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1 Pod redakcją:

Dr hab. inż. Agnieszki Gubernat

Prof. dr hab. inż. Piotra Wyszomirskiego

IX Międzynarodowa Konferencja Naukowo -Techniczna Kraków, 11 -14 września 2016

POLSKA

CERAMIKA 2 01 6

STRESZCZENIA

ABSTRACTS

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ORGANIZATOR/ORGANIZER

Komitet Nauki o Materiałach PAN

WSPÓŁORGANIZATORZY:

Instytut Ceramiki i Materiałów Budowlanych Polskie Towarzystwo Ceramiczne

WSPÓŁPRACA:

Polskie Towarzystwo Materiałoznawcze

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SPONSORZY/SPONSORS

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PATRONAT MEDIALNY/MEDIA PATRONAGE

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STRESZCZENIA REFERATÓW I POSTERÓW POLSKA CERAMIKA 2016

WORKSHOP CONTEMPORARY BIOCERAMICS

ORAL PRESENTATIONS AND POSTERS ABSTRACTS

POLISH CERAMICS 2016

WORKSHOP CONTEMPORARY BIOCERAMICS

Streszczenia wydrukowano w postaci dostarczonej przez Autorów.

W niektórych przypadkach wprowadzono drobne korekty redakcyjne.

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WORKSHOP

CONTEMPORARY BIOCERAMICS

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Bioceramic bone cements

Joanna Czechowska, Aneta Zima, Dominika Siek, Anna Ślósarczyk

AGH University of Science and Technology, Department of Ceramics and Refractories, 30 Mickiewicza Av. 30-059, Krakow, Poland, jczech@agh.edu.pl

Bone fracture and damage result in more than 2 million surgical procedures every year, and this number is predicted to increase. The population is aging and a large number of people receive implants to repair, replace or augment diseased or damaged bone. Major injuries can be treated in three ways: (I) by replacing lost tissues with prosthetic devices based on artificial implant materials, (II) by replacing with grafts (auto-, allo- or xenografts) or (III) by regenerative approaches where bioactive scaffolds with cells are used as hybrid materials (constructs) to generate tissues de novo.

Ceramic scaffolds on the basis of calcium phosphates (CaPs) have been widely applied as orthopedic and dental implants. Calcium phosphates meet a number of requirements for bone substitutes. Due to similarity in chemical and mineral composition to natural bone, CaPs exhibit high biocompatibility and bioactivity.

Clinical investigations indicate also that hydroxyapatite (HA) as well as α-tricalcium phosphate (-TCP) are osteoconductive materials [1]. The major disadvantage of current bioceramic bone substitutes is that they exist in a form requiring the surgical intervention to fit the surgical site around the implant or to carve the graft to the desired shape. The need for minimal invasive surgery has induced the development of self-setting bioceramic bone cements, which may be applied as injectable and/or mouldable bone substitutes [2, 3]. Calcium phosphate bone cements (CPCs) are produced by a chemical reaction between two phases –solid, consisting of calcium orthophosphates, and liquid. When cement components are mixed together they form a shapeable paste which can conform to osseous defects and progressively sets and hardens in situ into a solid mass.

Currently, there is a constant search for the materials that would exhibit a whole set of properties necessary to be simultaneously completely biocompatible and biofunctional. Despite numerous CPCs formulations, there are only two possible final products for the CPCs setting reaction brushite (dicalcium phosphate dihydrate, DCPD) or apatite (HA or CDHA) [4]. In our research group apatite bone cements on the basis of α-TCP as well as composites on the basis of calcium sulphate and modified hydroxyapatite has been investigated. Furthermore, various inorganic and organic additives, such as chitosan, sodium alginate, methylcellulose, have been added to improve material characteristics. A number of studies regarding setting time (Gilmore Needles), rheological behaviour (Physica MCR 3010 rheometer), phase composition (XRD, XRF, FT-IR, Raman), microstructure (SEM, AFM, MIP) and biocompatibility (in vitro tests in SBF, cell cultures) have been conducted. The effect of composition on the setting process as well as mechanical and biological properties of final materials have been tested. It was found that calcium phosphate

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8 cements due to their biocompatibility, good adaptation to shape and size of bone defect as well as excellent handling are a family of promising bone grafting materials and may constitute an alternative for traditional sintered bioceramics.

[1] De Aza P. N., De Aza A. H., De Aza S., Crystaline bioceramic materials, Bol Soc Esp Ceram 44 [3] (2005) 135-145

[2] Bohner M., Baroud G., Injectability of calcium phosphate pastes, Biomaterials 26 (2005) 1553–63

[3] Czechowska J., Zima A., Paszkiewicz Z., Lis J., Ślósarczyk A., Physicochemical properties and biomimetic behavior of α-TCP-chitosan based materials, Ceram Inter 40 (2014) 5523–5532 [4] Zhang J. , Liu W., Schnitzler V., Tancret F., M.Bouler J., Calcium phosphate cements for bone substitution: Chemistry, handling and mechanical properties. Review. Acta Biomater 10 (2014) 1035–1049

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Micropatterning of calcium phosphate

bioceramics, by femtosecond pulsed laser, for bone tissue engineering application

Marie LASGORCEIX

1

, Cédric OTT

1

, Laurent BOILET

1

, Stéphane HOCQUET

1

, Shaan CHAMARY

2

, Anne LERICHE

2

, Véronique LARDOT

1

, Francis CAMBIER

1

1BCRC, 4 Avenue Gouverneur Cornez, 7000 Mons, BELGIUM

2LMCPA, Boulevard Charles de Gaulle, 59600 Maubeuge, FRANCE

The bioactivity of synthetic bone implants is highly impacted by their surface topography, especially by the presence of micro-patterns likely to generate cells growth guidance. In this study, laser machining technology was employed in order to obtain controlled regular micro-patterns on dense calcium phosphate surfaces, without any contamination. In literature, this kind of laser patterningis usually performed on metallic alloys, but there are few works dealing with calcium phosphate ceramics because of unwanted phase transformations induced by the thermal impact of such a process. In our work, a femtosecond pulsed laser was used, in order to limit this thermal impact. Substrates with perfectly controlled micropatterning and without any secondary phase were obtained by optimization of the process parameters (laser power, scanning speed, pulse frequency). The microstructural characteristics were investigated by microscopy (optical, confocal, scanning electron) and the phase analyses were verified by XRD. This work allowed to highlight the effects of the process parameters on the patterning. The high benefits of the laser treatment on wettability was shown by contact angle assays.

Relationships between surface topography and wettability mechanisms were established thanks to a wide variety of micropatterned designs, allowed by the precision and the accurate control of the laser process. This technique seems to provide an interesting alternative to conventional surface treatments of calcium phosphates. In vitro experiments are currently being performed, to demonstrate the influence of the micro-patterns on cell behavior.

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CERAMIC IMPLANT MATERIALS: PREPARATION, STRUCTURE AND PROPERTIES

Katalin Balázsi, Csaba Balázsi

Centre for Energy Research, Hungarian Academy of Sciences, Konkoly-Thege M. str. 29-33, 1121 Budapest, Hungary, e-mail: balazsi. csaba@energia.mta.hu

There are more than 400 000 artificial hip joint operations made every year in the word and there are some 25 000 000 people who have either a partial or a total hip replacement. It has been estimated that the aged people population has increased tremendously in recent past and there will be seven times increase. Because the human body is at the same time both a very hostile and sensitive environment for foreign objects, the life span of a hip implant is limited. Whit time, the wear and risk of the implant loosening increases so that after 10 years 10-20% of the implants have to be renewed. The materials used for artificial implants by default are Titanium (TiAl6V4, Ti alloy), CoCrMo and ceramics. Despite application of different biocompatible materials the ultimate material with properties of native joints has not been found to date. Biomaterials used for implant should possess some important properties in order to long-term usage in the body without rejection. Materials used as different biomaterials should be made with certain properties as excelent biocompatibility, superior corrosion resistance in body environment, excellent combination of high strength and low modulus, high ductility and be without toxicity.

This new line research is focused to examination of ceramic based nanocomposites.

The three different types of bioceramics (TiC/a:C thin films, hydroxyapatite based coating on TiC/a:C thin film and hydroxyapatite composite) are developed from the same based material. The sputtered TiC/a:C thin films are developed as an optimal solution for protective applications. The formation of TiC based surface coating has a passivation effect to titanium implant and Ti ions will kept in the bulk implant introduced in the living organism. The nanosized hydroxyapatite coating on TiC thin films will help the quick and inflammation-free osiffication. The other main goal of this research is to develop a new type of coating onto medical implants, which simultaneously possesses antibacterial and biocompatible properties. Structure and other properties of bioimplants will be showed.

Keywords: hydroxyapatite, nanoceramics Acknowledgements:

This project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no 602398.

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Calcium-Magnesium Phospho-Silicate Bioceramic Cements for Dentistry and Orthopedics

Tom Troczynski

Materials Engineering, University of British Columbia, Vancouver B.C., Canada,

The novel Calcium Phosphate Silicate Cement (CPSC) combines the best biological and structural properties of Calcium Phosphate Cement (CPC) and of Calcium Silicate Cement (CSC). The resulting CPSC is relatively stronger than CPC and has extended and controlled degradability time range, as compared with CPC.

The current FDA-approved applications of CPSC include dental root sealers and root repair materials. The materials are distributed worldwide by Vancouver BC Canada company Innovative BioCeramix Inc (IBC), and through the associated network of distributors including Brasseler USA Inc. and Henry Schein Inc.

One area of active CPSC research for orthopedics concerns its setting time, as the currently known CPSC variants set within ~1 hr after water contact. There is a desire to shorten this time to < 10 min for certain dental and orthopaedic applications. One approach includes admixture of biocompatible/biodegradable and fast-setting Mg compounds to CPSC, rendering it now Calcium-Magnesium Phosphate Silicate Cement (CMPSC).

This work reviews our research progress on these novel, faster-setting bio-cements, including both CPSC, and the effects of Ca/Mg on the properties of CMPSC after hydration (setting) at 37ºC for various length of time, and its final properties (variation of pH, compressive and 3-point bending strength, in vitro bioactivity). The phase transformations in CMPSC during setting show that calcium hydroxide, produced during the hydration of calcium silicates, reacts with the phosphate additives to form hydroxyapatite. The in-situ formation of a nanocomposite from the hydroxyapatite and calcium silicate hydrates appears responsible for the significant enhancement in CMPSC strength, bioactivity, and biocompatibility, as compared to pure CSC.

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Biomimetic trends in modern bioceramics:

3D printing and hybrid composition

Annett Dorner-Reisel

University of Applied Sciences Schmalkalden, GERMANY

In nature, material grows drop by drop. The shape of bones, muscles and organs do not form in one step, like casting or forging. Natural soft and hard tissues grow layer by layer or segment by segment. The same is true for additive manufacturing.

The finally geometry is formed by a multitude of single layer sintered together. There is no material waste, but the option to print porous structures with much freedom of design. Fort that reason, additive manufacturing is very close to natural growing processes of tissue. It really is a biomimetic process. In the presentation, suitable additive manufacturing technologies for bioceramic are introduced.

The presentation mention recent advances in 3D printed bioceramic, i.e. for bone tissue engineering scaffolds along with current challenges and future perspectives.

Some of these inorganic scaffolds are biodegradable and have proven ideal for bone tissue engineering, sometimes even with site specific growth factor/drug delivery abilities. Other bioceramic parts should be implanted for longer time without strong degradation. The challenge here is the improvement of their low strength.

Here hybrid composition by i.e. incorporation of reinforcements are potential options.

Some aspects to improve fibre-matrix compatibility are introduced as well.

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A comparative study of chemically bonded calcium phosphate based bioceramics

Czechowska J., Zima A., Siek D., Ślósarczyk A.

AGH University of Science and Technology, Department of Ceramics and Refractories, 30 Mickiewicza Av. 30-059, Krakow, Poland, jczech@agh.edu.pl

The Calcium phosphate bone cements (CPCs) belong to the group of biocompatible chemically bonded materials with unique properties for bone regeneration applications. CPCs are produced using one or more calcium phosphates which upon mixing with liquid phase form pastes that are able to set and hardened in situ (Fig.1). As CPCs solid components hydroxyapatite (HA, Ca10(PO4)6(OH)2) and α-tricalcium phosphate (-TCP, -Ca3(PO4)2) are of particular interest.

Fig.1. Chemically bonded bioceramics a) injectable, b) non-injectable.

In our study chemically bonded bioceramics on the basis of -TCP, calcium sulphate, hydroxyapatite as well as chitosan and methylcellulose has been developed. The influence of CPCs initial composition on setting times (Gilmore Needles), phase composition (X-Ray Diffraction), microstructure (Scanning Electron Microscopy) and porosity (Mercury Intrusion Porosimetry) of the final cement bodies was investigated. Furthermore, cytocompatibility of the obtained biomaterials was tested using human bone-derived cells (hBDC).

It has been found that the composition of bone cements influenced both physicochemical and biological properties of biomaterials. The most promising results have been obtained in the case of CPCs consisting of -tricalcium phosphate. - TCP- based bioceramics exhibited appropriate physicochemical properties, excellent handling and good biocompatibility.

ID number/Numer identyfikacyjny: N-1

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Synthesis method affects the structure of bioactive glasses - FTIR, Raman, NMR and XPS investigation

Dziadek M.1, Zagrajczuk B.1, Jeleń P.1, Olejniczak Z.2, Cholewa-Kowalska K.1

1 AGH University of Science and Technology, Faculty of Material Science and Ceramics al. Mickiewicza 30, 30-059 Krakow

2 Institute of Nuclear Physics, Polish Academy of Sciences, Department of Magnetic Resonance Spectroscopy, 152 Radzikowskiego St., 31-342 Krakow, Poland

dziadek@agh.edu.pl

Wpływ sposobu otrzymywania bioszkieł na ich strukturę- analiza FTIR, Raman, NMR oraz XPS

Bioglasses are able to bond to bone through formation of carbonated hydroxyapatite in body fluids. Bioactivity is influenced by glass composition and structure but also by synthesis route: melt-quenching versus sol–gel. The recognition of the bioglass structure can allow one to determine the relationship between chemical composition, molecular structure and bioglass properties, i.e. dissolution rate, bioactivity and biological response. Therefore, the present work aims to prepare bioglasses with the same composition by the two methods and study its effect on glass structure.

The two most extensively studied bioglass systems: SiO2–CaO–Na2O–P2O5 (45S5 glass) and alkali-free SiO2–CaO–P2O5 (A2 glass) were obtained using low-temperature sol-gel technique and traditional melt-quenching method. The A2 and 45S5 gel-derived glasses were prepared in different media, namely alcohol-based and water-based system, respectively. The gel- derived and melt-derived glasses were milled and sieved to obtain the bioglass powders with particle size below 45 μm. The glasses were investigated in terms of their structure using X-ray diffraction, as well as FTIR, Raman, 29Si and 31P MAS–NMR and XPS spectroscopy.

Melt-quenched materials demonstrate amorphous glass structure, while gel-derived ones show the beginning of crystallisation of the following crystalline phases:

Na2Ca2Si3O9 (combeite), Na2Ca4(PO4)2SiO4(silicorhenanite) – 45S5 glass and Ca2SiO4, Ca5(PO4)3OH (hydroxyapatite) – A2 glass. Both 45S5_melt and 45S5_gel glasses mainly contain Q2 Si units, while A2 glasses vary in terms of silicon entities (Qn) as follows: A2_melt – Q2 (major) and Q3 (minor), A2_gel – Q3 (minor) and Q4 (major) units. This indicates that the polymerisation of the glass structure increases in the following order: 45S5_melt ≈ 45S5_gel < A2_melt A2_gel.

For both 45S5 glasses, Q2 Si units are associated with both Ca2+ and Na+ modifiers. NMR and Raman spectroscopy indicate the presence of both Q0 (major) and Q1 P (minor) entities and the absence of Si–O–P bonds in resulting glasses. This confirms that phosphorus acts as a glass network modifier rather than network former. The relative ratio of Q0/Q1 species depends on synthesis method and also chemical composition of the glass. These results clearly show that synthesis route affect the structure of bioactive glasses of both ternary and quaternary systems. Further investigations are needed to confirm real influence of the synthesis route on the glass dissolution and bioactivity.

This work was supported by the National Science Centre, Poland (2015/17/N/ST8/00226 and 2014/13/B/ST8/02973).

ID number/Numer identyfikacyjny: N-3

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CuO doped gel-derived bioglasses with potential osteogenic, angiogenic

and antibacterial properties

Dziadek M., Zagrajczuk B., Palczynski M., Rybczynski F., Cholewa-Kowalska K.

AGH University of Science and Technology, Faculty of Material Science and Ceramics al. Mickiewicza 30, 30-059 Kraków, dziadek@agh.edu.pl

Bioszkła pochodzenia żelowego modyfikowane CuO o potencjalnych właściwościach osteogennych, angiogennych

oraz antybakteryjnych

Bioactive glasses are recognized as one of the most important biomaterials due to their high biocompatibility, bone-bonding ability and also positive biological effects after implantation. However, for better regeneration of large bone defects, bioactive glasses should possess not only osteoconductivity but also the ability to stimulate both osteogenesis (for promoting new bone formation) and angiogenesis (for inducing vascularization). In addition, antibacterial activity to prevent postoperative bacterial infection is also desired. For these reasons, bioactive glasses are doped with different inorganic ions with known therapeutic action. In particular, Cu+2 ions can be considered as good candidates for the development of doped bioactive glasses due to their osteogenic, angiogenic and antibacterial characteristics.

The effect of CuO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Cu: (54-x)CaO–xCuO–6P2O5–40SiO2 and S2Cu: (16-x)CaO–xCuO–

4P2O5–80SiO2 (x=0, 1, 3 and 5) stabilized at 700°C on their structure and bioactive properties was investigated. The structure of resulting glasses was studied using FTIR spectroscopy and X- ray diffraction. Furthermore, bioactive properties of materials was assessed using SEM/EDX and FTIR methods after 7-day immersion in simulated body fluid (SBF).

The results show that the effect of copper substitution on the structure and crystallization ability of glass strongly depends on SiO2/CaO molar ratio in glass composition. XRD and FTIR studies indicate that gradual increase of CuO content in both A2 and S2 glasses results in the enhancement of crystallization process. The presence of 3–5 mol% of copper ions in calcium- rich glass (A2 group) leads to expansion and disruption of the silicon-oxygen network.

Whereas, the addition of Cu to the silica-rich glass (S2 group) does not significantly change the polymerisation of glass network. In vitro bioactivity test showed that with the increasing CuO content in both group of materials (A2 and S2) the apatite-forming ability remained at the same high level as for the unmodified A2 and S2 glasses.

This work was supported by the National Science Centre, Poland (2015/17/N/ST8/00226 and 2014/13/B/ST8/02973) and Polish Ministry for Science and Higher Education, AGH University of Science and Technology, Faculty of Materials Science and Ceramics (15.11.160.014).

ID number/Numer identyfikacyjny: N-3A

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Structural investigation on the gel-derived bioglasses from the

SiO

2

- CaO and the SiO

2

- CaO – P

2

O

5

systems

Zagrajczuk B.

1

, Dziadek M.

1

, Olejniczak Z.

2

, Cholewa-Kowalska K.

1

, Łączka M.

1

1 AGH University of Science and Technology, Faculty of Material Science and Ceramics al. Mickiewicza 30, 30-059 Krakow,

2 Institute of Nuclear Physics, Polish Academy of Sciences, Department of Magnetic Resonance Spectroscopy, 152 Radzikowskiego St., 31-342 Krakow, Poland

Gel derived glasses from the binary SiO2- CaO and ternary SiO2- CaO – P2O5 systems were obtained. Materials differed in the CaO/SiO2 molar ratio, which varied between 0.2 to 1.5. Starting materials in the sol-gel synthesis process were TEOS, TEP and calcium nitrate tetrahydrate. Materials were stabilized in 600°C (binary glasses) and 700 °C (ternary glasses). For all of the materials network connectivity parameter and optical basicity were calculated.

The XRD patterns were measured in order to investigate phase composition of obtained powders. Beginning of crystalization was observed as CaO content increased. There have been FTIR analysis performed in order to characterize the structure of materials. FTIR spectra showed changes in the materials structure depending on the CaO/SiO2 ratio. It has been proven that with increase of CaO/SiO2 ratio the number of bridging oxygens significantly decrease.

The local structure of silicon and phosphorus (ternary glass system) in obtained materials were examined with magic angle spinning nuclear resonance (MAS-NMR).

The 29Si MAS-NMR spectra revealed that silicon was present in Q2, Q3 and Q4 structural units. Moreover, 31P MAS-NMR indicated that phosphorus exist mainly as a monophosphate complex. It has been also shown that the presence of phosphorus in the structure induct the process of silica network repolimeryzation.

Bioactive properties of the powders were tested, through their immersion in simulated body fluid solution (SBF) for 7 days. Changes in the powders structure after incubation were characterized with FTIR spectroscopy and XRD analysis.

Considerable changes in the structure confirming, the appearance of apatite after immersion in SBF have been indicated.

This work was supported by the National Science Centre Poland Grant nos.

2014/13/B/ST8/02973.

ID number/Numer identyfikacyjny: N-4A

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Effect of the bioactive glass chemical composition on the bioactivity and degradation rate of polymer-

ceramics composites

Zagrajczuk B., Dziadek M., Cholewa-Kowlalska K., Łączka M.

AGH University of Science and Technology, Faculty of Material Science and Ceramics al. Mickiewicza 30, 30-059 Kraków,

Bioglasses are ceramics materials that are known for the ability of creation a strong bond with bone tissue. They can also significantly improve biological performance of materials. Incorporation of bioglass particle into polymer matrix enables to obtain composite materials with new deserved properties. The aim of this study was to describe the influence of the chemical composition of gel bioglasses on in vitro bioactivity and degradation of polymer-ceramics composite materials.

There were several gel-derived biogalsses from the SiO2-CaO and the SiO2-CaO- P2O5 system produced, differing in the molar ratio of CaO/SiO2. Bioglass powders were then incorporated into polymer (PLGA) matrix in order to obtain 2D composite films. In vitro bioactivity, described as the ability of forming apatite layer at the materials surface in contact with incubating solution, was examined in three different immersion solutions: simulated body fluid (SBF), phosphate-buffered saline (PBS) and cell culture medium. Changes in ions concentrations in immersion solutions were quantified with ICP. Degradation study was performed in PBS solution for 4 months.

SEM and EDX analysis confirmed presence of carbonate apatite on surfaces of all of the materials. Moreover, SEM analysis indicated differences in morphologies of apatite depending on the type of incubating solution and the chemical composition of materials. HCA layer formation was confirmed by FTIR spectroscopy. Changes in ions levels in immersion solutions depended on the glass compositions as well.

Degradation rate increased significantly after incorporation of bioglass particles into polymer matrix.

Our study confirmed that chemical composition of bioglasses affects the process of bioactivity as well as degradation rate of composite polymer-ceramics films. We proved that it is possible to modulate the chemical properties of this kind of composites dependoing on desires application.

This work was supported by the National Science Centre Poland Grant nos.

2014/13/B/ST8/02973 and by the Polish Ministry for Science and Higher Education, AGH University of Science and Technology, Faculty of Material Science and Ceramics Grant No. 11.11.160.365.

ID number/Numer identyfikacyjny: N-4

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Wpływ jonów antybakteryjnych na właściwości termiczne szkieł krzemianowo-fosforanowych

Wajda A., Sitarz M.

AGH Akademia Górniczo-Hutnicza, Wydział Inżynierii Materiałowej i Ceramiki, al. Mickiewicza 30, 30-059 Kraków

The influence of antibacterial ions on the thermal properties of silico-phosphate glasses

Celem badań jest otrzymanie szkieł krzemianowo-fosforanowych z układu NaCaPO4-SiO2 zawierających różne jony antybakteryjne oraz porównanie ich właściwości termicznych.

Szkła z badanego układu należą do jednych z bardziej atrakcyjnych biomateriałów ze względu na ich zdolność do tworzenia wiązania chemicznego z żywą tkanką poprzez wytwarzanie na ich powierzchni warstwy hydroksyapatytu w kontakcie z płynami fizjologicznymi. Podczas implantacji istniej ryzyko kolonizacji bakterii na powierzchni implantu, która może doprowadzić do infekcji w organizmie, a w rezultacie do zniszczenia lub odrzucenia implantu przez organizm. Zatem istnieje potrzeba opracowania bioaktywnych materiałów pozwalających zapobiegać wyżej wspomnianym infekcjom bakteryjnym. Bioaktywne szkła i materiały szkło-krystaliczne zawierające dodatek odpowiednich jonów antybakteryjnych mogą być drogą do rozwiązania tych problemów.

W niniejszej pracy porównano wpływ wybranych jonów bakteriobójczych (miedzi, cynku i ceru) na budowę strukturalną i właściwości termiczne likwacyjnych szkieł krzemianowo-fosforanowych.

ID number/Numer identyfikacyjny: N-64

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Charakterystyka szkieł pochodzenia żelowego z układu binarnego CaO-SiO

2

zawierających jony miedzi

Wajda A., Sitarz M.

AGH Akademia Górniczo-Hutnicza, Wydział Inżynierii Materiałowej i Ceramiki, al. Mickiewicza 30, 30-059 Kraków

Characterization of sol-gel derived glasses from binary system Ca-SiO

2

containing copper ions

Współczesne badania wykazują, że nie tylko szkła zawierające jony fosforu wykazują właściwości bioaktywne, ale także szkła z prostych układów binarnych (np. CaO-SiO2 oraz Na2O-SiO2), a nawet czysta krzemionka otrzymywane za pomocą syntezy zol-żel mogą również wykazywać te własności. Materiały te zyskują wyższą bioaktywność, ze względu na nanoporowatość i wynikające z tego rozwinięcie powierzchni. Jest to korzystne z punktu widzenia przerastania porowatego materiału tkankami - wiązanie biologiczne tkanki z implantem. Ponadto w strukturze takich szkieł obecna jest znaczna ilość grup OH-,a także jonów H+ odgrywających rolę modyfikatorów więźby szkła. Zwiększona liczba zerwanych mostków krzemo- tlenowych w szkłach otrzymywanych metodą zol-żel powoduje szybsze ich rozpuszczanie się, co znacząco przyspiesza powstawanie biomimetycznego HCA, a w konsekwencji zwiększa ich bioaktywność.

Celem badań była ocena własności szkieł z układu CaO-SiO2 domieszkowanych jonami miedzi otrzymanych za pomocą syntezy zol-żel. W tym celu wykonano badania spektroskopowe, termiczne oraz testy bioaktywności otrzymanych materiałów.

ID number/Numer identyfikacyjny: N-64A

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Processing and properties of Ca-TZP nanoceramics for biomedical applications

Łabuz A., Lach R., Wójtowicz B., Pyda W.

AGH Akademia Górniczo-Hutnicza, Wydział Inżynierii Materiałowej i Ceramiki, al. Mickiewicza 30, 30-059 Kraków

e-mail: alabuz@agh.edu.pl

Wytwarzanie i właściwości nanoceramiki Ca-TZP do zastosowań biomedycznych

Despite the excellent biocompatibility and great mechanical properties of 3Y-TZP ceramics, susceptibility to low temperature degradation which occurs in humid environment and involves the tetragonal to monoclinic transformation leading to microcracking and destruction of materials, pose a risk to medical applications.

Many efforts are carried out to manufacture tetragonal zirconia ceramics resistant to aging.

The present work reports a simple and efficient method for preparation of the calcia-zirconia nanopowder of a controlled chemical composition, which is sintered at low temperatures to fully-dense fully-tetragonal 4Ca-TZP ceramics with nanosized grains and improved aging resistance. Therefore, a physical mixture of zirconia gel and calcium hydroxide was a precursor of the partially calcium oxide stabilized zirconia nanopowder. The mixture was calcined at 500 ◦C for 1 h in air. The 4Ca-TZP sintered bodies with 100% of tetragonal symmetry, relative density above 99% and average grains size of 112.4nm were manufactured by pressureless sintering for 2 h at 1200 ◦C in air. The sintered material shows a bending strength and fracture toughness of about 730MPa and 14,5-20 MPa·m0,5, respectively. After a five-hour accelerated aging test in water vapour at 134°C, changes in phase composition and flexural strength were not observed in studied material. The 4Ca-TZP nanoceramics shows improved resistance to low-temperature degradation and may be used as a suitable replacement for Y-TZP in biomedical applications.

ID number/Numer identyfikacyjny: N-65

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21

REFERATY PLENARNE/PLENARY LECTURES

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22

Materials, Society, and Sustainable Development

Dr. Mrityunjay Singh

President, The American Ceramic Society Governor, Acta Materialia, Inc.

Chief Scientist, Ohio Aerospace Institute Cleveland, OH (USA)

The discovery of new and innovative materials has been known to culminate in major turning points in human history. The transformative impact and functional manifestation of new materials have been demonstrated in every historical era by their integration into new products, systems, assemblies, and devices. In modern times, the integration of new materials into usable products has a special relevance for the sustainable technological development and economic competitiveness. As increasing global population (over 9 billion inhabitants by 2040) drives to improve their standards of living, demand for energy, healthcare, housing, transportation, and industrial products also grows rapidly. However, the higher demand and production in all these areas leads to a dramatic increase in the overall consumption of resources and rate of pollution leading to climate change that creates the risk of irreversible changes in the ecosystem. Advances in new materials, technologies, and innovative solutions are required to address human and societal needs but their benefits in addressing various societal challenges have to be globally realized. This presentation will cover wide ranging topics and identify key challenges and opportunities for various technologies in sustainable societal development. The future energy and environment landscape could be dramatically impacted due to wide scale application of ceramics in all aspects of alternative and renewable energy production, storage, distribution, conservation, and efficiency. In addition, green and sustainable manufacturing approaches and their implementation challenges will also be discussed. Phyllosilicates revisited: from mixed suspension properties for advanced processing to nanocomposites

ID number/Numer identyfikacyjny: IL-1

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23

Slabs production and full digital decoration new plant proposals

Benedetto Spinelli

SACMI IMOLA s.c., Italy

In order to compete in the global market of ceramic tiles it is necessary to propose a wide range of products and different size and decoration possibilities.

In parallel it is also important to limit production costs.

Each new logic of production must foresee a high flexibility and to this purpose Sacmi proposes plant solutions based on the new available technologies.

One is surely represented by Digital Decoration, which allows easy realisation of a great number of products having excellent aesthetical quality with competitive costs.

A second opportunity is represented by plants for Large Sizes, which considerably simplify the production flow and allow to produce a great variety of modular sub- sizes.

Digital Decoration

The Digital Decoration has already widely established thanks to its unquestionable advantages, which hugely overcome the initial problems.

High graphic resolution, easy realization of prototypes and product changes, decoration without contact even on structured surfaces, little production lots, …., limited production costs.

So far the introduction of Digital Decoration occurred with two main aims:

- simplify the decoration lines and realise products of good quality with a lower number of applications

- implement the digital machines on the existing lines, by integrating traditional applications

On the contrary, the real revolution in glazing will be possible thanks to the introduction of full digital decoration, with effective reduction of lines length, greater automation, opportunity of connecting the effects deriving from both dry and wet decoration and easier running.

Therefore, the digital decoration aims at the application of traditional glazes and engobes but above all at the realisation of ceramic surfaces having new chromatic/optical (glossy/matt, iridescent effects, …) and tridimensional (relief structure) effects.

Lines for Large Sizes

Sacmi plant proposal, with the aim of achieving the highest production flexibility, is represented by recent introduction of lines for large size porcelain slabs.

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24 The advantages of a plant for large sizes are: easy running, higher quality of achievable products, possibility of producing modular sub-sizes by cutting without any die change, reduction of the number of stored finished products.

The most typical large size is 1200x1200 without doubt, which is multiple of standard 600 and 300-sizes.

The size 900x1800 is also interesting for exploiting the space between press columns.

Anyhow the large size par excellence is 3000x1500, with several combinations of interesting submultiples.

On the contrary, the production of only one size at kiln outlet hugely reduces warehouse cost (an intermediate warehouse is enough) but then the cutting costs are higher.

Sacmi proposals for the production of large sizes are:

- traditional line with PH10000 and fast die change, in case - Continua+

Traditional line with PH10000 and fast die change

It allows the realisation of 1200x1800-max. size and any thickness (3÷30 mm) with output up to 10.000 m2/day.

Continua+

It is the NEWEST compacting technology by roller from Sacmi, which allows to produce very large sizes (up to 1600x”unlimited”). It is suitable for thickness ranging from 3 to 20 mm, in function of which it is possible to achieve very high output (12.000 m2/day).

In particular, the new Continua+ technology shows a simple, linear and automated working flow and perfectly integrating with Digital Decoration technologies, such as Dry Digital Decoration, Digital Glazing and Inkjet Decoration.

As a consequence, Sacmi believes the production lines for Large Sizes integrated with digital technologies represent a valid solution for the development requests of the ceramic market because it deals with highly flexible solutions, able to realise products with high added value and with limited costs.

ID number/Numer identyfikacyjny: IL-2

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25

New Class of Refractory Ceramics for Thermal Barrier Coatings

Wei Pan

State Key Lab of New Ceramics and Fine Processing, School of materials science and engineering, Tsinghua University, Beijing, China

panw@mail.tsinghua.edu.cn

Increasing thermal efficiency and lower emissions require gas turbine designers to further increase the combustion temperature that leads to the high temperature components such as combustion chambers, blade and vanes surfaces face more rigorous conditions. Therefore, there is urgent demand to develop new ceramic coatings with even lower thermal conductivity, higher stability and durability than currently used thermal barrier coatings coating on the surface of high temperature alloy components.

In this presentation, we introduce the design and synthesis of new class of refractory ceramics as candidate materials for thermal barrier coatings. Evaluation method of thermal conductivity in porous oxides and non-constructive test of the growth of temperature generated oxides (TGO) at top-coating and bound coating interface will also to be introduced.

The current status of production and research on ceramics in China will also be introduced briefly.

ID number/Numer identyfikacyjny: IL-3

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26

Wzornictwo i technologia bolesławieckiej ceramiki od XVI do XX w.

Anna Bober-Tubaj

Muzeum Ceramiki w Bolesławcu, ul. Mickiewicza 13, 59-700 Bolesławiec

Design and technology of the ceramics of Bolesławiec from the 16th to 20th century

Bolesławieckie wyroby garncarskie od XVI wieku dzięki swoim walorom estetycznym i funkcjonalnym, a także stosunkowo niskim cenom, zdobywały sławę i uznanie. Początkowo w XVI - XVII w. garncarze wytwarzali głównie dzbany i butle zdobione technikami żłobkowania, radełkowania i plastycznymi nakładkami, a naczynia pokrywano brązowym szkliwem ziemnym, zielonym szkliwem ołowiowym bądź kobaltowym szkliwem skaleniowo-wapniowym. W XVIII w. wybór ceramicznych produktów został poszerzony o dzbanki do kawy i herbaty, mleczniki, puzdra, kałamarze, wazy i kufle. Naczynia te zdobione były bardzo charakterystycznymi białymi nakładkami, które nakładano na brązowe szkliwo ziemne. W XIX w. garncarz J.G. Altmann wprowadził delikatną masę kamionkową, szkliwo skaleniowe, a także dekorację o motywach antycznych. Przełomowe zmiany w historii bolesławieckiego garncarstwa nastąpiły dzięki działalności Zawodowej Szkoły Ceramicznej (Keramische Fachschule Bunzlau), otwartej w 1897 r. Zapoczątkowała ona zmiany w zakresie technologicznym. Pracę ręczną w garncarniach zastąpiono w dużym stopniu produkcją mechaniczną. Wprowadzono nowy, bardzo szeroki asortyment wyrobów oraz wiele nowych dekoracji: malatury podszkliwne i naszkliwne, szkliwa zaciekowe, krystaliczne, matowe, półmatowe, lustry, intarsje i emalie. Najbardziej rozpoznawalna bolesławiecka dekoracja wykonywana za pomocą stempelków pojawiła się pod koniec XIX w. i jest stosowana do dnia dzisiejszego. Współcześnie dzięki współpracy zakładów ceramicznych z wyższymi uczelniami produkowane wyroby utrzymywane są na wysokim poziomie artystycznym oraz technologicznym.

Słowa-klucze: ceramika bolesławiecka, J.G. Altmann, Zawodowa Szkoła Ceramiczna w Bolesławcu, dekoracja stempelkowa, techniki zdobienia ceramiki

Since the 16th century, pottery of Bolesławiec, thanks to its aesthetic and functional advantages, as well as relatively low prices, has become more and more popular and recognized. In the beginning, between the 16th and 17th century, potters were mostly producing jugs and demijohns decorated with the use of fluting, knurling, and plastic covers, and the vessels were covered with brown clay glaze, green lead glaze or cobalt feldspar-calcium glaze. In the 18th century, the choice of ceramic products was expanded by coffee and tea pots, milk pots, boxes, inkwells, tureens and mugs. These vessels were decorated with very characteristic white

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27 covers, placed on brown clay glaze. In the 19th century, the potter J.G. Altmann introduced a delicate vitrified clay, feldspar glaze and decorations with antique motifs. The crucial changes in the history of pottery of Bolesławiec took place thanks to the operations of Zawodowa Szkoła Ceramiczna (Keramische Fachschule Bunzlau) opened in 1897. It initiated the changes in the technological scope. Manual work was, to a large degree, replaced by mechanical work. A new, very broad assortment of products and numerous new decorations were introduced: sub-glaze and on-glaze paint layers, drip glaze, crystal, matt, half-matt, lusterware, marquetry and enamel. The most popular decoration of Bolesławiec, performed with the use of stamps, appeared in the end of the 19th century and is used until now. Currently, thanks to the cooperation of the ceramic plants with universities, produced goods maintain the high artistic and technological level.

Keywords: ceramics of Bolesławiec, J.G. Altmann, Zawodowa Szkoła Ceramiczna w Bolesławcu (Ceramic Vocational School of Bolesławiec), stamp decoration, ceramics decoration techniques

ID number/Numer identyfikacyjny: IL-4

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28

Chemia koloidów w otrzymywaniu

zaawansowanych materiałów ceramicznych i kompozytów

Mikołaj Szafran

Politechnika Warszawska, Wydział Chemiczny, Katedra Technologii Chemicznej, ul. Noakowskiego 3, 00-664 Warszawa

Colloidal chemistry in processing of advanced ceramics and composites

W referacie przedstawione zostaną badania nad zastosowaniem chemii koloidów w otrzymywaniu zawiesin proszków o rozmiarach nano- submikro- i mikrometrycznych do otrzymywania zaawansowanych tworzyw ceramicznych i kompozytów.

Właściwości takich zawiesin modyfikowane są przez dodatek odpowiednio dobranych substancji organicznych i polimerowych. Substancje te mogą spełniać rolę deflokulantów, spoiw, monomerów, substancji modyfikujących zwilżalność proszku ceramicznego, napięcie powierzchniowe, itp. Przedstawione zostaną badania nad zastosowaniem nowych wodorozcieńczalnych spoiw polimerowych o odpowiednich właściwościach amfifilowych w zastosowaniu do otrzymania kompozytów ceramika-polimer a także nowych wodorozpuszczalnych monomerów opartych na pochodnych sacharydów do modyfikacji właściwości reologicznych cieczy zagęszczanych ścinaniem. Tego typu monomery, w układach koloidalnych opartych na proszkach ceramicznych o wymiarach nanometrycznych i submikrometrycznych mogą spełniać jednocześnie funkcję spoiwa (po procesie ich polimeryzacji w ceramicznej masie lejnej), upłynniacza a także nie wymagają dodatku tzw. środa sieciującego. Możliwe jest to, dlatego, iż monomery takie zawierają kilka grup wodorotlenowych, co umożliwia ich wewnętrzne sieciowanie za pomocą wiązań wodorowych.

Zagadnienia te zostaną omówione na przykładzie układów koloidalnych projektowanych do otrzymywania materiałów do absorpcji energii, ferroelektrycznych kompozytów ceramika-polimer projektowanych dla potrzeb elektronicznych układów pracujących w zakresie częstotliwości sub-THz oraz porowatych tworzyw kompozytowych przeznaczonych do usuwania wirusów z wody.

Praca finansowana przez Politechnikę Warszawską

ID number/Numer identyfikacyjny: IL-5

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29

Funkcjonowanie Centrum Badawczo-Rozwojowego w zakładzie produkcyjnym na przykładzie

Zakładów Magnezytowych „ROPCZYCE” S.A.

Artur Bradecki, Józef Siwiec, Marian Darłak, Wiesław Zelik

Zakłady Magnezytowe „ROPCZYCE” S.A.

Activity of the Research and Development Center in the manufacturing plant, on example

ZAKŁADÓW MAGNEZYTOWYCH ROPCZYCE S.A.

Zakłady Magnezytowe "ROPCZYCE" S.A. są uznanym światowym producentem materiałów ogniotrwałych.

Spółka posiada 40 letnie doświadczenie w projektowaniu i produkcji wymurówek ogniotrwałych dla urządzeń cieplnych w przemysłach: stalowym, cementowym, wapienniczym, metali nieżelaznych, odlewniczym, szklarskim, koksowniczym i innych.

Kontynuacja sukcesu Spółki, rozumiana jako zapewnienie pozycji rynkowej i bezpieczeństwa finansowego, wymaga ciągłego rozwoju i dywersyfikacji oferty zarówno w zakresie nowych rozwiązań materiałowo-konstrukcyjnych jak i pozyskiwania nowych rynków w sensie zarówno branżowym jak i geograficznym.

Realizacja tych zadań w firmie produkcyjnej wymaga sprawnej organizacji, zdolnej do koordynacji działań w zakresie znajomości rynku, szybkości reakcji na potrzeby klienta, innowacyjności produktowej zgodnie z potrzebami rynku oraz efektywnym zarządzaniem produkcją. W celu realizacji powyższych zadań w Zakładach Magnezytowych "ROPCZYCE" S.A. z dniem 1 stycznia 2013 roku utworzone zostało Centrum Badawczo-Rozwojowe Materiałów Ceramicznych.

Własne Centrum Badawczo-Rozwojowe zapewnia rozwój technologiczny i techniczny Spółki, pozwala na dostosowanie oferty produktowej do aktualnych wymagań rynkowych, przy zapewnieniu wymaganego poziomu jakości i kosztów produkcji wyrobów.

Zadania Centrum B+R w Zakładach Magnezytowych „ROPCZYCE” S.A. są poszerzone w stosunku do zadań klasycznych centrów badawczych.

W celu realizacji zadań postawionych przed Centrum, jego zakres funkcjonowania musi uwzględniać bardzo dobrą znajomość rynku i współpracę z nim, znajomość procesów przemysłowych oraz nadzór nad całym cyklem życia wyrobów od produkcji, poprzez monitorowanie pracy wyrobów u klienta, aż do badania wyrobów po pracy.

W referacie szczegółowo przedstawiono i omówiono organizację Centrum Badawczo-Rozwojowego w Zakładach Magnezytowych „ROPCZYCE” S.A.

z uwzględnieniem dostosowania organizacji i zadań Centrum do specyfiki zakładu produkcyjnego.

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30 Zaprezentowano potencjał Centrum B+R w zakresie badań laboratoryjnych, modelowych, półprzemysłowych oraz związanych z monitorowaniem procesów produkcyjnych.

Przedstawiono nakłady na działalność rozwojową, wskaźnik innowacyjności oraz omówiono efekty projektów zrealizowanych przy wykorzystaniu europejskich funduszy strukturalnych.

Zakłady Magnezytowe (Magnesite Works)"ROPCZYCE" S.A. is recognized global producer of refractory materials.

The company has 40 years of experience in the design and manufacture of refractory linings for the high temperature vessels in the various industries like steel industry, cement, lime, non-ferrous metals, foundry, glass, coke and others.

Continuation of the Company's success, understood as maintaining market position and financial security requires continuous development and diversification of the offer, in terms of new material and design solutions as well as development of new markets both in terms of new industry application as well as new clients worldwide.

The implementation of those goals in a manufacturing company requires efficient organization capable of coordinating activities in the field of knowledge of the market, responsiveness to customer needs, product innovation according to market needs and efficient production management. In order to accomplish these tasks in Zakłady Magnezytowe "ROPCZYCE" S.A. on 1st January 2013 was established Research and Development Center of Ceramic Materials.

Own Research and Development Centre provides technical and technological development of the Company, allows to customize the products offer to current market requirements, while ensuring the required level of quality and cost of production.

Tasks of R & D Center in Zakłady Magnezytowe "ROPCZYCE" S.A. are broadened in relation to the tasks of classical research centers.

To fill all of its tasks, the R&D Center must combine a broad knowledge of the market and cooperation with clients, knowledge of industrial processes and oversight of the entire lifecycle of products from production through monitoring the products work at the clients’ site, to the study of the material after work.

In the paper the organization of Research and Development Center in Zakłady Magnezytowe "ROPCZYCE" SA is presented including the adjustment of the organization and tasks of the Centre to the needs of production plant.

The capability of the R&D Centre in the fields of conducting laboratory and semi- industrial tests and monitor production processes was presented in the paper. It shows expenditures on development, the rate of innovation and discusses the effects of the projects implemented with the use of European Structural Funds.

ID number/Numer identyfikacyjny: IL-7

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31

A review on the steric stabilization of aqueous ceramic based dispersions by anion and cation

type comb copolymers

Thomas Graule

1

, Vaidas Klimkevicius

1,2

and Ricardas Makuska

2

1 Empa, Swiss Laboratories for Materials Science and Technology, Laboratory for High Performance Ceramics, Überlandstrasse 129, CH-8600 Dübendorf; thomas.graule@empa.ch,

2 Vilnius University, Department of Polymer Chemistry, Naugarduko 24, LT-03225, Vilnius, Lithuania

The efficient stabilisation of ceramic based nanopowders is a prerequisite for the achievement of highly reliable ceramic materials. Agglomeration or re- agglomeration due to Van der Waals forces can be avoided using different concepts to increase the separation barrier by electrostatic or steric means. Recently we performed detailed studies applying anion and cation type copolymers for the surface modification and stabilisation of alumina and zirconia submicron and nanoparticles. The studies were performed in order to develop a basic understanding of the mechanism of steric stabilisation in aqueous media [1-5]. After giving an extensive review on the aspects of steric stabilisation we present here new concepts to apply cationic comb copolymers as a promising alternative in case of the stabilisation of titania and silica. The effectiveness of the anionic and cationic dispersants is evaluated on the basis of adsorption, zeta potential measurements, rheology and particle size measurements [6-7].

[1] Y. De Hazan, T. Reuter, D.Werner, R.Clasen, T. Graule, Interaction and dispersion stability of aluminium oxide colloid particles in electroless nickel coatings, J.Colloid Interf.Sci., 323 (2008) 293–300.

[2] Y. De Hazan, J.Heinecke, A.Weber, T.Graule, High Solids Loading Ceramic colloidal Dispersions in UV Curable Media via Comb polyelectrolyte Surfactans, J.Colloid Interf.Sci. 337 (2009) 66–74.

[3] M.Wozniak, Y. de Hazan, T.Graule, D.Kata, Rheology of UV curable colloidal silica dispersions for rapid prototyping applications, J.Eur.Cer.Soc. 2011, 31, 2221-2229.

[4] Y. de Hazan, V.Märkl, J.Heinecke, C.Aneziris, T.Graule, Functional ceramic and nanocomposite fibers, cellular articles and microspheres via radiation curable colloidal dispersions, J.Eur.Cer.Soc. 2011, 31, 2601-2600.

[5] Y. de Hazan, Wilkens-Heinecke,J.;Graule,T., Modeling the effect of molecular architecture of comb polymers on the behavior of Al2O3 dispersions using charge/composition factors (CCF), Colloid Polymer.

Sci. 2014, 292, 7, 1701-1710.

[6] V. Klimkevicius, T.Graule, R.Makuska, Effect of structure of cationic comb copolymers on their adsorption and stabilization of titania nanoparticles, Langmuir 2015, 31, 2074-2083.

[7] V. Klimkevicius, R.Makuska, T.Graule, Rheology of Titania Based Ceramic Nanodispersions Stabilized by Cationic Comb Copolymers; Applied Rheology, accepted January 2016

ID number/Numer identyfikacyjny: IL-8

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32

SESJA A

SUROWCE I PÓŁPRODUKTY CERAMICZNE

CERAMIC RAW MATERIALS AND POWDERS

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33

Opoczyńskie iły kaolinitowe wczoraj i dziś

Piotr Wyszomirski

AGH Akademia Górniczo-Hutnicza, Wydział Inżynierii Materiałowej i Ceramiki, al. Mickiewicza 30, 30-059 Kraków

Państwowa Wyższa Szkoła Zawodowa, 33-100 Tarnów, ul. Mickiewicza 8

The kaolinitic clays of the Opoczno region – the past and presents

Zainteresowanie lokalnymi surowcami ilastymi w rejonie Opoczna wiąże się z powstaniem z końcem XIX wieku dwóch fabryk ceramicznych, w których później zaczęto produkować płytki ceramiczne oraz szamotowe wyroby ogniotrwałe. W związku z tym w różnych okresach ubiegłego wieku wydobywano zróżnicowanej jakości iły ceramiczne, zarówno ogniotrwałe jak i nieogniotrwałe, w kopalniach Żarnów, Paszkowice, Rozwady, Mroczków, Jakubów i Zapniów. Ze względu na wyczerpanie zasobów i/lub pogorszenie jakości kopaliny eksploatacja ta została jednak zaniechana. W latach sześćdziesiątych i siedemdziesiątych ubiegłego wieku udokumentowano też dla potrzeb przemysłu szamotowych materiałów ogniotrwałych liczne złoża kopalin ilastych, m.in. w Borkowicach k. Przysuchy.

Eksploatacja tego złoża nie została jednak podjęta ze względu na zmniejszające się wówczas zainteresowanie wyrobami szamotowymi oraz likwidację w roku 1991 Opoczyńskich Zakładów Materiałów Ogniotrwałych. Początek wydobycia iłów ze złoża Borkowice nastąpił dopiero w roku 2013 dzięki inicjatywie firmy WIS-Group sp. Z o.o. z Opoczna.

W złożu Borkowice występuje głównie jasna i szara odmiana kopaliny ilastej, a także piaskowiec, który stanowi w nich przerosty. W jasnej odmianie iłu dominuje kaolinit zaś podrzędnymi składnikami są: illit i kwarc. Odmiana ta wyróżnia się małą zawartością tlenków barwiących (Fe2O3 = 0,87% mas., TiO2 = 1,15% mas.). Powoduje to, że jest też ona jasna po wypaleniu stanowiąc pełnowartościowy substytut surowców ilastych importowanych w ostatnich kilkunastu latach w dużej ilości z Ukrainy. W szarej odmianie iłu kaolinitowi towarzyszy większa ilość kwarcu, co znajduje odzwierciedlenie w składzie chemicznym i podwyższonej zawartości SiO2. Korzystny skład mineralny i chemiczny, zwłaszcza jasnej odmiany iłu z Borkowic rzutuje na jego przydatność do produkcji płytek ceramicznych stanowiąc cenne uzupełnienie szczuplej, krajowej bazy iłów biało- i jasnowypalających się.

Słowa kluczowe: ił kaolinitowy, glinki opoczyńskie, szamotowe wyroby ogniotrwałe, Borkowice, płytki ceramiczne

ID number/Numer identyfikacyjny: KL-1

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34

Development of stable clay mixtures for a long term supply of the Polish tile industry

Ralf Diedel

Stephan Schmidt KG, Bahnhofstraße 92, D- 65599 Dornburg / Langendernbach ralf.diedel@schmidt-tone.de

Triggered by new production technologies and consumer requirements as large- sized wall and floor tiles also the raw material suppliers are forced to develop new mixtures as well as technical solutions and logistic support. For example, only for the tile market more than 600.000 tpy are delivered by the Stephan Schmidt Group (SSKG).

The production of such large-sized tiles demands special requirements on dry bending strength, sintering behavior and resistance against hygroexpansivity and curvature. These requirements must be traced back to mineralogical, physical and chemical properties of the raw materials used, combined with the definition of lower and upper specification limits.

Essential fundamentals for the development of reproducible solutions are the availability and combination of technical equipment for extrusion and casting with reliable characterization methods. Exemplary it is important for pressed tiles that not only the mineralogy has to be controlled to guarantee the required plasticity, but also the rheology of the slip to produce spray dried granules within a defined range of plasticity.

Finally, it will be shown how a long term supply may be guaranteed based on the amount of open pits, the variety of clays, the technology for processing and blending different clays and the support of quality assurance and R&D projects.

ID number/Numer identyfikacyjny: KL-2

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35

Opracowanie technologii wytwarzania rdzeni ceramicznych do łopatek silnika GP7000

Gromada M., Świeca A.

Instytut Energetyki, Oddział Ceramiki CEREL, Instytut Badawczy, ul. Techniczna 1, 36-040 Boguchwała, gromada@cerel.pl

Development of the manufacturing technology of ceramic cores for GP7000 vanes engine

Opracowano technologię wytwarzania rdzeni ceramicznych metodą wtrysku wysokociśnieniowego, która umożliwia formowanie długich rdzeni o bardzo skomplikowanych kształtach i zmiennych przekrojach oraz wysokiej dokładności wymiarowej. Dobrano skład surowcowy tworzywa oraz termoplastyfikator, co pozwoliło na uzyskanie wysokiej wytrzymałości mechanicznej uformowanych i wypalonych rdzeni. Dokonano optymalizacji procesu technologicznego na wszystkich etapach wytwarzania rdzeni odlewniczych. Dobrano optymalne parametry urabiania masy wtryskowej i formowania próbnych rdzeni. Opracowano krzywe temperaturowe w procesie usuwania lepiszcza i wypalania końcowego w celu zapewnienia wymaganej wytrzymałości mechanicznej i jakości rdzeni odlewniczych oraz sprawdzono możliwość roztwarzania tworzywa w wodnych roztworach zasad.

Otrzymane tworzywo pozwoliło na uformowanie długich rdzeni o zmiennych przekrojach oraz cechowało się niską skurczliwością i pomijalną deformacją kształtu podczas formowania i spiekania a także stosunkowo małym współczynnikiem rozszerzalności cieplnej i niską chropowatością powierzchni. Uzyskana wytrzymałość mechaniczna umożliwia montaż rdzeni w formach odlewniczych a odpowiednia porowatość rdzeni pozwala na łatwe ich roztwarzanie. Otrzymane wyniki badań wskazują na uzyskanie tworzywa do wtrysku wysokociśnieniowego o odpowiednich właściwościach do zastosowania na rdzenie do segmentów aparatu kierującego turbiny niskiego ciśnienia silnika odrzutowego GP7000.

Projekt współfinansowany przez Unię Europejską w ramach Europejskiego Funduszu Rozwoju Regionalnego oraz Narodowe Centrum Badań i Rozwoju – Nr umowy INNOLOT/I/8/NCBR/2013 (2013-2018) - INNOCAST.

ID number/Numer identyfikacyjny: A-28

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Zastosowanie analizy wydzielanego gazu EGA w badaniach surowców do produkcji

ceramicznych materiałów budowlanych metodą analizy termicznej STA

Murzyn P.

AGH Akademia Górniczo-Hutnicza, Wydział Inżynierii Materiałowej i Ceramiki, al. Mickiewicza 30, 30-059 Kraków, murzyn@agh.edu.pl

The use of evolved gas analysis EGA in research of the raw materials for ceramic building materials by thermal analysis STA

The paper shows the results of measurements of different natural and waste raw materials used in ceramic industry by thermal analysis (DTA/TGA) simultaneously with analysis of evolved gaseous products. The survey confirms the usefulness of the traditional thermal methods in research of clayey raw materials in terms of their qualitative and quantitative analysis. One of the characteristics of this method that impede the interpretation is that the shape of the thermal curves is the sum of all processes and reactions ongoing while heating of the multicomponent sample. An example of such a coincidence of the processes in clayey raw materials and ceramic masses is ongoing in the same temperature range simultaneously exothermic process which is burning of organic matter and endothermic process which is dehydroxylation. The simultaneous processes can be identified and analyzed separately by using Evolved Gas Analysis (EGA) simultaneously with STA analysis. The EGA method can be carried out using mass spectrometer that can analyze the volatile phases evolved from the sample while heating by their mass to charge ratio m/z. Using this method primarily the kind of gaseous product can be identified, the temperature range of its release and the quantity by the TG signal, this is also important for monitoring gas emissions by the industrial furnace installation.

The article presents measurement results of some natural raw materials containing inter alia a mixture of clayey minerals, organic matter, carbonates and also industrial waste materials rich in organic matter and other constituents causing emission of gaseous products while heating.

ID number/Numer identyfikacyjny: A-34

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