Polymer Derived Ceramics

Group manager:

Group members:

The scope of Polymer Derived Ceramics (PDCs) research group includes formation, structural and microstructural analysis, and properties of the functional amorphous ceramic materials derived from the appropriately tailored preceramic polymers. We produce them by means of the sol-gel method using the wide spectrum of commercial organometallic monomers, putting an emphasis on organosilicon compounds, but also applying different derivatives of i.e. aluminum, titanium or boron. We obtain ceramic materials during the two-stage thermal treatment (aging, pyrolysis) of appropriate preceramic polymers (taking into account the applications). In this way, functional materials are developed in the form of bulk or layers (dip-coating, spin-coating) on various substrates for applications at elevated temperatures, in aggressive environments and medicine.

Struktura SiOC

The main subject of the research are variously modified materials based on silicon oxycarbide (SiOC) - the so-called black glasses. The black glasses are glasses with the structure of amorphous silica (v-SiO2) where some of oxide ions (O2-) are substituted by carbon ions (C4-) - this is the so-called anion substitution (Fig. 1). Because of the difference in valence two oxygen ions are replaced by only one carbon ion - such type of the substitution leads to a local increase in the density of bonds and therefore to a significant strengthening of the network. The silica glass structure can accept only a limited amount of carbon ions. Therefore the black glasses, in addition to Si-C and Si-O bonds, usually also contain the so-called free carbon (phase separation) which is responsible for their black color. The relations between the amount of carbon ions incorporated into the structure and the amount of free carbon determine the properties of the black glasses. The total carbon content in the black glasses may vary over a wide range from zero (theoretically) to tens of percent and therefore it gives a great opportunity to adjust their properties. Through the appropriate selection of the organosilicon precursors the amount of carbon introduced into the structure and the amount of free carbon could be controlled. These opportunities are provided by the use of ladder-like oligo- and polysilsesquioxanes prepared by the sol-gel method from the so-called structural units T and D with one or two attached alkyl groups, respectively (Fig. 2a,b). The ladder-like structures are formed during the reactions of hydrolysis and polycondensation of these units (Fig. 2c). If D units (Fig. 2b) are additionally included and/or the type of the substituent R = methyl, ethyl, phenyl etc. is changed the amount of introduced carbon could be deliberately controlled.

Structural units and ladder structure

Fig. 2. The structural units - T (a) and D (b); (c) the exemplary silsesquioxane ladder-like structure.

Currently, we execute studies in the field of formation, functionalization, and analysis of structure, microstructure and performance characteristics of the produced materials, within three research fields:

a)      application of different proportions and/or various precursors based on alkoxysilanes with particular functional groups (R=methyl, ethyl, phenyl, etc. – Fig. 2);

b)      doping with numerous ions: Al3+, B3+, Ce4+, P5+;

c)      doping with nanoparticles i.e. carbon nanotubes (CNT), nanohydroxyapatite and nanosilica.

Structural studies of PDCs, carried out at room temperature and in in-situ conditions, cover the full characteristic of: phase composition (XRD and GIXRD analysis, Raman spectroscopy – point, linear measurements and Raman imaging), elemental composition (point, linear and mapping EDS analysis, and XRF) and chemical bonds/molecules (Raman, FTIR, NMR and XPS spectroscopy). In turn, microstructure is visualized using SEM, AFM and Confocal Microscopy, and BET and SAXS. In order to evaluate the functional properties of black glasses, the applied research is conducted on the Faculty of Materials Science and Ceramics and in the cooperation with abundant research units.

Additionally, in recent years PDCs group has developed an extensive scientific cooperation with the renowned foreign research centers in the field of:

a)      biocompatibility and bactericidal studies - Friedrich-Alexander University Erlangen, Germany (prof. Aldo R. Boccaccini);

b)      thermal (TG+EGA+MS) and electrochemical studies - Technical University of Darmstadt, Germany (prof. Ralf Riedel);

c)      oxidation resistance - DFI DECHEMA ForschungsInstitut, Frankfurt, Germany (prof. Mathias Galetz);

d)      rapid prototyping of tailored 3D structures:

·         Laboratoire de Chimie de l'ENS de Lyon, France (prof. Stéphane Parola) – two mutual accomplished PhD dissertations (program Cotutelle) – PhD Eng. Joanna Kustra (2018) and PhD Eng. Mateusz Odziomek (2018);

·         Università degli Studi di Padova, Włochy (prof. Paolo Colombo).

Within the framework of currently executed studies, the formed materials are investigated taking into consideration the following applications:

1.                  Coatings on titanium-based substrates and austenitic steels as potential implants – currently, the research is focused on the enhancement of bioactivity and biocompatibility of layers based on silicon oxycarbide with simulteanous preservation of anticorrosive properties and excellent adhesion by means of the modification with various cations – (PhD dissertation of M.Sc. Eng. Magdalena Gawęda – 2020), and on the development of nanoceramic hybrid layers based on Ti­O2 i SiO2 (accomplished PhD dissertation of PhD Eng. Elżbieta Długoń – 2015);

2.                  Anticorrosive coatings on ferritic steels (i.e. for Solid Oxide Fuel Cells’ interconnects) and alloys based on intermetallic phases, including TiAl i FeAl for applications in automotive industry – studies are focused on the optimization of deposition parameters used during the dip-coating technique (withdrawal speed, number of immersions etc.), thermal treatment (heating curve), structural and microstructural analysis, performance characteristics’ tests (adhesion, oxidation resistance and electrical conductivity), and mechanical properties (hardness, friction coefficient) of received coatings – (PhD dissertation of M.Sc. Eng. Maciej Bik – 2021);

3.                  Functional porous materials i.e. for application as anode material in Li-Ion batteries – the research is focused on the design of materials’ structure (choice of precursors), microstructure (both amount and dimensions of pores), and their electrochemical properties along with thermal and chemical stability;

4.                  Ceramic catalyst’s support carriers of designed microstructure – studies aim to correlate structural parameters of carrier layers, produced using different techniques (EPD, dip-coating) with catalyst activity, for coating materials based on black glasses and aluminum oxide, and optimization of catalyst composition for the investigated process (PhD dissertation of M.Sc. Eng. Izabela Rutkowska – 2023)

5.                  3D scaffolds for application in tissue engineering – studies include the preparation of inorganic and hybrid (organic-inorganic) scaffolds – formed by means of preceramic polymers’ processing using 3D printing methods, and detailed characteristic of their physicochemical and biological properties (postdoctoral fellowship (post-doc) of PhD Eng. Jakub Marchewka);

6.                  Functional adhesive layers for the consolidation of amorphous ribbons – research conducted in cooperation with ABB Corporate Technology Center CTC in Cracow is focused on the consolidation of magnetic core, nowadays built most often from amorphous ribbon, in order to limit the noise produced by magnetostriction phenomenon (PhD dissertation of M.Sc. Eng. Jolanta Nieroda )– 2021.

The presented works would not have been possible without the well-equipped laboratories of the Department of Silicate Chemistry and Macromolecular Compounds:

a)      Achromatic reflective LabRAM HR UV-Vis-NIR (200-1600 nm) Raman spectrometer equipped with 532 nm Nd:YAG laser and Olympus BX-41 optical microscope and Witec Alpha 300M + Raman spectrometer equipped with 488 nm and 633 nm diode lasers and Zeiss optics - measurements of solid and liquid samples, including high temperatures up to 1500 ° C, Raman maps;

b)      Bruker Vertex 70v MIR and FIR spectrometer (vacuum) operating in the 8000-370 and 700-30 cm -1 range respectively and BIO-RAD FTS3000 Excalibur MIR spectrometer equipped with an IR microscopy attachment working in the 4000-700 cm -1 range - measurements of solid, liquid and gas samples, including high temperature up to 700 ° C, various techniques (e.g. in KBr or PE pellet, DRS and DRIFTS, reflection for powders and coatings, ATR with ZnSe or diamond crystal);

c)      Desktop high resolution scanning electron microscope Phenom XL from ThermoFisher Scientific with CeB 6 cannon with secondary electron detector (SED) cooperating with EDS spectrometer - topography imaging sample surface with a resolution from nanometric to micrometric with software for automatic image analysis, x-ray microanalysis of the elemental composition;

d)      Bruker MULTIMODE 8 Atomic force microscope with Scanning Probe Microscopy (SPM) - imaging the surface topography of the sample with nanometric resolution;

e)      Philips X'Pert Pro X-ray diffractometers (now PANalytical) and PANalytical Empyrean with additional equipment - XRD (X-Ray Diffraction) measurements - qualitative and quantitative phase analysis including in situ (temperature) measurements, GIXRD (Grazing Incidence Diffraction), XRR (X-Ray Reflectivity) and SAXS / WAXS (Small Angle X-ray Scattering / Wide Angle X-ray Scattering);

f)       PANalytical Axios mAX WDXRF Spektrometer with 4kW Rh lamp - elemental composition analysis in solid samples;

g)      Krüss DSA25E Goniometer - liquid surface tension analysis, static and dynamic contact angle, determination of free surface energy under controlled temperature conditions using a specialized dispenser using the so-called a needle ( Liquid Needle );

h)      Olympus SZX7 Optical microscope (Olympus, Japan) with a magnification range of 8x to 56x;

i)       Sol-gel laboratory - conducting chemical syntheses;

j)       A set of Nabertherm (work up to 1750 ° C) and tubular furnaces (work up to 1200 ° C) - thermal treatment of the obtained materials in controlled atmosphere;

k)      FDM 3D printers UBOT 3D S + and DLP Wanhao Duplicator D7 Plus - obtaining three-dimensional structures of designed construction.

LIST OF THE MOST IMPORTANT PUBLICATIONS IN INTERNATIONAL COOPERATION:

Nb.

Autors

Title

Journal, number (year) pages

IF

MNiSW
Points

Citations
(Scopus)

1.

M. Odziomek, F. Chaput, A. Rutkowska, K. Świerczek, D. Olszewska, M. Sitarz, F. Lerouge, S. Parola

Hierarchically structured lithium titanate for ultrafast charging in long-life high capacity batteries

Nature Com.
8 (2017) 15636

11.88

200

45

2.

M. Odziomek, F. Chaput, F. Lerouge, M. Sitarz, S. Parola

Highly luminescent YAG:Ce ultra-small nanocrystals, from stable dispersions to thin films

J. Mat. Chem. C 5 (2017) 12561-12570

6.641

140

9

3.

J. Kustra, E. Martin, D. Chateau, F. Lerouge, C Monnereau,
C. Andraud, M. Sitarz, P.L. Baldeck, S. Parola

Two-photon controlled sol–gel condensation for the microfabrication of silica based microstructures. The role of photoacids and photobases

RSC Advances 7 (2017) 46615-46620

3.049

100

3

4.

M. Acosta, R. Detsch, A. Grunewald, V. Rojas, J. Schultheib, A. Wajda, R. W. Stark, S. Narayan, M. Sitarz, J. Koruza,
A. R. Boccaccini

Cytotoxicity, chemical stability, and surface properties of ferroelectric ceramics for biomaterials

J. Amer. Ceram. Soc. 101 (2017) 440-449

3.094

100

6

5.

M. Odziomek, F. Chaput, F. Lerouge, C. Dujardin, M. Sitarz, S. Karpati, S. Parola

From Nanoparticle Assembly to Monolithic Aerogels of YAG, Rare Earth Fluorides, and Composites

Chem. Mater. 30 (2018) 5460-5467

10.159

200

2

6.

M. Odziomek, F. Chaput, C. Dujardin, F. Lerouge, P. Cassette, M. Sitarz, S. Parola

Design and Application of High Optical Quality YAG:Ce Nanocrystal-Loaded Silica Aerogels

ACS Appl. Mater. Inter. 38 (2018) 32304-32312

8.456

200

1

7.

M. Gawęda, P. Jeleń, E. Długoń, A. Wajda, M. Leśniak, W. Simka, M. Sowa, R. Detsch, A. R. Boccaccini, M. Sitarz

Bioactive layers based on black glasses on titanium substrates

J. Amer. Ceram. Soc. 101 (2018) 590-601

3.094

100

16

8.

A. Wajda, W. H. Goldmann, R. Detsch, A. Grunewald, A. R. Boccaccini, M. Sitarz

Structural characterization and evaluation of antibacterial and angiogenic potential of gallium-containing melt-derived and gel-derived glasses from CaO-SiO2 system

Ceram. Int. 44 (2018) 22698-22709

3.45

100

4

9.

M. Odziomek, F. Chaput, F. Lerouge, A. Rutkowska, K. Świerczek, D. Carlier, M. Sitarz, S. Parola

Impact of the synthesis parameters on the microstructure of nano-structured LTO prepared by glycothermal routes and 7Li NMR structural investigations

J. Sol-Gel Sci. Tech. 89 (2019) 225–233

1.986

70

1

10.

A. Wajda, W. H. Goldmannm R. Detsch, A. R. Boccaccini,
M. Sitarz

Influence of zinc ions on structure, bioactivity, biocompatibility and antibacterial potential of melt-derived and gel-derived glasses from CaO-SiO2 system

J. Non-Cryst. Solids, 511 (2019) 86-99

2.6

70

7

.

PATENT:

1.„Method for obtaining bioactive coatings based on silicon oxycarbide”. Inventor: Maciej Sitarz, Elżbieta Długoń, Piotr Jeleń, Magdalena Gawęda; Patend description PL 229805 B1. Granted 2018-03-23, Publicated 2018-08-31.

OTHER MAJOR PUBLICATIONS OF THE GROUP

Nb.

Autors

Title

Journal, number (year) pages

IF

MNiSW
Points

Citations
(Scopus)

1.

M. Handke, M. Sitarz, E. Długoń

Amorphous SiCxOy coatings from ladder-like polysilsesquioxanes

J. Mol. Struct. 993 (2011)
193-197

2.12

70

21

2.

M. Sitarz, C. Czosnek, P. Jeleń, M. Odziomek, Z. Olejniczak,
M. Kozanecki, J. F. Janik

SiOC glasses produced from silsesquioxanes by the aerosol-assisted vapor synthesis method

Spectrochim. Acta A 112
(2013) 440-445

2.931

100

32

3.

M. Sitarz, W. Jastrzębski, P. Jeleń, E. Długoń, M. Gawęda

Preparation and structural studies of black glasses based on ladder-like silsesquioxanes

Spectrochim. Acta A 132
(2014) 884-888

2.931

100

20

4.

P. Jeleń, M. Bik, M. Nocuń, M. Gawęda, E. Długoń, M. Sitarz

Free carbon phase in SiOC glasses derived from ladder-like silsesquioxanes

J. Mol. Struct. 1126 (2016)
172-176

2.12

70

17

5.

R. Jadach, E. Długoń, K. Pach, M. Gawęda, A. Wajda,
M. Leśniak, A. Benko, M. Dziadek, M. Sowa, W. Simka,
M. Sitarz

Anticorrosive ZrO2 and ZrO2-SiO2 layers on titanium substrates for biomedical applications

Surf. Coat. Technol. 331
(2017) 221-229

3.192

100

6

6.

M. Bik, M. Stygar, P. Jeleń, J. Dąbrowa, M. Leśniak,
T. Brylewski, M. Sitarz

Protective-conducting coatings based on black glasses (SiOC) for application in Solid Oxide Fuel Cells

Int. J. Hydr. Energy 42
(2017) 27298-27307

4.08

140

10

7.

P. Jeleń, M. Szumera, M. Gawęda, E. Długoń, M. Sitarz

Thermal evolution of ladder-like silsesquioxanes during formation of black glasses

J. Therm. Anal. Calorim. 103
(2017) 103-111

2.471

70

9

8.

M. Gawęda, E. Długoń, P. Jeleń, R. Jadach, M. Sitarz

Examination of doped zirconia-based layers deposited on metallic substrates

J. Mol. Struct. 1166 (2018)
321-325

2.12

70

0

9.

P. Nieroda, K. Mars, J. Nieroda, J. Leszczyński, M. Król,
E. Drożdż, P. Jeleń, M. Sitarz, A. Koleżyński

New high temperature amorphous protective coatings for Mg2Si thermoelectric material

Ceram. Int. 45 (2019)
10230-10235

3.45

100

6

10.

M. Gawęda, E. Długoń, M. Sowa, P. Jeleń, J. Marchewka,
M. Bik, K. Mroczka, P. Bezkosty, K. Kusz, W. Simka,
M. Błażewicz, M. Sitarz

Polysiloxane-multiwalled carbon nanotube layers on steel substrate: microstructural, structural and electrochemical studies

J. Electrochem. Soc. 166 (2019) AD707–D717

3.12

100

1

11.

M. Bik, A. Gil, M. Stygar, J. Dąbrowa, P. Jeleń,E. Długoń,
M. Leśniak, M. Sitarz

Studies on the oxidation resistance of SiOC glasses coated TiAl alloy

Intermetallics, 105 (2019) 29-38

3.353

100

6

12.

J. Leszczyński, P. Nieroda, J. Nieroda, R. Zybała, M. Król,
A. Łącz, K. Kaszyca, A. Mikuła, M. Schmidt, M. Sitarz,
A. Koleżyński

Si-O-C amorphous coatings for high temperature protection of In0.4Co4Sb12 skutterudite for thermoelectric applications

J. Appl. Phys. 125 (2019) 215113

2.328

70

5

13.

M. Bik, P. Jeleń, E. Długoń, E. Bik, K. Mroczka,
M. Barańska, M. Sitarz

SiAlOC glasses derived from sol-gel synthesized ladder-like silsesquioxanes

Ceram. Int. 45 (2019) 1683-1690

3.45

100

4

14.

M. Bik, J. Szewczyk, P. Jeleń, E. Długoń, W. Simka, M. Sowa, J. Tyczkowski, J. Balcerzak, E. Bik, K. Mroczka, M. Leśniak,
M. Barańska, M. Sitarz

Optimization of the formation of coatings based on SiAlOC glasses via structural, microstructural and electrochemical studies

Electrochim. Acta 309 (2019) 44-56

5.383

100

0

15.

J. Leszczyński, A. Mizera, J. Nieroda, P. Nieroda, E. Drożdż, M. Sitarz, A. Koleżyński

Application of TPO/TPR methods in oxidation investigations of CoSb3 and Mg2Si thermoelectrics with and without a protective coating of “black glass”

J. Therm. Anal. Calorim. 2020 DOI:10.1007/s10973-019-08994-z

2.471

70

0

16.

J. Cebulski, D. Pasek, M. Bik, K. Świerczek, P. Jeleń,
K. Mroczka, J. Dąbrowa, M. Zajusz, J. Wyrwa, M. Sitarz

In-situ XRD investigations of FeAl intermetallic phase-based alloy oxidation

Corros. Sci. 164 (2020) 108344

6.355

140

0

17.

J. Marchewka, P. Jeleń, E. Długoń, M. Sitarz, M. Błażewicz

Spectroscopic investigation of the carbon nanotubes and polysiloxane coatings on titanium surface

J. Mol. Struct. 1212 (2020) 128176

2.12

70

0