable alternative to
3+
preparation of brown pigments. Majority of brown pigments contain Cr ions and
whose preparation can be problematic in terms of toxicity. Further, the perovskite
compounds have a good thermal and chemical stability, which makes them suitable
candidates for use as inorganic pigments [2, 3].
The raw materials used for the preparation of SrSn1-xMnxO3 pigments were SnO2,
MnO2 and SrCO3. The pigments of stoichiometric composition corresponding to x
ranging from 0.1 to 0.5 (with step 0.1) were obtained by classical ceramic method.
Initial reagents were homogenized by grinding in a ceramic mortar. After
homogenization, the reaction mixtures were calcined in an electric resistance
furnace with a heating rate 10 °C/min and the firing temperature 1200 – 1500 °C for
4 hours. The prepared powders were crushed in a ceramic mortar and then their
properties were determined. The pigments were applied into organic binder (Luxol,
Akzo Nobel Coatings a.s.) and colour coordinates were evaluated in the colour
space CIE L*a*b*. The colour properties were measured by spectrophotometer Ultra
Scan VIS (Hunterlab, USA). A standard illuminant D65, 10° standard observer and
d/8° measuring geometry were used. The particle size distribution of the prepared
pigments was measured using Mastersizer 2000/MU (Malvern Instruments Ltd.,
UK).
The particle size distribution and colour coordinates of perovskites are summarised
in Table 1. The pigments have interesting brown colour after calcination at the firing
temperature 1200 °C. Colour coordinates a* and b* decrease with increasing
calcining temperature and range of substitution of tin ions by manganese ions. It
means that the colour of the pigments is turned from chocolate brown colour to dark
brown (1300 °C) and next to black colour (1500 °C). Values of L* coordinate
decrease with increasing firing temperature and amount of manganese cations
therefore the pigments have a darker colour. The colour coordinates L* have values
in the range of 25.38 – 33.07. The mean particle size d50 rises from 1.42 µm to
1.95µm (for calcining temperature 1200 °C) and from 3.94 µm to 5.83 µm for
th
COLOUR PROPERTIES OF PEROVSKITE SrSn1-xMnxO3 PREPARED BY CERAMIC METHOD
J. Hroch, Ž. Dohnalová
calcining temperature 1500 °C. These values have influence on the application of
the pigments into organic binder.
Table 1 The colour coordinates and particle size distribution of SrSn 1-xMnxO3
Firing d50
Substitution L* a* b* span
Temperature [µm]
Mn - cations
[°C]
1200 33.07 6.71 7.93 1.42 4.65
x = 0.1
1500 25.38 4.08 2.97 3.94 6.37
1200 29.31 3.42 3.64 1.51 3.22
x = 0.2
1500 25.46 0.69 0.27 4.35 4.61
1200 28.20 2.43 2.35 1.59 2.98
x = 0.3
1500 26.47 0.16 -0.09 4.22 2.86
1200 28.16 2.03 1.77 1.75 3.12
x = 0.4
1500 26.51 0.14 -0.06 5.26 4.35
1200 28.78 1.50 1.12 1.95 3.48
x = 0.5
1500 26.59 0.10 -0.12 5.83 4.09
Acknowledgements: This work has been supported by University of Pardubice, Czech

Republic, project SGS_2019_004.
References
[1] Yuan L., Han A., Ye M., Chen X., Yao L., Ding Ch.: Synthesis and characterization of
environmentally benign inorganic pigments with high NIR reflectance: Lanthanum-doped
BiFeO3, Dyes and Pigments, 148 (2018) 137-146.
[2] Shukla A., Parey V., Thakur R., Srivastava A., Gaur K.N.: Thermal properties of
perovskite RCeO3 (R = Ba, Sr), Therm. Act., 614 (2015) 213-217.
[3] Ozel E., Unluturk G., Turan S.: Production of brown pigments for porcelain insulator
applications, J. Eur. Ceram. Soc., 26 (2006) 735-740.
Jahodná, Slovakia
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P3
Lenka Šimková, Petra Šulcová

Department of Inorganic Technology, Faculty of Chemical Technology,
University of Pardubice, Studentská 95, 532 10 Pardubice, Czech Republic
e-mail: lenka.simkova1@student.upce.cz
Keywords: hydroxyapatite, precipitation, XRD, XPS, corrosion test.
Corrosion is an unfavourable phenomenon that induces degradation of the material

and the successive reduction of its properties, or actually completes destruction [1].
The metal corrosion constitutes substantial economic losses, estimated in the Czech
Republic up to 25 billion Czech crowns per year. The corrosion costs involve the
losses connected with the undertaking of precaution against corrosion, reformation
or even replacement of the equipment and losses induced by reduction or
suspension of production due to equipment damage. Hence, the development of
new effective corrosion inhibitors is a very relevant research subject [2].
Anti-corrosion pigments (e.g.: phosphates) help to prevent corrosion, by growing the
probability of a chemical reaction, which creates a protective coating on the metal
surface. As regards to hydroxyapatite (Ca10(PO4)6(OH)2, HAP), it is important
technological material. The main applications of hydroxyapatite are its use as a
coating of metallic prostheses, which has two important functions: to defend the
implant against corrosion and to improve implant’s biocompatibility with the human
body [3]. Because hydroxyapatite is very appropriate and useful for the protection of
implants against corrosion it can be very functional for steel protection like other
phosphate pigments [4]. Since this consideration has not been previously studied, it
has become the major subject of this work.
The objectives of this work are to designate the effect of precipitation conditions on
the synthesis of hydroxyapatite and characterization of its properties for
anticorrosion intention. This work is particularly concentrated on the possibility of
synthesis of hydroxyapatite by the precipitation method. The selected suitable
conditions (Ca/P = 1, 1.67, 3; pH = 7, 12) were modified to synthesize pure
hydroxyapatite form Ca10(PO4)6(OH)2. The obtained precipitates were aged during 1
day, filtered, washed with distilled water to neutral pH and dried at 80 °C for 6 hours.
Prepared pigments were judged for phase (Rigaku Miniflex 600, Japan) and
elemental composition (ESCA 2SR, Scienta-Omicron) and for anti-corrosion
purposes. For their potential anticorrosion application, preliminary corrosion tests
were performed, which include: determination of pH and resistivity of aqueous
suspensions of pigments (10 %), gravimetric determination of weight loss of steel
plates and determination of corrosion indicators.
th
L. Šimková, P. Šulcová
From the results of XRD analysis is clear, that two distinct structures of
hydroxyapatite have been identified: monoclinic and hexagonal. These structural
types of hydroxyapatite were selected based on the lowest value of FOM (figure of
merit), i.e., based on the best match. On the basis of measured values from the
preliminary corrosion tests, it has been shown, that hydrolysis of pigment ions favors
the formation of acid species, leading to a reduction of pH. The conductivity of the
samples was very different, but in general, it increased indicating that the
concentration of dissociated ions has increased over time. The aqueous
suspensions of the pigments were filtered and the pigments extracts were used for
the assessment of weight loss of steel plates, which were immersed in it for 2
months. During the test, an expressive color change of the extracts due to the
release of corrosion products was observed. Next, corrosion indicators were
calculated on the basis of corrosion losses of steel plates. From the values of the
corrosion indicators, the samples can be divided into 3 groups according to their
anticorrosion efficiency. The first group involves samples with high corrosion
efficiency which prevents corrosion processes. The concentration of phosphates in
these extracts is sufficient to inhibit corrosion and phosphate protective coating is
formed (Vivianite). The second group includes samples without anticorrosive
properties. The concentration of phosphates in these extracts is deficient for
corrosion efficiency and the major corrosion product is created (FeO(OH)). The third
group incorporates samples that promote corrosion. In these samples, the corrosion
processes were greatly intense, which may be explained by the intensive reaction
between the leachate and the steel substrate.
Acknowledgements: This work has been supported by University of Pardubice, Czech

Republic, project SGS_2019_004.
Authors appreciate financial support from grant LM2015082 from the Ministry of Education,
Youth and Sports of the Czech Re-public and European Regional Development Fund-Project
"Modernization and upgrade of the CEMNAT" (No. CZ.02.1.01/0.0/0.0/16_013/0001829).
References
[1] Šustek S. Diplomová práce, Univerzita Pardubice, (2009).
[2] Kalenda P., Veselý D., Antoš P. Univerzita Pardubice, Pardubice (2003).
[3] Huang Y., Hao M., Nian X. Ceramics Int., 42 (2016) 11876.
[4] Gorodylova N., Dohnalová Ž., Šulcová P. et.al. Prog Org Coat. 93 (2016) 77.
Jahodná, Slovakia
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P4
PROPERTIES AND MICROSTRUCTURE OF CALCIUM PHOSPHATE

CEMENT COMPOSITE CONTAINING Si3N4 MICROGRANULES
a a a
Ľubomír Medvecký , Radoslava Štulajterová , Mária Giretová ,
a b c
TiborSopčák , Miroslav Hnatko , Taťána Fenclová
a
Institute of Materials Research, Slovak Academy of Sciences, Kosice, Slovakia
b
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia
c
Faculty of Metallurgy and Materials Engineering, Technical University of Ostrava,
Ostrava, Czech Republic
e-mail: lmedvecky@saske.sk
Keywords: tetracalcium phosphate/nanomonetite biocement, Si 3N4 microgranules,

mechanical properties, composites, bioactivity
Tetracalcium phosphate cement, due to its excellent osteoconductivity,

biocompatibility and bone-bonding ability, has been used in a number of orthopaedic
and dental procedures [1]. Silicon nitride as non-oxide ceramics offers several
advantages in comparison to oxide bioceramics like a significantly higher fracture
toughness and wear resistance resulting in high reliability of implants. The
mechanical properties of hydroxyapatite (HA) ceramics are not sufficient for high
load applications, therefore HA is often used in composites or as coating [2].
Alumina and titania particles are the best choices for making composite with HA due
to their good mechanical properties and bio inertness [3]. The 5 wt % addition of
strontium doped HA whiskers almost twice enhanced the mechanical properties of
calcium phosphate cement (CPC) [4]. The mechanical and physico-chemical
properties as well as microstructure of calcium phosphate cement modified with
silicon nitride/ tricalcium phosphate microgranules (Simicro) and mutual
interconnection between cement matrix and microgranules were evaluated.
Composite cement was prepared by mechanical mixing of tetracalcium
phosphate/monetite cement mixture (TTCPMH) with Simicro. The TTCPMH powder
mixture was synthesized by reaction between TTCP and diluted solution of
orthophosphoric acid (86 %, analytical grade, Merck) in solution with water/ethanol
= 1:4 in the planetary ball mill. The starting powder mixtures for Simicro were
prepared by wet homogenization of Si3N4 (UBE-SN-E10) and Ca3(PO4)2 (Lachema,
p.a.) with isopropyl alcohol in atritor for 4 hours. The volume ratio of Si 3N4/
Ca3(PO4)2 was 3:7 (Simicro1), 1:1 (Simicro2) and 7:3 (Simicro3). Microgranules
were prepared by freezing of suspensions. Three porous ceramic Simicro fractions
with particle size between 25-71 (fine), 71-125 (middle) and 125-300 (coarse) µm
were obtained by sieving. Composite cement powder mixtures (CPC 1-3) were
prepared by homogenization of TTCPMH and Simicro in Ultra Turrax Tube (IKA)
desintegrator in ethanol for 5 min at 4000 rpm. The contents of Simicro in CPC were
10 and 30 wt.%. The compressive strength (CS) of dry and wet samples was
th
PROPERTIES AND MICROSTRUCTURE OF CALCIUM PHOSPHATE CEMENT COMPOSITE CONTAINING
Si3N4 MICROGRANULES Ľ. Medvecký, R. Štulajterová, et.al.
measured. A very thin coating composed of extremely fine nanometric particles

newly formed phase was revealed on origin particles of all Simicro after soaking in
simulated body fluid while no other changes in particle morphology were found. In all
cements, HA nanoparticles create islands or globular agglomerates growth on origin
particles of microgranules (especially small size in CPC3) or were in the form of
more compact agglomerates in cement matrix. From comparison resulted the
dependence of HA particle dimensions at Simicro boundaries on amount α-TCP in
microgranules. Wet and dry compressive strengths of CPC1-3 are compared in
Tab.1. CS of all composite cements with 30 wt % addition of Simicro were much
lower (about 30 %) than TTCPMH (CPC0) cement. It was revealed that the
reduction in Simicro content in CPC caused rise in CS which clearly verified
negative influence of Simicro addition on mechanical properties of composite
cements. The highest CS´s from composite cements had CPC1 where Simicro 1
which contained large amount of α-TCP was used. The density of composite
cements was lowered after addition of Simicro around 20 % due to higher porosity of
microgranules (CPC0 had about 43 % porosity contrary to 59 % porosity of CPC1-
3). The setting time rose with decrease in α-TCP in microgranules and
transformation rate of calcium phosphate phases in cements which is demonstrated
longer around 16±1 min setting time of CPC3.
Table 1 Compressive strengths (CS), setting times (ST) of wet and dry of composite cement
powder mixtures
CS [MPa] ST [min]
30 wt % Simicro 30 wt % Simicro 10 wt % Simicro
Samples wet dry
CPC 0 24±3 45±2 5±1
CPC 1 17±2 33±2 7±1 6±1
CPC 2 15±2 26±3 11±2 8±1
CPC 3 13±2 24±2 16±1 10±2
Acknowledgements: This work was supported by the Slovak Grant Agency of the Ministry of
Education of the Slovak Republic and the Slovak Academy of Sciences, Project VEGA
2/0047/17.
References
[1] Xu HHK, Smith DT, Simon CG. Strong and bioactive composites containing nano-silica-
fused whiskers for bone repair. Biomaterials. 2004; 25: 4615-4626.
[2] Precnerová M, Bodišová K, Frajkorová F, Galusková D, Varchulová Nováková Z,
Vojtaššák J, Lenčéš Z, Šajgalík P. In vitro bioactivity of silicon nitride-hydroxyapatite
composites. Ceramics international. 2015; 41: 8100-8108.
[3] Aminzare M, Eskandari A, Baroonian MH, Berenov A, Razavi Hesabi Z, Taheri M,
Sadrnezhaad SK. Hydroxyapatite nanocomposites: Synthesis, sintering and mechanical
properties. Ceramics International. 2013; 39: 2197-2206.
[4] Viswanath B and Ravishankar N. Interfacial reactions in hydroxyapatite/ alumina
nanocomposites. Scripta Materialia. 2006; 55: 863-866.
Jahodná, Slovakia
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P5
EFFECT OF ALGINATE HYDROGELS ON MECHANICAL PROPERTIES

OF TETRACALCIUM PHOSPHATE/NANOMONETITE BIOCEMENT
a a a
Radoslava Štulajterová , Ľubomír Medvecký , Mária Giretová ,
a b
Tibor Sopčák , Jaroslav Briančin
a
Institute of Materials Research of SAS, Watsonova 47, 040 01 Kosice, Slovakia
b
Institute of Geotechnics of SAS, Watsonova 45, 040 01 Kosice, Slovakia
e-mail: rstulajterova@saske.sk
Keywords: sodium alginate, tetracalcium phosphate/ nanomonetite biocement, mechanical

properties, composites, bioactivity
Hydrogels are three-dimensional, hydrophilic, polymeric networks capable to absorb

large amounts of water or biological fluids. Many calcium phosphate cements (CPC)
pastes tend to disintegrate upon early contact with blood or other aqueous body
fluids. For prevention of insufficient cohesion, the cohesion promotors such as
sodium alginate are added [1]. The mechanical properties of alginate scaffolds have
been improved by mixing with calcium phosphates like hydroxyapatite (HA) [2]. A
crosslinking reaction occurs between sodium alginate and calcium released by CPC
during setting, resulting in the formation of water-insoluble calcium alginate gel [3].
The effect of addition of two different types of sodium alginate (differ in viscosity) on
properties of tetracalcium phosphate/nanomonetite (TTCPMH) cement mixture was
investigated. The TTCPMH was synthesized by in situ reaction between TTCP and
diluted solution (1:4) of orthophosphoric acid in ethanol. The sodium
alginate/TTCP/nanomonetite composite system was prepared by mixing TTCPMH
powder mixture with hardening liquid containing 2 wt % NaH2PO4 (analytical grade,
Sigma-Aldrich) and sodium alginate. The final content of sodium alginate in
composites was 0.25; 0.50; 1.0; 2.0 wt % and 0.25, 0.5 wt % for low (LOW) (Alginic
acid sodium salt from brown algae, BioReagent, plant cell culture tested, low
viscosity, Sigma-Aldrich) and medium (MED) (Alginic acid sodium salt from brown
algae, medium viscosity, Sigma-Aldrich) viscously sodium alginate respectively.
Results of the analysis of stress/strain curves are shown in Fig.1. The comparison of
curves verifies the same character of dependence with a strong reduction of both
parameters (around 70 % and 30 % decrease in the work of fracture (WOF) and
Young´s modulus respectively) after 0.25 wt.% addition of low alginate.
The dependences of compressive strength (CS) on content or alginate viscosities
can be observed in Fig. 2 which clearly demonstrate about the 50 % reduction of CS
in 0.25 or 0.5 and 1 LOW biocements with further about 50% reduction in 2 LOW
cement. A more inhibition effect of MED alginate on setting process and the
decrease in CS of composites was found which demonstrates favorable properties
of LOW alginate for utilization as the additive in TTCPMH cement.
th
EFFECT OF ALGINATE HYDROGELS ON MECHANICAL PROPERTIES OF TETRACALCIUM PHOSPHATE
/NANOMONETITE BIOCEMENT R. Štulajterová, Ľ. Medvecký, M. Giretová, T. Sopčák, J. Briančin
Fig. 1 Dependence work of fracture and Young´s modulus on alginate content (wt %)
Fig. 2 Effect of compressive strength and porosity of cements on addition of sodium alginate
Acknowledgements: This work was supported by the Slovak Grant Agency of the Ministry of
Education of the Slovak Republic and the Slovak Academy of Sciences, Project VEGA
2/0047/17.
References
[1] Khairoun I, Driessens FCM, Boltong MG, Planell JA, Wenz R. Addition of cohesion
promotors to calcium phosphate cements. Biomaterials. 1999; 20: 393-398.
[2] Olderøy MO, Xie M, Andreassen JP, Strand BL, Zhang Z, Sikorski P. Viscoelastic
properties of mineralized alginate hydrogel beads. J.Mater.Sci.:Mater.Med. 2012; 23:
1619-1627.
[3] Ishikawa K, Miyamoto Y, Takechi M, Toh T, Kon M, Nagayama M, Asaoka,K. Non-decay
type fast-setting calcium phosphate cement: hydroxyapatite putty containing an increased
amount of sodium alginate. J. Biomed. Mater. Res. 1997; 36: 393-399.
Jahodná, Slovakia
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P6
TITANIA SOL-GEL COATING ENRICHED BY Ag, Ca, P PREPARED

BY DIP COATING TECHNIQUE
Kristýna Švagrová, Diana Horkavcová, Aleš Helebrant

of Chemistry and Technology Prague, Technická 5, 166 28 Prague, Czech Republic
e-mail: svagrovk@vscht.cz
Keywords: sol-gel, titania coating, silver, calcium-phosphate, dip-coating, adhesion test
Biomaterials have to meet strict biological, mechanical, as well as chemical

requirements before the implantation into the human body [1]. The surface of a
material can be adjusted using various techniques and many types of coatings. The
sol-gel process is a wet-chemical technique for the fabrication of various products,
also coatings on differently shaped materials, in which controlled hydrolysis and
polycondensation of alkoxides generates stable, firm coatings with diverse
properties [2]. Thin coatings can be produced on a substrate’s surface by dip, spin
or spray coating and many others techniques [3].
In this work, three types of sol-gel coatings were prepared and, subsequently, tested
on chosen properties. Titanium sheet (grade 5) was cut into plates with size 10 x 30
x 1 mm, ground SiC: P400, P600, P800. Samples were cleaned in an ultrasonic bath
with acetone and ethanol. The roughness of the titanium substrate was defined by
profilometer Hommel Tester T1000. The first type of sol was basis titania sol (T)
prepared by mixing of tetra-n-butyl-orthotitanate, acetylacetonate, triton, ethanol and
nitric acid. Second sol (TA) contained also silver in form silver nitrate with the
-1
concentration of 0,06 mol∙l . Last sol (TACP) was with the addition of silver nitrate,
calcium nitrate tetrahydrate and triethyl phosphate. Treated substrates were coated
using the dip-coating technique during stirring at the room temperature. Chosen
-1 -1
speed of dipping was 20 cm∙min , dwell time 30 s and withdrawal speed 6 cm∙min .
Coated substrates were fired at 400 °C for 2 hours. The fired coatings were
characterized by optical (Olympus BX 50) and electron microscope (Hitachi S4700).
Adhesion (the ability of a coating to adhere to the substrate) was determined using
the tape test according to ASTM D 3359-02. A lattice pattern of 6 x 6 parallel cuts
with 1 mm gap between them was made through the coating down to the substrate.
The special tape was placed on the lattice pattern area and after 90 seconds torn
off. Surfaces of the coatings after the tape test were examined with optical
microscope and adhesion of each type of the coating was evaluated by comparison
with side illumination according to the percentage of the removed area.
By profilometer was found out the roughness of the substrate. The real measured
length of titanium substrates was 1.5 mm and three measurements on one treated
sample were performed. The surface was homogenous, without big inequalities or
scratches and its roughness was ranged from the minimum - 0,8 to the maximum
th
TITANIA SOL-GEL COATING ENRICHED BY Ag, Ca, P PREPARED BY DIP COATING TECHNIQUE
K. Švagrová, D. Horkavcová, A. Helebrant
0,9 μm. Coatings prepared by sol-gel process contained interconnected cracks all
over the surface. Quantity of these cracks increased with the number of additives in
the basic titania sol. Coating T had the smallest amount of cracks and, contrary,
TACP coating contained the highest amount of cracks. Nevertheless, all types of
coatings were homogeneous and they perfectly copied relief of the substrate. Tape
test showed, that even the coatings contained cracks detected on the entire
coating's surface, it had no influence on the final adhesion. On the coating's surface
of types T and TA, the glue from adhesive tape was found. Coatings stayed
undamaged and adhesive ability of all coatings was evaluated like very good, grade
5.
Acknowledgement: This work was supported from specific university research MSMT No 21-
SVV/2019.
References
[1] Gupta, R.F., Kumar, A. (2008). Bioactive materials for biomedical applications using sol-
gel technology. Biomedical materials, 3 3, 034005.
[2] Qu Jie, Lu Xiong, L, Dan, Ding Yonghui, Leng Yang, Weng Jie, Qu Shuxin, Feng Bo,
Watari Fumio (2011). Silver/hydroxyapatite composite coatings on porous titanium
surfaces by sol-gel method. Journal of biomedical materials research. Part B, Applied
biomaterials. 97. 40-8. 10.1002/jbm.b.31784.
[3] Horkavcová, D., Novák, P. ,Fialová, I.,Černý, M., Jablonská, E.,Lipov, J., Ruml, T.,
Helebrant, A. (2017). Titania sol-gel coatings containing silver on newly developed TiSi
alloys and their antibacterial effect. Materials Science and Engineering C. 76. 25-30.
Jahodná, Slovakia
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P7
IN VITRO TESTING OF CHEMICAL SOLUBILITY OF THERMAL

INSULATION FIBRES
Ingrid Czudková, Aleš Helebrant, Helena Hradecká

Department of Glass and Ceramics, University of Chemistry and Technology,
Prague, Technická 5, 166 28 Prague 6 - Dejvice, Czech Republic
e-mail: czudkovi@vscht.cz
Keywords: glass fibres, dissolution, in-vitro, dynamic test
Glass fibres belong among the most widely used materials for thermal-insulating
applications. However, they are also potential source of respirable fibres, which can
be inhaled to the lungs and can cause various diseases leading to lung cancer [1].
From that reason there is an effort to make new glass fibres, which should be
soluble in lungs fluids and should have a low biopersistence. The health risks of
fibres can be observed by in-vivo and in-vitro methods. In-vitro methods are based
on leaching of fibres in model lung fluid. By these tests, the initial information could
be obtained about solubility and corrosion of fibres.
In this work, the dissolution of three types of thermal-insulating glass fibres (E-fibres,
Promaglaf HTI 1200 and 1250) was observed. These fibres are declared as being
harmless and having a low biopersistence. The dissolution of fibres was tested
by dynamic (flow-through) tests, which properly simulate the human lung system
(37 °C, the flow rate of simulated lung fluid (SLF) 120 ml/day, SLF with pH 7.4) [2].
In solutions, the pH values were measured and concentrations of Si, Ca and Mg
were evaluated by AAS technique. The changes in weight loss of fibres were
observed. Also the values of the time dependence of the normalized leach amount
of glass components (NLi) were computed and were compared with the data of NL i
obtained from kinetic model of Department of Glass and Ceramics (UCT Prague) [3].
The changes in appearance and composition of the fibres were evaluated
with SEM-EDS techniques. In addition, the simple mathematical model was derived
in order to estimate the extent of the effect of the shrinking glass surface (Graph 1).
It considers that the fibres have a cylindrical shape and they dissolve only in the
radial direction. The back precipitation and saturation effect are neglected. The
model assumes that the fibres are dissolving congruently.
From results obtained, it is perceptible that E-fibres had the best dissolving ability,
after 135 days of leaching the fibres were nearly dissolved. Less soluble were fibres
Promaglaf HTI 1200 and the least Promaglaf HTI 1250. As follows
from experimental time dependencies NLi, E-fibres dissolve congruently, compared
to fibres Promaglaf HTI 1200 resp. 1250, which dissolve incongruently. It is caused
by production of precipitates – calcium-phosphate resp. silica gel layers (Fig. 1). The
values of NLi are in accordance with data obtained from kinetic model of Department
of Glass and Ceramics (UCT Prague).
th
IN VITRO TESTING OF CHEMICAL SOLUBILITY OF THERMAL INSULATION FIBRES
I. Czudková, A. Helebrant, H. Hradecká
a) b)
Fig. 1 Glass fibres after leaching tests

a) E-fibres,
b) Promaglaf HTI 1200 and
c) Promaglaf HTI 1250)
c)
Fig. 2 Experimental values of weight

loss in comparison with data
obtained from mathematical
model
Acknowledgement: Financial support from specific university research (MSMT No 21-

SVV/2019).
References
[1] Skácel, F.; Guschlová, Z.; Tekáč, V. Azbestová a minerální vlákna ve vnitřním ovzduší.
Chem. listy 2012, 106, 961–970.
[2] Sebastian, K.; Fellman, J.; Potter, R.; Bauer, J.; Meringo, A.; Zoitos, B. EURIMA test
guideline: In-vitro acellular dissolution of man-made vitreous silicate fibres. Glass. Sci.
Technol. 2002, 75 (5), 263–270.
[3] Helebrant, A; Tošnerová, B. A mathematical model used to compare durability tests
under different flow conditions. Glass Technology 1989, 30 (6), 220–223.
Jahodná, Slovakia
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P8
Maryna Kyslytsyna, Pavel Raschman, Gabriel Sučik

Technical University of Košice, Faculty of Materials, Metallurgy and Recycling, Letná
9, 04 200 Košice, Slovak Republic
e-mail: maryna.kyslytsyna@gmail.com
Keywords: leaching, magnesite, kinetics, mathematical modelling, experiments
To obtain successful results of experiment it is necessary to precisely define and

control the conditions of a scientifically based procedure. One of the most important
processes in hydrometallurgy is leaching of the ore, because it determines the
effectiveness of the whole technological process. Therefore, the methodology of
leaching kinetics experimental research is the focus of present work. The process of
leaching of poor magnesite was analysed, as a practical example. Hydrochloric acid,
nitric acid and acetic acid were used as the leaching agents. The effect of varying
acid concentration and temperature on leaching rate was investigated. The paper
presents a comparison of the results obtained at the initial stage of the study, when
not all aspects of the experiment were yet under control, with the latest results. The
procedure of experiments was improved by changes, which are discussed in the
paper. In addition, our results and the results of similar kinetic studies published by
other authors were used to compare the accuracy and reliability of the routes
applied, applying mathematical modelling and non-porous shrinking particle model
(NSPM).
The obtained results of leaching of magnesite in hydrochloric acid are summarized
in Fig. 1Fig. 1, Fig 2 and Fig. 3.
Fig. 1 shows the results of the “older” experiments, Fig. 2 shows the results obtained
by the improved experimental procedure, and Fig. 3 shows the transformed results
of other authors [1]. The results in Fig. 1 and Fig. 2 show high correlations between
the model NSPM and experiment and evidence that the reproducibility of results has
been improved by improving the experimental procedure. From the results of
Özdemir et al. [1] in Fig. 3 we can conclude, that the experimental points lie on
almost one curve, and the reproducibility of the results seems very good. However, if
we assume that the reaction between MgCO3 and HCl is irreversible, then the
stabilization of the process at the value of conversion of about 90 % is due to either
chemical analysis or ambiguously defined degree of conversion, x. This conclusion
confirms that experimental study of the kinetics (especially at higher temperatures)
of the complex heterogeneous reaction of magnesite leaching is rather difficult.
The same procedure was applied to the results of the leaching tests carried out
using nitric and acetic acid.
Concerning the results of the analysis of the magnesite leaching reaction with three
inorganic acids, it can be concluded that the developed and validated experimental
procedure provides accurate and reliable results in the study of the leaching kinetics.
th
M. Kyslytsyna, P. Raschman, G. Sučik
120 120
100 100
Conversion x (%)
Conversion x (%)
80 80
60 60
40 40
20 20
0 0
0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0
t/t0.5 t/t0.5
Fig. 1 Mg conversion vs. t/t0.5 dependence Fig. 2 Mg conversion vs. t/t0.5 dependence
for various hydrochloric acid for various hydrochloric acid
concentrations – the results were concentrations – the results were
measured using the original measured using the improved
experimental procedure experimental procedure
100
90
80
Conversion x(%)
70
60
50
40
30
20 Fig. 3 Mg conversion vs. t/t0.7 dependence
10 for the hydrochloric acid leaching
0 of magnesite – the results were taken
0.0 5.0 10.0 15.0
t/t0.7 from the literature [1] and adapted
Acknowledgements: This work was supported by the Scientific Grant Agency of the Ministry
of Education of the Slovak Republic and by the Slovak Academy of Sciences (grant
1/0592/17).
References
[1] Özdemir, M., Çakir, D., Kipçak, İ.: Magnesium recovery from magnesite tailings by acid
leaching and production of magnesium chloride hexahydrate from leaching solution by
evaporation. In: Int. J. Miner. Process. 93 (2009) 209–212.
Jahodná, Slovakia
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P9
a a,b a a
Pavol Vadász , Dávid Medveď , Beatrice Plešingerová , Gabriel Sučik ,
c,d a d
Ľuboš Ďurík , Ľuboš Popovič , Ľudovít Parilák
a
Letná 9, 042 00 Košice, Slovak Republic
b
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47,
040 01Košice, Slovak Republic
c
Žiaromat, a.s., Továrenská 1, 985 01 Kalinovo, Slovak Republic
d
ŽP VVC s.r.o., Kolkáreň 35, 976 81 Podbrezová, Slovak Republic
e-mail: pavol.vadasz@tuke.sk
Keywords: corrosion test, refractory castable, slag, corundum
The monolithic refractory materials gain a broader application in the metallurgical

industry, nowadays. These materials are applied in area under the slag-line (bottom
and walls of ladle) mainly. The increasing corrosion resistance of refractory
materials prolongs the life of lining and improves the steel quality. The refractory
materials of linings are source of impurities and inclusions in steel. The use of high
quality refractory materials which are resistant to wear has a positive effect on total
cost of production and reduction of post-mortem refractory waste.
The results of the static crucible tests of refractory alumina concretes with high
content of fused corundum and MA–spinel are presented in this work.
Two types of refractory materials: A–standard low cement castable (LCC) and B–
ultra-low cement castable (ULCC) were tested. The tested LCC and ULCC
refractory castables are products of company ŽIAROMAT, a.s., Kalinovo and their
base characteristics are shown in work [1].
Sample A: 90 wt.% Al2O3; 5.5 % MgO; 1.,2 % CaO;
Sample B: 93 wt.% Al2O3; 3.5 % MgO;
The castables are prepared from the raw materials: tabular corundum, reactive
oxide - Al2O3, MA-spinel (Al2O3-SiO2) and spinel concrete. The corrosion tests were
conducted with the real calcium-alumina slag (CaO-Al2O3-(SiO2-MgO) generated in
the steel production. The cylindrical hole ( = 20 mm) was drilled into every piece of
refractory material and these cubic crucibles with a hole were fired in electric
resistance furnace. Then the hole was filled with slag (10 g) and sample were
annealed at the temperature of 1450 °C for 5 hours in a static air atmosphere. The
corrosion of materials was evaluated comparing the results of the chemical analyses
of slag before and after corrosion tests, followed by the macroscopic and
microscopic observations of the vertical cuts along the line at the refractory - slag
boundary and X-ray phase analyses.
The samples were cross cut after static corrosion test as it can be seen in Fig. 1. At
first, the s-l phase boundaries were studied. Then the sampling for the microscopic
th
P. Vadász, D. Medveď, B. Plešingerová, G. Sučik, Ľ. Ďurík, Ľ. Popovič, Ľ. Parilák
observations), EDX semi-quantitative analyses and for the phase and chemical
analyses was performed.
Fig. 1 A and B samples with corrosive slag after corrosion test
The phase analyses confirmed that corundum and spinel are major components of
sample. Hibonite (CaO(Al2O3)6) was detected after the annealing in minor quantity.
The corundum, spinel and hibonite were detected also in the corroded material in
comparable quantity.
The test results show that the slag releases and dissolves Al 2O3 and MgAl2O4
grains. The melted slag wets well the tested refractory materials. The shape
changes of crucibles after the corrosion point to a surface and sub-surface attacks.
An intensive flow of slag creates a pot-hole in the refractory materials at surface of
slag and a vertical flow intensifies the degradation of crucible walls. The A sample
was intensively attacked; the alumina-spinel from matrix was more dissolved by slag
comparing to B sample. The dissolution process is control by the diffusion at which
2+ v-
mobility of Mg cations in melt is higher than of Al-Ox complexes. The corrosion
alumina-spinel castables of A sample (LCC) with higher content of MgO by CaO-
Al2O3-(SiO2-MgO) slag are therefore more intensive corroded than of B sample
(ULCC).
Acknowledgements: This study was financially supported by project APVV-17-0483

professional cooperation with ŽP VVC, s.r.o., Podbrezová and Žiaromat, a.s, Kalinovo and the
Slovak Grant Agencies through “VEGA – MŠVVaŠ SR a SAV” project No.1/0015/18.
References
[1] Ďurík, Ľ., Švantner, J., Brenkus, M.. Parilák, Ľ.,: In: Conference of ŽP VVC 2018, 4.-6.9.
2018, Hotel Stupka – Tále, SR
Jahodná, Slovakia
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P 10
CORROSION OF REFRACTORY MATERIALS IN ALUMINUM

PRODUCTION
Eva Grambálová
Institute of Metallurgy, Letná 9, 042 00 Košice, Slovak Republic
e-mail: eva.grambalova@tuke.sk
Keywords: corrosion test, corrosion test analysis methods, Al2O3 - SiO2, refractory material
Industrial production of aluminum as well as other metallic and non-metallic

materials is a necessity of the present time. In these processes, different types of
wear of the refractory materials occur, for example by mechanical or chemical –
corrosion [1].
The aim of this paper is to present the results of a corrosion test on four kinds of
refractory materials used in aluminum production. Specifically, these were unshaped
Al2O3 - SiO2 based refractory materials [2]. The chemical analysis results of the
tested refractory materials (experimentally labeled as A, M, R1, R2) are summarized
in the following table (Table 1.)
Table 1 Results of chemical analysis of tested refractory concretes

Tested Chemical analysis [wt.%]
samples Al Ca Si Fe Ti Na Mg K
A 38,73 4,30 1,75 1,14 0,95 0,22 0,25 0,15
M 38,25 4,40 1,75 0,38 1,04 0,27 0,20 0,19
R1 36,76 2,35 7,00 1,25 0,66 0,51 0,09 0,22
R2 34,22 3,15 0,30 0,22 0,06 0,48 0,08 0,02
The phase composition of the aluminosilicate samples was verified by phase

diffraction analysis (XRD) performed on a Difractomer Rigaku MiniFlex 600
(radiation [emission CuKα Ni filter), Bragg-Brentano goniometer, Theta-2Theta
arrangement, excitation voltage 40kV, 15 mA). As the corrosive medium, a coating
salt from aluminum production was used. Cover salts separate pure aluminum from
the furnace atmosphere, preventing its oxidation. The problem is that the cover salt
corrodes the aluminosilicate building materials used in refining or smelting-refining
furnaces, which significantly reduces the lifespan of the lining. The chemical
composition of the corrosive medium used is shown in Table 2.
Table 2 Elemental chemical analysis of corrosive medium (cover salt)

Chemical analysis [wt. %]
Corrosive medium -
Mg K Ca Na Cl
(cover salt)
21,17 16,77 0,24 0,105 40,67
th
ORROSION OF REFRACTORY MATERIALS IN ALUMINUM PRODUCTION
E. Grambálová
The corrosion test was carried out by a static corrosion crucible test in a laboratory
resistance furnace at 850 °C. The temperature of the experiment ensured the
existence of a homogeneous melt during the corrosion test. The 2 hour expiration
time at the maximum temperature of the corrosion test was selected. The
dimensions of the tested refractory materials were 100 mm x 100 mm x 100 mm.
The opening for the corrosive medium was drilled in the center of the sample with a
diameter of 25 mm and a bore depth of 35 mm. Samples were dry-cut after the
experiment with a diamond disc. The results of the corrosion test were evaluated by
macroscopic, microscopic, chemical and semi-quantitative EDX analysis.
Macroscopic observations were realised by visual assessment of the cross-section
of the samples. As a result of this observation, all test samples were penetrated by
corrosive medium after the corrosion test. Each sample was soaked in a different
way and to different depth from the sample opening (Fig.1).
Fig. 1 Samples after corrosion test
Microscopic evaluation of various sample areas was performed on an Axio Observer

1M light microscope (inverted optical microscope - Carl Zeiss, Germany). Areas of
penetration into both the side and bottom portions of the melt penetration into the
sample opening were assessed. Chemical analysis was performed using the AAS
method on a Perkin Elmer 3100 instrument. A sample for chemical analysis was
obtained by drilling into the respective regions of the corroded samples. Semi-
quantitative elemental EDX analysis was performed on an EVO MA15 electron
microscope with EDX / WDX.
Acknowledgements: This study was financially supported by project of Slovak Grant

Agencies through “VEGA – MŠVVaŠ SR a SAV” project No.1/0015/18.
References
[1] A.G. Furness, “The Importance of Refractory Materials in Aluminium Production,”
Proceedings of International Symposium on Refractories (1988), pp. 539–548.
[2] B. Clavaud and Y. Jost, “Refractories Used in Melting Furnaces for Aluminium Alloys,”
Interceram Proceedings XXIII Intl. Colloquium on Refractories, (1981), pp. 306–314.
Jahodná, Slovakia
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P 11
CHARACTERIZATION OF DIFFERENT TYPES OF WOOD ASHES USED

IN HISTORICAL GLASSMAKING
1 1 2
Karolína Pánová , Dana Rohanová , Hedvika Sedláčková
1
ofChemistry and Technology in Prague, Technická 5, 166 28 Prague,
CzechRepublic
2
Archaia Brno, o.p.s., Bezručova 15, 602 00 Brno, Czech Republic
email: karolina.panova@vscht.cz
Keywords: historical glass, glassmaking technology, wood ash, glass melting
When talking about historical glasses, one of the first things that we have to consider
is the chemical composition. Generally, archaeological glass originating from
southern Europe, near East and Egypt is sodium or sodium-calcium glass. It was
made using natron (a natural mineral consisting mainly of Na 2CO3.10H2O and
NaHCO3) or ashes from halophytic plants (i.e. Salicornia, Salsola). On the other
hand, glass produced in Central and Western Europe was made with wood ash or
wood ash potash. In the regions northern from the Alps, wood ash has been used as
a flux for glassmaking since the middle ages. In general, wood ashes contain a high
amount of potassium and/or calcium oxides that, when mixed with suitable sand,
allow for potassium-calcium glass to be formed even without any other additives.
The aim of this work was to evaluate the use and effect of different types of
th
potassium-calcium ashes. In his work dated to the early 12 century, Theophilus
th
mentions the use of beech ash. It is also stated in the work of Agricola from the 16
century. Several other sources claim that different types of ashes could be used as
well – pine, spruce, birch or bracken [1, 2]. It is believed that beech was widely used
in Central Europe (Bohemia, Eastern Germany, Southern Poland etc.) [3], while
bracken is mainly considered to be used in less wooded areas such as the British
Isles [4].
For this study, three types of ashes were chosen – beech (Fagus sylvatica), spruce
(Picea abies) and bracken (Pteridium aquilinum). A series of model glass samples
were prepared using 1 weight part of glassmaking sand and 2 weight parts of wood
ash. This ratio of the two raw materials was chosen according to the ratio stated by
Theophilus which also corresponds with the batch of early medieval and some types
of medieval archaeological glasses. To ensure thorough melting and to follow
historical technology, the homogenized batches were firstly made into ‘frit’ by
heating them at 700 °C for 4 hours. After cooling, the frits were crushed and
homogenized and then melted at 1250 °C for another 4 hours. After melting, the
samples were quenched in water and analysed via XRF analysis to determine the
glass composition.
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CHARACTERIZATION OF DIFFERENT TYPES OF WOOD ASHES USED IN HISTORICAL GLASSMAKING
K. Pánová, D. Rohanová, H. Sedláčková
It is evident that beech, spruce and bracken ash do provide very different glass
compositions. Big differences have been observed in the amount of K 2O and CaO
and in their ratio as well. For beech ash glass the ratio is around 2.3, for spruce ash
glass 4.3 and for bracken ash glass only 0.3. Those ratios correspond very tightly
with the ratios in raw ashes. Interestingly, the content of P 2O5 remains almost the
same for all of the samples. The knowledge of the chemical compositions of different
types of ashes is therefore very valuable and can be used to distinguish between
various production technologies of early glasses from Central Europe.
Acknowledgement: This work received financial support from specific university research
(MŠMT No. 21-SVV/2019) and from the Czech Science Foundation (GA 19-05677S).
References
[1] STERN, W. B., GERBER, Y. Ancient Potassium-Calcium Glass and its raw materials
(Wood-Ash, Fern-Ash, Potash) in Central Europe. Mitteilungen der Naturforschenden
Gesellschaften beider Basel, 2009, vol. 11, p. 107-122.
[2] JACKSON, C. M., SMEDLEY, J. W. Medieval and post-medieval glass technology: A
review of the use of bracken in glassmaking. Glass Technology, 2002, vol. 43, n. 6, p.
221-224.
[3] WEDEPOHL, K. H., SIMON, K. The chemical composition of medieval wood ash glass
from Central Europe. Chemie der Erde, 2010, vol. 70, p. 89-97.
[4] MEEK, A. S. The chemical and isotopic analysis of English forest glass. Dissertation,
University of Nottingham, 2011.
Jahodná, Slovakia
th th
25 -27 June, 2019 201
P 12
LONG TERM ENVIRONMENTAL THREATS FROM WORLDWIDE

INDUSTRIAL WASTE
Damir Hršak, Anita Štrkalj, Ivan Jandrlić, Ljerka Slokar, Zoran Glavaš
University of Zagreb Faculty of Metallurgy, Sisak, Croatia
e-mail: hrsakd@simet.hr
Worldwide there is lot of long term environmental threats for human health and biological
diversity from industrial waste, including preparation of ceramic materials processes, which
can be solve only with strict international control of all major industrial pollutant. Unlimited
industrial development and sustainable quality of environment are in contradiction and we
need to find acceptable balance.
Keywords: environmental threats, industrial waste, ecology
Introduction
All kinds of industries wastes, including waste of preparation of ceramic materials,
can be classified as solid wastes, liquid wastes, or air pollutants. Often different
wastes are managed by different people in different departments. In lot of countries
this separate categories of wastes are regulated by distinct bodies of laws, but in
reality three categories of waste are closely interrelated [1].
If we want sustainable environmental quality for our and future generation we need,
in present days, to take proper care and permanently remediate all kinds of
industrial waste.
Principles of solving environmental threats
st
Beginning of 21 century is period of techno-scientific era in which humankind is
faced with destruction issues that regard other living beings attack nature as a
whole. If we want to act efficiently we need broad networking of various sciences,
and professions views, which is known as multi-, inter- and trans-disciplinarity, and
pluriperspectivism [2].
There are no state borders for pollution products and no other planet for humankind
emigration in dystopian future. We need to establish efficient international control of
waste disposal in all industrial processes including preparation and use of all
ceramic materials. In close future it should be obligation of every UN member state
or pollution products will be beyond reasonable control.
Furthermore, we as scientists always need to ask ourselves are certain production
that produces long-term waste really necessary to be done.
Conclusion
Regardless of the presence of governmental or economic limitations effective
industrial waste treatment is directed towards the removal of all contaminants that
have significant impact on air, water and land. If we want to eliminate long term
negative influence of industrial waste on local and global environment we must be
th
LONG TERM ENVIRONMENTAL THREATS FROM WORLDWIDE INDUSTRIAL WASTE
D. Hršak, A. Štrkalj, I. Jandrlić, L. Slokar, Z. Glavaš
able to compel including the costs of these constraints, in all industrial production
decisions including processes of preparation advanced ceramics materials.
References
[1] F. Woodard, Industrial Waste Treatment Handbook, Batterworth Heinemann, Boston,
2001.
[2] H. Jurić, Facta Universitatis 15 (2017) 2, 127-144.
Jahodná, Slovakia
th th
25 -27 June, 2019 203
AND RECYCLING
Study programme
Study programme
Study branch
Bachelor studies Master studies Doctoral studies
4.3.2  Waste Treatment  Waste Treatment  Waste Treatment
Environmental andRecycling and Recycling and Recycling
Engineering  Environmental chemistry
 Materials  Material  Material Science
5.2.26
 Construction Materials Engineering  Plastic
Materials
inAutomotive Industry  Materials Forming Deformations
 Metallurgy  Metallurgy  Metallurgy
 Control and Modeling of
Metallurgical Processes  Foundry
 Foundry for Automotive
5.2.39
Industry
Metallurgy
 Chemical Processes in
Materials Production
 Heat engineering  Heat engineering  Heat engineering
andgas industry and gas industry
 Integrated  Production
5.2.57 Quality  Integrated Management
Management Quality
of Production Systems
Systems Engineering
Contact: Faculty of Materials, Metallurgy and Recycling

Technical University in Košice
Letná 9, Block A, IV. Floor, 042 00 Košice
Tel: +421 55/602 2023
e-mail: dekanat.fmmr@tuke.sk, http://fmmr.tuke.sk/
Proceedings - XIIIth International Conference
PREP AR ATION OF CER AMIC M ATERI ALS
Copyright  Technical University of Kosice 2019
June 2019
I. Edition
Number of Copies – 75
Number of Pages – 206
Edited by:
Reviewers:
Assoc. Prof. Ing. Miroslav Hnatko, Ph.D.
RNDr. Martin Fabián, Ph.D.
Ing. Diana Horkavcová, Ph.D.
Ing. Dana Ivanová, Ph.D.
ISBN: 978-80-553-3314-4
PREPARATION OF CERAMIC MATERIALS | 13
Jahodná, 25 – 27 June 2019
2019 | 13
ISBN 978-80-553-3314-4
25th – 27 th June 2019 Jahodná, Slovakia

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TECHNICAL UNIVERSITY OF KOŠICE

FACULTY OF MATERIALS, METALLURGY

PREPARATION OF CERAMIC MATERIALS

Slovak Silicate Society

Institute of Materials Research  Slovak Academy of Sciences, Kosice

PREPARATION OF CERAMIC MATERIALS

Proceedings - XIIIth International Conference

The publication of proceedings was supported by

SCOPES OF THE CONFERENCE:

L1 Ľ. Ďurik , J. Švantner, Ľ. Parilák, M. Brenkus 11

L 24 P. Dvořáková, F. Oujiří, A. Kloužková, M. Kavanová, 153

P1 E. Kurovics, L. A. Gömze 180

PREPARATION OF CERAMIC MATERIALS

DEVELOPMENT OF ULTRALOW-CEMENT SPINEL CASTABLE

ULCC with MA-spinel addition

Fig.1 Binary diagram of MgO-Al2O3

Fig. 3 Effect of spinel grain size on spinel refractory infiltration depth

Table 1 Typical properties of top ULCC spinel castable

Table 2 Typical properties of low-cement castable ŽN 1750 SP

Based on a thorough research and analysis of ULCC castable in 2017, a test

Table 3 Typical properties of developed ULCC spinel castable ŽNU 1800 SP

 higher cold crushing strength by 57 MPa, i.e. 114 % increase

Acknowledgement: This work was supported by the Slovak Research and

EXAMINATION OF DIFFERENT WASTE MATERIALS FOR ROAD

Bella Udvardi, Róbert Géber, István Kocserha

mine tailings to replace conventional aggregates used in asphalt pavements. They

Fig.1 Particle size distribution of fillers

Chemical element composition and microstructure

Table 1 Chemical composition of fillers

Limestone Aluminum dross

Brick powder Concrete powder

Determination of hydrophilic coefficient

Fig. 3 Method of German Filler Test

[8] J. M. Ried.: The use of alternative materials in road construction

CONVERSION OF BATCH-TO-GLASS ANALYSIS: APPLICATION

Processing of the cold-cap is not always as straightforward as batch-to-glass

waste glass: Implications for the processing and immobilization of technetium-99,”

PREPARATION OF LIGHTWEIGHT AGGREGATES FROM INDUSTRIAL

Roman Bystrický, Miroslav Hnatko, Jaroslav Sedláček

Table 1 Major oxides in industrial waste in mass%

Table 2 Composition of starting mixtures

The powder mixtures were homogenized in homogenizer Dr.Fritsch PM10 at 80rpm

SiO2(s) + 3C(s) → SiC(s) + 2CO(g) (1)

Table 3 Phase composition of the samples after heat treatment at 1500 °C

Samples Phases determined by XRD

Table 4 Density and compressive strength of granules prepared at different temperatures

VIAC AKO 60 ROKOV SKÚSENOSTÍ

magnéziové, magnéziovo-spinelitické, magnéziovo-chromité,

dusacie, torkrétovacie, zásypové, malty, troskotvorné prísady,

opravárenské hmoty, kaustická magnézia

ELECTRICAL CONDUCTIVITY IN Ca DOPED LaAlO3 PEROVSKITES

The results of electrical measurements showed that undoped LaAlO 3 is an insulator

Fig. 3 Temperature dependence of total electrical conductivity of La1-xCaxAlO3- δ ceramics

Analysis of the impedance spectroscopy data showed that electrical properties of

TERAHERTZ TIME-DOMAIN SPECTROSCOPY OF THE BORON DOPED

The nanoparticle morphology can be influenced easily by presence of additives

vibration were found [8, 9]. The IR spectrum of elongated-spindle-like nanoparticles

* Found slight, wider shift for like elongated - spindle –nanoparticles

Pellets of ZnO material were measured using THz-TDS. Frequency dependent

Pseudo-hexagonal nanoparticles Elongated-spindle nanoparticles

Pseudo-hexagonal nanoparticles Elongated-spindle nanoparticles

[5] Zelechovska. K. (2014) Methods of ZnO nanoparticles synthesis, BioTechnologia, vol.

GLASSES IN THE PbO-Bi2O3-Ga2O3 SYSTEM WITH ADDITION OF Ag2O

of magnitude higher than those of inorganic materials is limited by their lower