Maris Rundans

Sintered porous mullite-alumina ceramics are obtained from the concentrated suspension of powdered raw materials such as kaolin, gamma and alpha Al₂O₃, and amorphous SiO₂, mainly by a solid-state reaction with the presence of a liquid phase. The modification of mullite ceramic is achieved by the use of micro- and nanosize TiO₂ powders. The phase compositions were measured using an X-ray powder diffraction (XRD) Rigaku Ultima+ (Tokyo, Japan) and microstructures of the sintered specimens were analysed using scanning electron microscopy (SEM) Hitachi TM3000-TableTop (Tokyo, Japan). The shrinkage, bulk density, apparent porosity, and water uptake of the specimens was determined after firing using Archimedes’ principle. The apparent porosity of the modified mullite ceramic is 52–69 ± 1%, water uptake is 33–40 ± 1%, pore size distributions are 0.05–0.8 μm, 0.8–10 μm and 10–1000 μm, and bulk density are variated from 1.15 ± 0.05 to 1.4 ± 0.05 g/cm³. The microsize TiO₂ and nanosize TiO₂ speed up the mullitisation process and allow the decrease in the quantity used as raw material amorphous SiO₂, which was the purpose of the study. The use of nanosize TiO₂ additive increases the porosity of such a ceramic, decreasing the bulk density and linear thermal expansion.

Alkaline and alkaline-thermal activation were used in an attempt to synthesize zeolites using the sedimented illite fraction of raw Devonian clays from the Kuprava clay pit in Latvia. The Si/Al molar ratio of these clays is 2.79. Thermal and hydrothermal treatments were conducted using 6M and 10M NaOH solutions, along with different curing environments. The treated samples were analyzed using XRD, FTIR, and SEM, and were compared to the raw and calcined illite fraction samples. The main phase that forms after alkaline treatment is hydrosodalite (Na8[AlSiO₄]₆(OH)₂∙2H₂O). Using a higher concentration of NaOH leads to a significant increase in hydrosodalite formation. Increasing the curing temperature from 120°C to 600°C slightly reduces hydrosodalite formation due to the crystallization of the nepheline (Na₃K(Al₄Si₄O₁₆)) phase. This phase forms relatively intensively when the chemically treated samples are cured in a nitrogen environment at 600°C, thereby reducing the formation of hydrosodalite. The characteristic layered-fused structure of clay minerals remains in all chemically treated samples when cured at 600°C in air, but it does not remain when cured at the same temperature in nitrogen. The intensive formation of hydrosodalite is mainly achieved through hydrothermal treatment, along with a primary treatment using 10M NaOH. Considering the calculated size of the crystallites, treatment with 6M NaOH and curing at 120°C can also be seen as beneficial for hydrosodalite formation.

Mullite and mullite–alumina ceramics materials with dominance of the mullite phase are used in different areas of technology and materials science. Porous mullite ceramics materials can be used simultaneously as refractory heat insulators and also as materials for constructional elements. The purpose of this work was to investigate the WO₃ nanoparticle influence on the evolution of the aluminum tungstate and zircon crystalline phases in mullite ceramics due to stabilization effects caused by different microsize ZrO₂ and WO₃. The use of nano-WO₃ prevented the dissociation of zircon in the ceramic samples with magnesia-stabilized zirconia (MSZ), increased porosity by approximately 60 ± 1%, increased the intensity of the aluminum tungstate phase, decreased bulk density by approximately 1.32 ± 0.01 g/cm³, and increased thermal shock resistance by ensuring a loss of less than 5% of the elastic modulus after 10 cycles of thermal shock.

Rigid polyurethane (PUR) foams have outstanding properties, and some of them are successfully used even today as cryogenic insulation. The fourth-generation blowing agent Solstice^® LBA and commercial polyols were used for the production of a low-density cryogenic PUR foam composition. A lab-scale pouring method for PUR foam preparation and up-scaling of the processes using an industrial spraying machine are described in this article. For the determination of the foam properties at cryogenic temperature, original methods, devices, and appliances were used. The properties at room and cryogenic temperatures of the developed PUR foams using a low-toxicity, bismuth-based, and low-emission amine catalyst were compared with a reference foam with a conventional tin-based additive amine catalyst. It was found that the values of important cryogenic characteristics such as adhesion strength after cryoshock and the safety coefficient of the PUR foams formed with new reactive-type amine-based catalysts and with the blowing agent Solstice^® LBA were higher than those of the foam with conventional catalysts.

Mullite ceramics are well known as materials with a high temperature stability, strength and creep resistance. In this research, the effect of a modification with magnesia-stabilized zirconia and yttria-stabilized zirconia, separately, as well as in a mixture with WO₃, in 1:1 and 1:2 ratios on the thermal properties of porous mullite ceramics was investigated. The porous mullite-containing ceramics were prepared by a slip casting of the concentrated slurry of raw materials with the addition of a suspension of Al paste for the pore formation due to the H₂ evolution as a result of the reaction of Al with water. The formed samples were sintered at 1600 °C and the holding time was 1 h. The materials were characterized using X-ray diffractometry, scanning electron microscopy, mercury porosimetry, the laser flash contactless method, thermal shock resistance testing and the non-destructive impulse excitation method for determining the elasticity modulus. The modification of the porous mullite ceramic with a mixture of ZrO₂ and WO₃ oxides had a positive effect by decreasing the thermal conductivity, due to the increased porosity, in comparison to the undoped samples and samples with only ZrO₂. The doubling of the WO₃ amount in the modifying oxide mixtures improved the ceramic thermal shock resistance. The porous mullite ceramics which were modified with magnesia-stabilized zirconia (2.8 mol% MgO) and WO₃ had a lower thermal conductivity and improved thermal shock resistance than the samples with yttria-stabilized zirconia (8 mol% Y₂O₃) and WO₃.

Darbs veltīts poras saturošas kordierīta keramikas izstrādes pētījumam, kā poru veidotājus izmantojot viegli kūstošus divu veidu illītu mālus. Darbā ir klasiskās zinātniskā darba daļas – ievads, literatūras apskats, materiālu un metožu apraksts, rezultātu izklāsts, kā arī secinājumi. Darba teorētiskajā daļa aprakstīts kordierīts kā svarīga minerālā fāze, tās polimorfisms, kā arī no šīs fāzes veidotas keramikas iegūšana, īpašības un lietojums. Materiālu un metožu daļā detalizēti aprakstīti darbā izmantotie materiāli un metodes. Darba praktiskajā daļā aprakstīta kordierīta keramikas iegūšana un tās fizikāli mehāniskās un termiskās īpašības, kā arī veikta iegūto materiālu struktūras analīze. Parādīts, ka, variējot sintēzes tehnoloģiskos parametrus, iegūstama dažādas morfoloģijas poraina kordierīta keramika. Iegūtie materiāli vērtējami kā ekonomiski izdevīgāka alternatīva jau esošajiem sintētiskajiem materiāliem, turklāt – ar uzlabotām materiāla īpašībām: lieces un spiedes stiprību, termiskās izplešanās koeficientu un termisko vadītspēju.

This work is dedicated to the study of the development of porous cordierite ceramics using two types of illite clays as pore formers. The work has the structure of a classical scientific paper containing the following sections – introduction, literature review, description of materials and methods, presentation of results, and conclusions. The theoretical part of the Thesis describes cordierite as an important mineral phase, its polymorphism, as well as the production, properties and application of ceramics formed from this phase. The materials and methods section details the materials and methods used in the work. The practical part of the Thesis describes the production of cordierite ceramics and its physical-mechanical and thermal properties as well as the analysis of the structure of the obtained materials. It shows that by varying the technological parameters of synthesis different morphology porous cordierite ceramics can be obtained. The resulting materials are considered to be the most economically viable alternative to existing synthetic materials due to their improved material properties – bending and compression strength, thermal expansion coefficient and thermal conductivity.

Darbā dots ieskats par iespējām izmantot Latvijas minerālās izejvielas kā bāzi vai piedevu keramikas materiālu (eko-materiālu) izstrādei ar dažādu pielietošanas aspektu, to skaitā parādīt iespēju šo materiālu ieguves tehnoloģisko procesu optimizēšanai virzībā uz to apdedzināšanas temperatūras samazināšanu, līdz ar to reducējot kaitīgu gāzveida izmešu nonākšanu vidē. Parādīti darbu rezultāti laika periodā no 2007. g. līdz 2017. g. Tiek apskatīti un analizēti sekojoši pētījumi:neapstrādāta māla pielietošana atkritumu deponēšanas vietu noblīvēšanai;daļēji dehidratizēta māla pielietošana Cr3+, Cr6+, Zn2+ un Cu+ jonu sorbcijai, kas veidojas galvanisko procesu notekūdeņos; poru saturošas augsttemperatūras keramikas izstrāde no jauktiem izejvielu maisījumiem, kas nodrošina pietiekamu gāzveida fāzes izveidošanos keramikas apdedzināšanas procesā, veidojot poras, lai pielietotu par filtrēšanas/attīrīšanas materiālu;illīta māla piedevu izmantošana, lai pazeminātu augsttemperatūras blīvas keramikas saķepināšanas/apdedzināšanas temperatūru, iegūstot ilgspējīgu mehāniski un termiski izturīgu produktu; kā arī tehnoloģiskie procesi, kas nodrošina porainas, siltumu izolējošas keramikas materiāla ieguvi pie pazeminātām temperatūrām (ģeopolimēru metode).Mineral Raw Materials of Latvia for Development of Eco-CeramicsThe paper gives an insight into the possibilities to use Latvian mineral raw materials as a base or additives for the development of ceramic materials (eco- materials) with different application aspects, including showing the possibility of optimizing the technological processes of these materials towards the reduction of their firing temperature, thereby reducing the release of harmful gaseous effluents into the environment.The results of the works that are reported in the period were obtained from 2007 to 2017. The following studies are reviewed and analyzed: the use of untreated clay for the sealing of waste deposits; the use of partly dehydrated clay for sorption of Cr3+,6+, Zn2+ and Cu2+, which have formed in galvanic processes; the development of porous high temperature ceramics from mixes of mineral raw materials and synthetic additives that provide a sufficient gas phase formation in the firing process and consecutively to form pores in obtained ceramic material; the use of illite clay additives to reduce the temperature of sintering of high temperature dense mechanical and thermally durable ceramics, as well as technological processes that ensure the production of porous, heat-insulating ceramic materials at reduced temperatures (geopolymer method).

Parādīta piedevu (mālu minerāla – illīta, Si₃N₄, SiAlON), kā arī izejas pulveru izstrādes veida ietekme uz mullīta-ZrO₂ keramikas saķepināšanas procesu (pielietojot tradicionālo saķepināšanas procesu un plazmas izlādes saķepināšanas procesu jeb SPS), fāžu sastāvu, struktūru, mehāniskajām un keramiskajām īpašībām. Mālu piedeva sekmē pulvera daļiņu izmēru samazināšanos, veicina keramikas paraugu sablīvēšanos tradicionālā saķepināšanas procesā, bet dod pretēju efektu, pielietojot SPS procesu. Silīcija nitrīda un SiAlON nanopulveru piedevas ir efektīvas SPS procesā, sasniegta paraugu spiedes izturība ap 600 MPa Si3N4 piedevas gadījumā, termiskā trieciena izturību un elastības moduļa vērtības 180 – 220 GPa, kuras termiskā trieciena 1000/20 °C rezultātā samazinās pieļaujamās robežās. Šīs vērtības ir par aptuveni 20–25 % zemākas, pielietojot SiAlON piedevu. Keramikas paraugu, kas saķepināti tradicionāli un pielietojot SPS procesu, mikrostruktūrā ir mullīta vai pseidomullīta kristāliski veidojumi ar ieslēgtiem ZrO₂ graudiem, kas pārsvarā ir kubiskā modifikācijā. Galvenā atšķirība starp abos saķepināšanas procesos iegūtajiem paraugiem ir tā, ka tradicionāli saķepināto paraugu mikrostruktūrā ir novērojama ‘tukšumu’ veidošanās, kuri aizpildās ar mullīta kristāliem, it sevišķi palielinoties Si₃N₄ piedevai. Mikrostruktūra keramikas paraugiem, kas saķepināti ar SPS tehnoloģiju ir blīvāka – mullīta kristāli ir blīvi izvietojušies, un tiem nav mullītam raksturīgās prizmatiskās formas. Dense high-temperature mullite-ZrO2 ceramics The influence of some additives (clay mineral illite, Si₃N₄, SiAlON) and the processing of the initial powders on sintering of mullite-ZrO₂ ceramics (using traditional or plasma dispersion sintering processes), composition, structure, mechanical and ceramic properties of phases is shown. The clay additive contributes to the reduction of the particle size of the powder, facilitates the densification of the ceramic samples in the traditional sintering process, but vice versa if SPS is used. Silicon nitride and SiAlON nanopowder additives are effective in the SPS process; samples reach a compressive strength of approximately 600 MPa in the case of Si₃N₄ additive; thermal shock resistance and elastic modulus are in the range of 180–220 GPa, which under a thermal shock of 1000/20 °C will reduce within the permissible limits. These values are about 20–25 % lower if SiAlON additive is used. The microstructure of the ceramic samples traditionally sintered or sintered using a SPS process is formed by crystalline mullite or pseudomulite crystals with enclosed ZrO₂ grains that mostly are in the cubic modification. The main difference between the samples obtained in both sintering processes is that formation of voids filled with mullite crystals can be observed in the microstructure of traditionally sintered samples, especially if the amount of Si3N4 additive is increased. The microstructure of the ceramic samples sintered with SPS technology is denser – the mullite crystals are densely distributed and do not have the prismatic shape that is characteristic to mullite.