Uticaj parametara sinteze i dopanata na strukturu i svojstva barijum bizmut-titanatne keramike

Abstract

U okviru ove doktorske disertacije proučavan je uticaj uslova sinteze tj. mehaničke aktivacije na formiranje strukture barijum bizmut-titanata, kao i na svojstva dobijene keramike. Detaljno i sistematski je proučavan uticaj La3+ kao izovalentnog dopanta i Nb5+ kao donorskog dopanta na dielektrična i električna svojstva barijum bizmut-titanatne keramike.Smeša prahova BaO, TiO2 i Bi2O3 u ekvivalentnom odnosu je mehanički aktivirana u planetarnom mlinu u toku 0 - 6 h. Dinamika formiranja novih faza praćena je metodom rendgenske difrakcije. Utvrđeno je da nakon 6 h mlevenja dolazi do formiranja slojevite Aurivilijusove strukture. Termičkim tretmanom na 850 oC tokom 1 h od mehanički aktivirane smeše oksida tokom 6 h, sintetisan je BaBi4Ti4O15.Konvencionalnim postupkom reakcije u čvrstom stanju dobijeni su prahovi čistog i dopiranog barijum bizmut-titanata. Formiranje odgovarajuće strukture u prahovima koji su dobijeni ovim postupkom praćeno je metodom rendgenske difrakcije, tako da je utvrđen mehanizam formiranja barijum bizmut-titanata. Temperatura na kojoj se formira čista faza barijum bizmut-titanta je 950 oC nakon 1 h sinterovanja. Laserskim difraktometrom određena je prosečna veličina čestica prahova dobijenih konvencionalnim postupkom sinteze i praha koji je prethodno mehaniči aktiviran. Na osnovu ovih rezultata i rezultata skenirajuće elektronske mikroskopije uočen je bitan uticaj mehaničke aktivacije na smanjenje veličine čestica aktiviranog praha, što dovodi do povećanja njegove reaktivnosti.Jednoosnim presovanjem i izotermskim sinterovanjem prahova na temperaturama 1120 - 1150 oC (u zavisnosti od sastava) dobijeni su keramički uzorci čistog i dopiranih uzorka barijum bizmut-titanata. Električna svojstva dobijenih materijala merena su u opsegu temperatura od 27 do 727 °C i oblasti frekvencija od 1,21 kHz do 1 MHz u atmosferi vazduha. Rezultati dielektričnih merenja ukazuju na bitne promene vrednosti dielektrične permitivnosti sa dodatkom dopanata. Uočeno je pomeranje temperature faznog prelaza (iz polarne u nepolarnu fazu) ka nižim vrednostima, širenje pikova, kao i povećanje stepena relaksacije faznog prelaza usled inkorporacije jona u kristalnu strukturu jedinjenja. Potvrđeno je da mehanička aktivacija utiče na smanjenje veličine zrna, pa samim tim i na promenu vrednosti dielektrične permitivnosti na Kiri temperaturi. Korišćenjem modifikovanog Kiri-Vajs zakona uočeno je da mehanička aktivacija utiče na povećanje stepena difuzivnosti dok je, korišćenjem Vogel-Fučerove zavisnosti, potvrđeno smanjenje stepena relaksacije faznog prelaza...

In this doctoral dissertation the influence of synthesis conditions, i.e. mechanical activation on the structure formation and properties of barium bismuth titanate ceramics was studied. The influence of La3+, as an isovalent dopant and Nb5+, as a donor dopant on the dielectric and electrical properties on this type of ceramics was also systematically studied.An equimolar BaO, TiO2 and Bi2O3 powder mixture was mechanically activated in a planetary mill for 0 - 6 h. The dynamics of new phases formation was monitored by X-ray diffraction. It was found that 6 h of milling leads to the formation of layered Aurivillius structure. Oxide mixtures mechanically activated for 6 h was heat treated at 850 °C for 1 h when BaBi4Ti4O15 was formed.Powders of pure and doped barium bismuth titanate were obtained by conventional solid state reaction method. Determination of appropriate structures in powders obtained by this procedure was followed by X-ray diffraction. The mechanism of the formation of barium bismuth titanate was established. The temperature at which it forms a pure phase was specified to be 950 °C after 1 h of sintering. The average particle size of powders obtained by conventional method and mechanical activated powder was determing using laser diffraction measurement. Based on these results and the results of scanning electron microscopy a significant influence of mechanical activation on the reduction of pawder particle size was noticed, leading to an increase of reactivity.Using uniaxial press and isothermal sintering at temperatures of 1120-1150 oC (depending on the composition) ceramic samples of pure and doped barium bismuth titanate were obtained. Electrical measurements of the obtained materials were performed in the temperature range from 27 to 727 °C and the frequency range of 1.21 kHz to 1 MHz, in air atmosphere. The results of dielectric measurements indicate a significant change in the dielectric constant value with the addition of dopants. Phase transition temperature shift and broadening of peaks were noticed as well as the increase of the degree of phase transition relaxation due to the incorporation of ions in the crystal structure of compounds. Exploring the influence of mechanical activation, it was confirmed that the mechanical activation effects the reduction of grain size and thus the change of dielectric constant value at the Curie temperature. Using a modified Curie-Weiss law was observed that mechanical activation increases the degree of diffusion while, using a Vogel-Fulcher relationship, was confirmed reduction in the degree of relaxation of phase transition...