Effect of grain size on ferroelectric domain and electrical properties of submicron sized sodium potassium niobate ceramics

Mirva Eriksson (et al.).

Piezoelectric ceramics of the composition Na_0.5K_0.5NbO₃ (NKN) with grain sizes in the range of 0.2 - 1 mm were fabricated by Spark Plasma Sintering using normal pressure dies and a high pressure cell designed for pressures up to 500 MPa with the purpose of investigating the effect of grain size on domain structures and electrical properties. Optimized processing conditions enabled ceramics of high densities (>99.5%TD) to be made at T≥850°C. It was found that domain size decreases with decreasing grain size and that non-180° ferroelectric domains walls were still visible in 200 nm sized grains. The room temperature dielectric constant firstly increased with decreasing grain size and then decreased in the low grain size regime. The materials with finer grain size displayed a broad ferro-paraelectric phase transition and a depression of the dielectric maximum at the Curie point. They also displayed an increase in the coercive field and approximately unchanged remnant polarization. The material sintered at 850°C represents a very good candidate for lead-free piezoelectric applications, because of its high piezoelectric constant (d₃₃ = 160±2 pC/N).

Transparent hydroxyapatite nanoceramics by high pressure spark plasma sintering at the minimized sintering temperature

Mirva Eriksson (et al.).

For direct observation of the bio-interfacial reactions with improved spatial and temporal resolution by confocal microscopy transparent hydroxyapatite nanoceramics are demanded. The aim of the present study was to, through detailed kinetics study and micostructural characterization, define a processing window within which transparent HAp nanoceramics can be produced by spark plasma sintering of dry powders. A lab-made hydrothermally processed bulky powder composed of loosely aggregated nanorods and a commercial granulated-powder composed of irregular shaped nanorods were tested. The use of a high pressure cell allows the application of pressure up to 500 MPa. It was found that applying of high pressure is beneficial for widen up the processing window for attaining dense HAp ceramics with nano grained microstructure. The high transparency of HAp nanoceramics obtained in this study is ascribed to the high density and homogeneous nano-structure achieved besides the unique intrinsic optical properties of the HAp crystal, i.e. its low refractive index and very small birefringence. Achieving full densification at the minimized sintering temperature allows for the first time the preparation of transparent HAp nanoceramics with stoichiometric composition, i.e. avoiding the loss of water that commonly encountered during the conventional ways of sintering.

Mechanical properties and electromagnetic shielding performance of single-source-precursor synthesized dense monolithic SiC/HfCxN1-x/C ceramic nanocomposites

2019. Qingbo Wen (et al.). Journal of Materials Chemistry C 7 (34), 10683-10693

Article

For the first time, single-source-precursor synthesized dense monolithic SiC/HfCxN1-x/C ceramic nanocomposites with outstanding electromagnetic (EM) shielding performance at temperatures up to 600 degrees C are reported. The total shielding effectiveness (SET) of the SiC/HfCxN1-x/C monolith is >40 dB at 600 degrees C, which is superior than most of the reported EM shielding materials under the same conditions. Compared with a Hf-free SiC/C monolith, the SiC/HfCxN1-x/C monolith possesses superior EM shielding performance due to the presence of a highly conductive HfCxN1-x phase. Moreover, the HfCxN1-x-particles are covered by a carbon layer forming core-shell nanoparticles connected with graphite-like carbon ribbons, which result in electrically conductive networks within the semiconducting beta-SiC matrix. In addition, the hardness, Young's modulus and flexural strength of the dense SiC/HfCxN1-x/C monolith are measured to be 29 +/- 4 GPa, 381 +/- 29 GPa and 320 +/- 25 MPa, respectively. The outstanding EM shielding performance combined with excellent mechanical properties of the dense monolithic SiC/HfCxN1-x/C nanocomposites provides a novel strategy to fabricate EM shielding materials for applications in harsh environments and/or under high mechanical load.

Self-supported yttria-stabilized zirconia mesocrystals with tunable mesopores prepared by a chemi-thermal process

2019. Leifeng Liu (et al.).

Article

Mesoporous mesocrystals are highly desired in catalysis, energy storage, medical and many other applications, but most of synthesis strategies involve the usage of costly chemicals and complicated synthesis routes, which impede the commercialization of such materials. During the sintering of dense ceramics, coarsening is an undesirable phenomenon which causes the growth of the grains as well as the pores hence hinders the densification, however, coarsening is desired in the sintering of porous ceramics to expand the pore sizes while retaining the total pore volume. Here we report a chemi-thermal process, during which nanocrystallite aggregates were synthesized by hydrothermal process and then converted to the product by sintering. Through this strategy, we synthesized mesoporous self-supported mesocrystals of yttria-stabilized zirconia with tunable pore size and the process was then scaled-up to industrial production. The thermal conductivity measurement shows that the mesoporous powder is a good thermal isolator. The monolith pellets can be obtained by SPS sintering under high pressure and the mesoporosity is retained in the monolith pellets. This work features facile and scalable process as well as low cost raw chemicals making it highly desirable in industrial applications.

The influence of Be addition on the structure and thermal properties of alkali-silicate glasses

2019. N. A. Wójcik (et al.). Journal of Non-Crystalline Solids 521

Article

Be-Na-(Li)-Si oxide glasses containing up to 15 mol% of BeO were prepared. Their structure was characterized by X-ray powder diffraction and Raman as well as infrared spectroscopic techniques, while their chemical compositions were examined by Inductively Coupled Plasma Optical Emission Spectrometry. All materials were found to be amorphous and contain Al contaminations from minor dissolution of the alumina crucibles. The results of Raman and IR spectroscopies showed that BeO addition to Na-(Li)-Si glass systems resulted in the formation of [BeO4/2](2-) tetrahedra which are inserted into the silicate glass network, demonstrating the intermediate glass-forming role of BeO. In parallel, the effective destruction of Si-O-Si bridges was observed by vibrational spectroscopy. The glass transition temperature was studied by Differential Thermal Analysis and found to range from about 431 degrees C to 551 degrees C. A significant increase in T-g by 70 degrees C was found as SiO2 was substituted by up to 15 mol% BeO.

Tougher zirconia nanoceramics with less yttria

2019. Ji Zou (et al.). Advances in Applied Ceramics 118 (1-2), 9-15

Article

Reducing the grain size in zirconia ceramics has shown to decrease its toughness by size-dependent stabilisation of the tetragonal phase that, in turn, hinders the stress-induced phase transformation from tetragonal to monoclinic. The stability of the tetragonal phase increases with the decrease of grain size but decreases with the reduction of the amount of yttria added, implying the need for adjustment of the yttria content when a nano-grained structure is of concern. In this study, low-yttria compositions were investigated. The ceramics were prepared with two sintering methods namely spark plasma sintering (SPS) and pressureless sintering. A clear tendency was noted for the indentation toughness increase with the reduction of yttria content, and a higher toughness achieved in as-SPSed samples in comparison with the annealed samples. The origins of the increased toughness were discussed in terms of yttria content, carbon contamination and increased oxygen vacancies after sintering at reducing atmosphere in SPS.

Influence of synthesis conditions on glass formation, structure and thermal properties in the Na2O-CaO-P2O5 system doped with Si3N4 and Mg

2018. N. A. Wójcik (et al.). Journal of Non-Crystalline Solids 494, 66-77

Article

Oxynitride phosphate glasses and glass-ceramics were prepared using new synthesis routes for phosphate glasses. Materials were melted from pre-prepared glass samples in the system Na-Ca-P-0 with addition of Mg and/or Si3N4 powders under different preparation conditions. The melting process was conducted at 1000-1500 degrees C either under air or nitrogen atmosphere to obtain materials with different nitrogen content. Their topography and structure were characterized by Confocal Microscopy, Scanning Electron Microscopy, X-ray powder diffraction and Raman and infrared spectroscopy techniques, while their chemical compositions were examined by Energy Dispersive X-ray spectroscopy (EDS). All materials prepared under nitrogen atmosphere were found to contain a relative low quantity of nitrogen and high amount of Nb leached from the crucible. The reaction with the Nb crucible was not previously observed for silicon-based oxynitride glasses. The synthesized materials form two groups: glasses and glass-ceramics. The first ones, were prepared under air and nitrogen atmospheres at temperatures up to 1400 degrees C, and were found to be amorphous and homogeneous. Raman and infrared spectroscopy measurements confirm the presence of amorphous phosphates in the synthesized materials. The samples of the second group were prepared at temperatures above 1400 degrees C and were found to be translucent and partially crystallized. They contain nanocrystallites of calcium and sodium phosphates including hydroxyapatite (HAp). The thermal properties of samples were studied by Differential Scanning Calorimetry (DSC). The obtained glass transition temperatures range from about 360 degrees C to 640 degrees C and exhibit high values for glass-ceramic materials. Stability is improved in the studied glass-ceramics because of the increased degree of network polymerization of the remaining glassy matrix. The approximate fragility index decreases two times for oxynitride materials compared to the primary glass. The synthesized new materials may be competitive to well-known bioactive phosphate glasses thanks to their improved stability by Mg, Si, N and Nb doping.

Fractography of self-glazed zirconia with improved reliability

2017. Zhijian Shen (et al.). Journal of the European Ceramic Society 37 (14), 4339-4345

Article

The fractography of a new grade of zirconia ceramics, known as self-glazed zirconia, was investigated. The as-sintered intact top surface was made with superior smoothness that mimicked the optical appearances of the natural teeth enamel. The beneath surface opposite to this was made hierarchically rough with microscopic pits of the size up to 60 mu m together with grain-level roughness of about 2 mu m. The three-point bending test of the samples made with the hierarchically rough surface being tensile one demonstrated an average bending strength of 1120 +/- 70 MPa and a Weibull modulus of as high as 18 ascribed to the improved structural homogeneity. Surface topography was found the main origins of crack initiation leading to fracture. The observed unusually predominant transgranular fracture mode of submicron-sized grains disclosed a possible toughening mechanism of disassembling of mesocrystalline grains that differs significantly from the commonly quoted phase transformation toughening of this category of ceramics.

Ordered coalescence of nano-crystals in alkaline niobate ceramics with high remanent polarization

2017. Zhijian Shen (et al.).

Article

Lead-free alkali niobates Na0.5K0.5NbO3 (NKN) ceramics, with significantly enhanced ferroelectric remanent polarization (P-r), were prepared using Spark Plasma Sintering (SPS). Three types of boundaries were observed in the ceramics, being grain boundaries between faceted grains, domain boundaries that separate ferroelectric domains inside individual grains, and nanoscale sub-grain boundaries that reveal the nano-scale mosaicity of individual grains. Part of the sub-grain boundaries were from initial powder particles. The other sub-grain boundaries were built by ordered coalescence of nano-crystals during rapid SPS process. It was worthwhile to emphasize that the ordered coalescence of nano-crystals in bulk ceramics during sintering takes place and completes within minutes. These sub-grain features would disappear at higher temperature by long time sintering. Rapid Spark Plasma Sintering allowed us to capture this transient microstructure. The significantly enhanced ferroelectric P-r of NKN was attributed to nanoscale sub-boundaries, which stimulated the dynamics of ferroelectric domain formation and switching.

Micro-hydrothermal reactions mediated grain growth during spark plasma sintering of a carbonate-containing hydroxyapatite nanopowder

2014. Yi Liu (et al.). Journal of the European Ceramic Society 34 (16), 4395-4401

Article

A carbonate-containing hydroxyapatite nanopowder was consolidated by spark plasma sintering at the temperatures ranging from 650 to 1100 degrees C. It was found that the water released by dehydroxylation was trapped inside the nanopores in the densified HAp bodies over 900 degrees C. Based on the analysis by the X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscope, the water-nanopore system was evaluated and its effect on the grain growth was also investigated. It was revealed that the water existed inside the closed nanopores most probably resulted in the formation of local micro-hydrothermal environments inside bulk HAp ceramics during SPS. Therefore, the grain growth was enhanced by the local micro-hydrothermal reactions activated above 900 degrees C. In addition, abnormal grain growth was also observed when a higher temperature or higher heating rate was employed, which may be attributed to the local highly active hydrothermal reactions.

Effect of grain size on domain structures, dielectric and thermal depoling of Nd-substituted bismuth titanate ceramics

2013. Giuseppe Viola (et al.). Applied Physics Letters 103 (18), 182903

Article

The microscopic origin of the grain size effects on the dielectric, piezoelectric, and thermal depoling properties of Aurivillius phase Bi3.15Nd0.85Ti3O12 was investigated. Using atomic force microscopy, domain walls were observed in micrometer grain size ceramics, but gradually disappeared with reducing grain size and were not found in ceramics with 90 nm grain size. In strain-electric field butterfly loops, the strain decreased with decreasing grain size indicating a decreasing contribution of non-180 degrees domain walls switching to the strain. Lattice distortion (a-b)/b decreased with decreasing grain size. The thermal depoling resistance decreased with decreasing grain size, due to increasing internal mechanical stresses.

Spark plasma sintering of wc, cemented carbide and functional graded materials

2013. Mirva Eriksson, Mohamed Radwan, Zhijian James Shen. International journal of refractory metals & hard materials 36, 31-37

Article

Spark plasma sintering (SPS) is an extremely fast solidification technique for compounds that are difficult to sinter within the material group's metals, ceramics, or composites thereof. SPS uses a uniaxial pressure and a very rapid heating cycle to consolidate these materials. The heating is generated by Joule effect when a strong, pulsed electric current passes the conductive graphite die and also through the sample, if conductive. Cemented carbides (hard metals) are mostly used for metal cutting and drilling, wood cutting or rock drilling tools and are consolidated either by pressureless sintering (PLS), hot pressing (HP), or hot isostatic pressing (HIP). With SPS the main benefit is the ability to control the WC grain size due to the short sintering times at high temperature. In addition, unwished reactions between WC and cobalt to form other phases are minimized. By SPS the amount of cobalt can be reduced towards zero in fully dense WC materials. With this technique it is easy to prepare gradient materials where a ductile weldable metal can be joined with the cemented carbide part.

Can the use of pulsed direct current induce oscillation in the applied pressure during spark plasma sintering?

2012. David Salamon (et al.). Science and Technology of Advanced Materials 13 (1), 015005

Article

The spark plasma sintering (SPS) process is known for its rapid densification of metals and ceramics. The mechanism behind this rapid densification has been discussed during the last few decades and is yet uncertain. During our SPS experiments we noticed oscillations in the applied pressure, related to a change in electric current. In this study, we investigated the effect of pulsed electrical current on the applied mechanical pressure and related changes in temperature. We eliminated the effect of sample shrinkage in the SPS setup and used a transparent quartz die allowing direct observation of the sample. We found that the use of pulsed direct electric current in our apparatus induces pressure oscillations with the amplitude depending on the current density. While sintering Ti samples we observed temperature oscillations resulting from pressure oscillations, which we attribute to magnetic forces generated within the SPS apparatus. The described current-pressure-temperature relations might increase understanding of the SPS process.

Ferroelectric Domain Structures and Electrical Properties of Fine-Grained Lead-Free Sodium Potassium Niobate Ceramics

2011. Mirva Eriksson (et al.). Journal of The American Ceramic Society 94 (10), 3391-3396

Article

Piezoelectric ceramics of the composition Na(0.5)K(0.5)NbO(3) (NKN) with grain sizes in the range of 0.2-1 mu m were fabricated by spark plasma sintering. Ferroelectric domain size decreases with decreasing grain size and non-180 degrees ferroelectric domains walls were still visible in 200 nm sized grains. The Curie point of the ceramics was grain size independent. This suggests that the critical grain size for a single domain single grain structure for NKN is <200 nm. Optimized processing conditions enabled ceramics of high densities (>99.5% theoretical density) to be made at T >= 850 degrees C. For the dense ceramics (grain size >= 350 nm), the room temperature dielectric constant and coercive field increased with decreasing grain size. The remnant polarization was grain size independent. The material sintered at 850 degrees C is a very good candidate for lead-free piezoelectric applications because of its high piezoelectric constant (d(33) = 160 +/- 2 pC/N).

Transparent hydroxyapatite ceramics with nanograin structure prepared by high pressure spark plasma sintering at the minimized sintering temperature

2011. Mirva Eriksson (et al.). Journal of the European Ceramic Society 31 (9), 1533-1540

Article

A hydrothermally processed bulky powder composed of loosely aggregated nano-sized rods was consolidated by spark plasma sintering. The use of a high pressure cell allows the application of pressure up to 500 MPa. It was found that applying of high pressure is beneficial for widening up the kinetic window for attaining dense HAp nanoceramics. The high transparency of HAp nanoceramics obtained in this study is ascribed to the high density and homogeneous nano-grained structure achieved besides the unique intrinsic optical properties of the HAp crystal itself, i.e. its low refractive index and very small birefringence. Achieving full densification at the minimized sintering temperature allows for the first time the preparation of transparent HAp nanoceramics with stoichiometric composition, i.e. avoiding the loss of structural water that commonly takes place during the conventional ways of sintering.

Low temperature consolidated lead-free ferroelectric niobateceramics with improved electrical properties

2010. Mirva Eriksson (et al.). Journal of Materials Research 25 (2), 240-247

Article

There is a concerted effort to develop lead-free piezoelectric ceramics. ((Na0.5K0.5)NbO3 based ceramics have good electrical properties, and are a potential replacement material for lead zirconate titanate piezoelectric ceramics. In this work a commercial powder based on (Na0.5K0.5)NbO3 with an initial particle size of 260 nm was consolidated by plasma sintering (SPS). To avoid volatilization, high mechanical pressures were used to minimize the densification temperature. It was found that under a uniaxial pressure of 100 MPa, fully densified compacts can be prepared at 850. Ceramics densified at such a low temperature demonstrate an unusually high remanent polarization (30 mC/cm2) and high d33 (146 pC/N). The improved ferroelectric properties are ascribed to the homogeneous, dense, and submicron grained microstructure achieved.

Spark Plasma Sintering Enhancing Grain Sliding, Deformation and Grain Size Control

2010. Mirva Eriksson, Zhijian Shen, Takashi Goto.

Thesis (Doc)

The unique features of the Spark plasma sintering (SPS) were used to investigate the sintering and deformation behaviour of titanium and titanium–titanium diboride composites, and to control the sintering and grain growth of ferroelectric Na_0.5K_0.5NbO₃(NKN) and of hydroxyapatite (HAp). In the SPS the samples experience a temperature different from that recorded by the thermocouple (pyrometer) used and this temperature difference has been estimated for Ti and NKN.

Sintering and deformation of titanium was investigated. Increasing heating rate and/or pressure shifted the sintering to lower temperatures, and the sintering and deformation rates changed when the α→β phase transition temperature was passed. Fully dense Ti/TiB₂ composites were prepared. The Ti/TiB₂ composites could be deformed at high temperatures, but the hardness decreased due to the formation of TiB.

The kinetic windows within which it is possible to obtain fully dense NKN and HAp ceramics and simultaneously avoid grain growth are defined. Materials have a threshold temperature above which rapid and abnormal grain growth takes place. The abnormal grain growth of NKN is due to a small shift in the stoichiometry, which in turn impairs the ferroelectric properties. Fully transparent HAp nanoceramics was prepared, and between 900 and 1050 ^oC elongated grains are formed, while above 1050 ^oC abnormal grain growth takes place.NKN samples containing grains of the sizes 0.35–0.6 µm yielded optimum ferroelectric properties, i.e. a high remanent polarization (P_r = 30 µC/cm²) and high piezoelectric constant (d₃₃= 160 pC/N). The ferroelectric domain structure was studied, and all grains exhibited a multi-domain type of structure.

The grain size effect on the properties of Aurivillius phase Bi3.15Nd0.85Ti3O12 ferroelectric ceramics

2009. Hongtao Zhang (et al.). Nanotechnology 20 (38), 385708/1-385708/5

Article

Spark plasma sintering and deformation of Ti-TiB2 composites.

2008. Mirva Eriksson (et al.). Materials Science & Engineering, A: Structural Materials: Properties, Microstructure and Processing 1-2 (A475), 101-104

Article

Spark plasma sintering (SPS) was used to investigate the densification and deformation behaviour of Ti–TiB₂ composites. Fully densified samples were prepared with Ti addition larger than 5%. The prepared composites can be deformed under compression at 1700 °C to achieve a strain of 50% without cracking. At lower temperatures, cracks were initiated due to low ductility of TiB₂ and low content of Ti. During the sintering and deformation, TiB is formed via a reaction between Ti and TiB₂. To elucidate the formation mechanism of TiB in the SPS process, reactive sintering of TiB using element precursors was also performed. Fully dense samples were prepared but it was not possible to prepare pure uniphase TiB. The reactive sintering resulted in the formation of TiB and TiB₂ mixtures at low temperatures and a mixture of TiB₂ and Ti₃B₄ at high temperature

Fast densification and deformation of titanium powder

2005. Mirva Eriksson, Zhijian Shen, Mats Nygren. Powder Metallurgy 48 (3), 231-236

Article

A coarse titanium powder containing 0.2 wt-% oxygen with an average particle size of 45 micrometers was rapidly densified using the spark plasma sintering (SPS) technique. The fully consolidated specimens were also deformed in compression in the SPS unit and in a conventional hot pressing (HP) furnace. The densification and deformation behaviours were investigated by microstructural observation and examining the shrinkage and shrinkage rate recorded in real time. The efforts were focused on clarifying to what extent the possible spark discharging and intensive Joule heating at the particle contact points contribute to the densification, and what effect if any the pulsed electrical heating has on the densification. The results showed that what contributed to the densification were neither spark discharging nor anisotropic heating, but the particle deformation. Deformation occurs throughout the entire particle both in SPS and HP conditions, with a higher strain rate under SPS condition especially in the a phase region.

Mirva Eriksson

About me

Teaching

Publications

Effect of grain size on ferroelectric domain and electrical properties of submicron sized sodium potassium niobate ceramics

Transparent hydroxyapatite nanoceramics by high pressure spark plasma sintering at the minimized sintering temperature

Mechanical properties and electromagnetic shielding performance of single-source-precursor synthesized dense monolithic SiC/HfCxN1-x/C ceramic nanocomposites

Self-supported yttria-stabilized zirconia mesocrystals with tunable mesopores prepared by a chemi-thermal process

The influence of Be addition on the structure and thermal properties of alkali-silicate glasses

Tougher zirconia nanoceramics with less yttria

Influence of synthesis conditions on glass formation, structure and thermal properties in the Na2O-CaO-P2O5 system doped with Si3N4 and Mg

Fractography of self-glazed zirconia with improved reliability

Ordered coalescence of nano-crystals in alkaline niobate ceramics with high remanent polarization

Micro-hydrothermal reactions mediated grain growth during spark plasma sintering of a carbonate-containing hydroxyapatite nanopowder

Effect of grain size on domain structures, dielectric and thermal depoling of Nd-substituted bismuth titanate ceramics

Spark plasma sintering of wc, cemented carbide and functional graded materials

Can the use of pulsed direct current induce oscillation in the applied pressure during spark plasma sintering?

Ferroelectric Domain Structures and Electrical Properties of Fine-Grained Lead-Free Sodium Potassium Niobate Ceramics

Transparent hydroxyapatite ceramics with nanograin structure prepared by high pressure spark plasma sintering at the minimized sintering temperature

Low temperature consolidated lead-free ferroelectric niobateceramics with improved electrical properties

Spark Plasma Sintering Enhancing Grain Sliding, Deformation and Grain Size Control

The grain size effect on the properties of Aurivillius phase Bi3.15Nd0.85Ti3O12 ferroelectric ceramics

Spark plasma sintering and deformation of Ti-TiB2 composites.

Fast densification and deformation of titanium powder