BaTiO3-BiFeO3 based lead-free ceramics for actuator applications

A crystallochemical framework is proposed based on electronegativity difference (en) and tolerance factor (t) for BiMeO3 dopants to optimise the piezoelectric and electrostrictive response in BaTiO3-BiFeO3 based ceramics. Compositions in the series 0.05Bi(Me)O3-0.25BaTiO3-0.70BiFeO3 (BMe-BT-BF, Me: Y, Sc1/2Y1/2, Mg2/3Nb1/3, Sc, Zn2/3Nb1/3, Zn1/2Ti1/2, Ga, and Al) were fabricated using solid state synthesis. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) revealed that only Bi(Mg2/3Nb1/3)O3 and BiScO3 dopants, which lie in a narrow range of en vs. t, form homogeneous ceramics, free from secondary phases reflected in their superior piezoelectric coefficients (d33 ~ 145 pC/N). The promising initial properties of Bi(Mg2/3Nb1/3)O3 and BiScO3 doped compositions prompted further studies on 0.05Bi(Mg2/3Nb1/3)O3-(0.95-x)BaTiO3-(x)BiFeO3 (BMN-BT-BF, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) and 0.05BiScO3-(0.95-x)BaTiO3-(x)BiFeO3 (BS-BT-BF, x = 0.55, 0.60, 0.625, 0.65, and 0.70) ceramics. For Me = Mg2/3Nb1/3, SEM revealed a homogeneous microstructure for x< 0.75. XRD suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63<x<0.70, characterised by the coexistence of phases. The temperature dependence of relative permittivity, polarisation-electric field hysteresis loops, bipolar strain-electric field curves revealed that BMN-BT-BF transformed from relaxor-like to ferroelectric behaviour with an increase in x and the largest effective piezoelectric coefficient (d33*) was 544 pm/V at 5 kV/mm for x = 0.63 at 5 kV/mm, at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state. For Me = Sc, the trends were similar but Sc-doped samples retained ferroelectric behavior to slightly lower values of x than Mg2/3Nb1/3 samples. The potential for BMN-BT-BF compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved similar % strain to monolithic ceramics and up to 3 μm displacement with good temperature stability up to 150oC

Optimising dopants and properties in BiMeO3 (Me = Al, Ga, Sc, Y, Mg2/3Nb1/3, Zn2/3Nb1/3, Zn1/2Ti1/2) lead-free BaTiO3-BiFeO3 based ceramics for actuator applications

A crystallochemical framework is proposed based on electronegativity difference (en) and tolerance factor (t) to optimise the BiMeO3 dopants and therefore the piezoelectric and electrostrictive response in BaTiO3-BiFeO3 based ceramics. Compositions in the series 0.05Bi(Me)O3-0.25BaTiO3-0.7BiFeO3 (BMe-BT-BF, Me: Y, Sc1/2Y1/2, Mg2/3Nb1/3, Sc, Zn2/3Nb1/3, Zn1/2Ti1/2, Ga, and Al) were fabricated using solid state synthesis and furnace cooled. Scanning electron microscopy and X-ray diffraction revealed that only Bi(Mg2/3Nb1/3)O3 and BiScO3 dopants, which lie in a narrow range of en vs. t, form homogeneous ceramics, free from secondary phases reflected in their superior piezoelectric coefficients (d33 ~145 pC/N). All other BiMeO3 additions exhibited either secondary phases (Y) and/or promoted a two-phase perovskite matrix (Zn, Ga and Al). The promising initial properties of BiScO3 doped compositions prompted further studies on 0.05BiScO3-(0.95-x)BaTiO3-(x)BiFeO3 (BS-BT-BF, x = 0.55, 0.60, 0.625, 0.65, and 0.70) ceramics. As x increased the structure changed from predominantly pseudocubic to rhombohedral, resulting in a transition from a relaxor-like to ferroelectric response. The largest d33 * (465 pm/V) was achieved for x = 0.625 under 5 kV/mm at the crossover from relaxor to ferroelectric behaviour. BS-BT-BF with x = 0.625 showed >0.3% strain under 6 kV/mm up to 175ºC, demonstrating its potential for actuator applications

Improved Resection and Outcome of Colon-Cancer Liver Metastasis with Fluorescence-Guided Surgery Using In Situ GFP Labeling with a Telomerase-Dependent Adenovirus in an Orthotopic Mouse Model.

Fluorescence-guided surgery (FGS) of cancer is an area of intense development. In the present report, we demonstrate that the telomerase-dependent green fluorescent protein (GFP)-containing adenovirus OBP-401 could label colon-cancer liver metastasis in situ in an orthotopic mouse model enabling successful FGS. OBP-401-GFP-labeled liver metastasis resulted in complete resection with FGS, in contrast, conventional bright-light surgery (BLS) did not result in complete resection of the metastasis. OBP-401-FGS reduced the recurrence rate and prolonged over-all survival compared with BLS. In conclusion, adenovirus OBP-401 is a powerful tool to label liver metastasis in situ with GFP which enables its complete resection, not possible with conventional BLS

Continuously controllable optical band gap in orthorhombic ferroelectric KNbO3-BiFeO3 ceramics

The optical band gap of orthorhombic ferroelectric KNbO3 is shown to be continuously controllable via Bi and Fe co-substitution according to a K1-xBixNb1-xFexO3 doping mechanism. Room temperature X-ray diffraction data combined with Raman spectroscopy analysis show the polar orthorhombic crystal structure to persist up to x=0.25, while the bandgap narrows monotonically by 1 eV (~33%). In-situ Raman spectroscopy corroborates the polar nature of all compositions in the temperature range -100 to 200 C. The ability to control the band gap while maintaining the spontaneous polarisation makes the K1-xBixNb1-xFexO3 system interesting for photoinduced processes in a wide temperature range

Helping-Like Behaviour in Mice Towards Conspecifics Constrained Inside Tubes

Prosocial behaviour, including helping behaviour, benefits others. Recently, helping-like behaviour has been observed in rats, but whether it is oriented towards rescue, social contact with others, or other goals remains unclear. Therefore, we investigated whether helping-like behaviour could be observed in mice similar to that in rats. Because mice are social animals widely used in neuroscience, the discovery of helping-like behaviour in mice would be valuable in clarifying the psychological and biological mechanisms underlying pro-sociability. We constrained mice inside tubes. Subject mice were allowed to move freely in cages with tubes containing constrained conspecifics. The subject mice released both cagemates and stranger mice but did not engage in opening empty tubes. Furthermore, the same behaviour was observed under aversive conditions and with anesthetised conspecifics. Interestingly, hungry mice opened the tubes containing food before engaging in tube-opening behaviour to free constrained conspecifics. Mice showed equal preferences for constrained and freely moving conspecifics. We demonstrated for the first time that mice show tube-opening behaviour. Furthermore, we partly clarified the purpose and motivation of this behaviour. An effective mouse model for helping-like behaviour would facilitate research on the mechanisms underlying prosocial behaviour

Layer-specific expression of extracellular matrix molecules in the mouse somatosensory and piriform cortices

In the developing central nervous system (CNS), extracellular matrix (ECM) molecules have regulating roles such as in brain development, neural-circuit maturation, and synaptic-function control. However, excluding the perineuronal net (PNN) area, the distribution, constituent elements, and expression level of granular ECM molecules (diffuse ECM) present in the mature CNS remain unclear. Diffuse ECM molecules in the CNS share the components of PNNs and are likely functional. As cortical functions are greatly region-dependent, we hypothesized that ECM molecules would differ in distribution, expression level, and components in a region- and layer-dependent manner. We examined the layer-specific expression of several chondroitin sulfate proteoglycans (aggrecan, neurocan, and brevican), tenascin-R, Wisteria floribunda agglutinin (WFA)-positive molecules, hyaluronic acid, and link protein in the somatosensory and piriform cortices of mature mice. Furthermore, we investigated expression changes in WFA-positive molecules due to aging. In the somatosensory cortex, PNN density was particularly high at layer 4 (L4), but not all diffuse ECM molecules were highly expressed at L4 compared to the other layers. There was almost no change in tenascin-R and hyaluronic acid in any somatosensory-cortex layer. Neurocan showed high expression in L1 of the somatosensory cortex. In the piriform cortex, many ECM molecules showed higher expression in L1 than in the other layers. However, hyaluronic acid showed high expression in deep layers. Here, we clarified that ECM molecules differ in constituent elements and expression in a region- and layer-dependent manner. Region-specific expression of ECM molecules is possibly related to functions such as region-specific plasticity and vulnerability

High strain (0.4%) Bi(Mg2/3Nb1/3)O3-BaTiO3-BiFeO3 lead-free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg2/3Nb1/3)O3-(0.95-x)BaTiO3-xBiFeO3 (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core-shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X-ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63<x<0.70, characterised by the coexistence of phases. The temperature dependence of relative permittivity, polarisation-electric field hysteresis loops, bipolar strain-electric field curves revealed that BBFT transformed from relaxor-like to ferroelectric behaviour with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41 % for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d33*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d33 (148 pC/N) was obtained for x = 0.70. We propose that d33* is optimised at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d33 is optimised in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175oC, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 m displacement at 150 oC

BiFeO3-BaTiO3: A new generation of lead-free electroceramics

Lead-based electroceramics such as Pb(Zr.Ti)O3 (PZT) and its derivatives have excellent piezoelectric, pyroelectric and energy storage properties and can be used in a wide range of applications. Potential lead-free replacements for PZT such as potassium sodium niobate (KNN) and sodium bismuth titanate (NBT) have a much more limited range of useful properties and have been optimized primarily for piezoelectric applications. Here, we review the initial results on a new generation of lead-free electroceramics based on BiFeO3-BaTiO3 (BF-BT) highlighting the essential crystal chemistry that permits a wide range of functional properties. We demonstrate that with the appropriate dopants and heat treatment, BF-BT can be used to fabricate commercially viable ceramics for applications, ranging from sensors, multilayer actuators, capacitors and high-density energy storage devices. We also assess the potential of BF-BT-based ceramics for electrocaloric and pyroelectric applications