The influence of synthesis parameters and dopants on structure and properties of barium bismuth-titanate ceramics

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..

Aurivillius BaBi4Ti4O15 based compounds: Structure, synthesis and properties

The discovery of some Aurivillius materials with high Curie temperature or fatigue-free character suggests possible applications in high temperature piezoelectric devices or non-volatile ferroelectric random access memories. Furthermore, increasing concerns for environmental issues have promoted the study of new lead-free piezoelectric materials. Barium bismuth titanate (BaBi4Ti4O15), an Aurivillius compound, is promising candidate to replace lead-based materials, both as lead-free ferroelectric and high temperature piezoelectric. In this review paper, we report a detailed overview of crystal structure, different synthesis methods and characteristic properties of barium bismuth titanate ferroelectric materials

Barium titanate thick films prepared by screen printing technique

The barium titanate (BaTiO3) thick films were prepared by screen printing technique using powders obtained by soft chemical route, modified Pechini process. Three different barium titanate powders were prepared: i) pure, ii) doped with lanthanum and iii) doped with antimony. Pastes for screen printing were prepared using previously obtained powders. The thick films were deposited onto Al2O3 substrates and fired at 850°C together with electrode material (silver/palladium) in the moving belt furnace in the air atmosphere. Measurements of thickness and roughness of barium titanate thick films were performed. The electrical properties of thick films such as dielectric constant, dielectric losses, Curie temperature, hysteresis loop were reported. The influence of different factors on electrical properties values was analyzed

La-doped and La/Mn-co-doped Barium Titanate Ceramics

Barium titanate ceramics doped with 0.3 mol.% lanthanum and co-doped with 0.3 mol.% lanthanum and 0.05 mol.% manganese were investigated. The powders were prepared by a modified polymeric precursor method based on the Pechini process. The ceramics were obtained by sintering at 1300 degrees C for 8 h. The influence of dopants on structural changes and grain size reduction was analyzed. The presence of dopants influenced the tetragonality of the barium titanate crystal structure. Reduction of polygonal grain size with dopant addition was noticed. In the doped ceramics, characteristic phase transitions were shifted to lower temperatures in comparison with pure barium titanate. The dielectric permittivity value showed the tendency of a slight increase with lanthanum addition and further increase with adding of manganese. La as a single dopant increased the diffuseness of phase transitions indicating the formation of a diffuse ferroelectric material but in the co-doped ceramics the phase transition diffuseness decreased. The resistivity of the co-doped ceramics was higher than for lanthanum doped ceramics, indicating possible segregation of manganese at grain boundaries that influenced the total resistivity of the material

Study of Barium Bismuth Titanate Prepared by Mechanochemical Synthesis

Barium-bismuth titanate, BaBi4Ti4O15 (BBT), a member of Aurivillius bismuth-based layer-structure perovskites, was prepared from stoichiometric amounts of barium titanate and bismuth titanate obtained via mechanochemical synthesis. Mechanochemical synthesis was performed in air atmosphere in a planetary ball mill. The reaction mechanism of BaBi4Ti4O15 and the preparation and characteristics of BBT ceramic powders were studied using XRD, Raman spectroscopy, particle analysis and SEM. The Bi-layered perovskite structure Of BaBi4Ti4O15 ceramic forms at 1100 degrees C for 4 h without a pre-calcination step. The microstructure of BaBi4Ti4O15 exhibits plate-like grains typical for the Bi-layered structured material and spherical and polygonal grains. The Ba2+ addition leads to changes in the microstructure development, particularly in the change of the average grain size

PZT-NZF/CF ferrite flexible thick films: Structural, dielectric, ferroelectric, and magnetic characterization

The preparation and properties of thick flexible three-phase composite films based on lead zirconium titanate (PZT) and various ferrites (nickel zinc ferrite (NZF) and cobalt ferrite (CF)) were reported in this study. Properties of three-phase composite films were compared with pure polyvinylidene fluoride (PVDF) and PZT-PVDF films. X-ray diffraction data indicated the formation of well crystallized structure of PZT and NZF/CF phases, without the presence of undesirable phases. Scanning electron micrographs showed that the ceramic particles were dispersed homogeneously in the PVDF matrix and atomic force microscopy confirmed that the size of the particles is around 30 nm. Non-saturated hysteresis loops were evident in all samples due to the presence of highly conductive ferrite phases. Under magnetic field of 10 kOe, composite films exhibited a typical ferromagnetic response. Dielectric properties were investigated in the temperature range from -128 to 250 degrees C and frequency range of 400 Hz-1 MHz. The results showed that the value of dielectric constant of the PVDF/PZT/ferrite composites increased about 25% above the one obtained for pure PVDF

Magneto-dielectric properties of ferrites and ferrite/ferroelectric multiferroic composites

Ni-Zn ferrites, with the general formula Ni1-xZnxFe2O4 (x = 0.0, 0.3, 0.5, 0.7, 1.0), CoFe2O4, BaTiO3 and PbZr0.52Ti0.48O3 powders were synthesized by auto-combustion method. The composites were prepared by mixing the appropriate amounts of individual phases, pressing and conventional sintering. X-ray analysis, for individual phase and composites, indicated the formation of crystallized structure of NiZnFe2O4, BaTiO3 and PbZr0.52Ti0.48O3 without the presence of secondary phases or any impurities. SEM analyses indicated a formation of uniform grain distribution for ferromagnetic and ferroelectric phases and formation of two types of grains, polygonal and rounded, respectively. Magneto-dielectric effect was exhibited in all samples because of the applied stress occurring due to the piezomagnetic effect and the magnetic field induced the variation of the dielectric constant. For all samples the dielectric constant was higher in applied magnetic field. At the low frequency, the dispersion of dielectric losses appeared, while at the higher frequency the value of tan δ become constant (Maxwell-Wagner relaxation). Investigation of J-E relation between leakage and electric field revealed that both nickel zinc ferrite and composites have three different regions of conduction: region with ohmic conduction mechanism, region with the trap-controlled space charge limited current mechanism and region with space charge limited current mechanism

History and challenges of barium titanate: Part I

Barium titanate is the first ferroelectric ceramics and a good candidate for a variety of applications due to its excellent dielectric, ferroelectric and piezoelectric properties. Barium titanate is a member of a large family of compounds with the general formula ABO(3) called perovskites. Barium titanate can be prepared using different methods. The synthesis method depends on the desired characteristics for the end application. The used method has a significant influence on the structure and properties of barium titanate materials. In this review paper, Part I contains a study of the BaTiO3 structure and frequently used synthesis methods

Bulk composite multiferroics: BaTiO

Multiferroic composite materials are usually consisted of ferrite materials as a main component on the one side and ferroelectric materials on another. Preparations and properties of bulk composites such as BaTiO3-NiFe2O4, BaTiO3-NixZn1-αxFe2O4, and BaTiO3-CoFe2O4 will be presented. The main problem in preparing of these composite materials is possible reaction at the interfaces between the ferroelectric and magnetic phases during sintering. The optimization of sintering process should be performed in order to obtain di-phase composite material of desired composition. New aspects concerning the magnetic and dielectric properties and their relationship with composition are reported

Review of the most common relaxor ferroelectrics and their applications

Relaxor ferroelectrics were discovered almost 50 years ago among the complex oxides with perovskite structure. In recent years, this field of research has experienced a revival of interest. The dielectric relaxation phenomenon in ferroelectric materials reflects the delay in the frequency response of a group of dipoles when submitted to an external applied field. Also, relaxor ferroelectrics show a high strain response and are actively being investigated for transducers and dielectric applications. The other promising field for relaxor applications is piezoelectric transducers and multilayer ceramic capacitors. This review presents properties and applications some of the most common relaxors such as PMN (Pb(Mg1/3Nb2/3)O3, PLZT (Pb1-αxLax(Zr1-αyTiy)1-αx/4O3), PZN (Pb(Zn1/3Nb2/3)O3 and some less investigated such as Ba-based layered perovskites (BaBi4Ti4O15, BaBi2Ta2O9, and BaBi2Nb2O9)