Enhanced thermal stability by short-range ordered ferroelectricity in K0.5Na0.5NbO3-based piezoelectric oxides.

Industrial application of lead-free piezoelectric ceramics is prevented by intrinsic thermal instability. Herein, we propose a method to achieve outstanding thermal stability of converse piezoelectric constant () in lead-free potassium sodium niobate (KNN)-based ceramics by inducing a synergistic interaction between the grain size and polar configuration. Based on computational methods using phase-field simulations and first-principles calculations, the relationship between the grain size and polar configuration is demonstrated, and the possibility of achieving improved thermal stability in fine grains is suggested. A set of KNN systems is presented with meticulous dopant control near the chemical composition at which the grain size changes abnormally. Comparing the two representative samples with coarse and fine grains, significant enhancement in the thermal stability of is exhibited up to 300 °C in the fine grains. The origin of the thermal superiority in fine-grained ceramics is identified through an extensive study from a microstructural perspective. The thermal stability is realized in a device by successfully demonstrating the temperature dependence of piezoelectricity. It is notable that this is the first time that lead-free piezoelectric ceramics are able to achieve exceptionally stable piezoelectricity up to 300 °C, which actualizes their applicability as piezoelectric devices with high thermal stability.

Lead-Free Piezoelectric Acceleration Sensor Built Using a (K,Na)NbO3 Bulk Ceramic Modified by Bi-Based Perovskites.

Piezoelectric accelerometers using a lead-free (K,Na)NbO3 (KNN) piezoceramic modified by a mixture of two Bi-based perovskites, Bi(Na,K,Li)ZrO3 (BNKLZ) and BiScO3 (BS), were designed, fabricated and characterized. Ring-shaped ceramics were prepared using a conventional solid-state reaction method for integration into a compression-mode accelerometer. A beneficial rhombohedral-tetragonal (R-T) phase boundary structure, especially enriched with T phase, was produced by modifying intrinsic phase transition temperatures, yielding a large piezoelectric charge coefficient d33 (310 pC/N) and a high Curie temperature Tc (331 °C). Using finite element analyses with metamodeling techniques, four optimum accelerometer designs were obtained with high magnitudes of charge sensitivity Sq and resonant frequency fr, as evidenced by two key performance indicators having a trade-off relation. Finally, accelerometer sensor prototypes based on the proposed designs were fabricated using the KNN-BNKLZ-BS ceramic rings, which exhibited high levels of Sq (55.1 to 223.8 pC/g) and mounted fr (14.1 to 28.4 kHz). Perfect charge-to-acceleration linearity as well as broad flat frequency ranges were achieved with excellent reliability. These outstanding sensing performances confirm the potential application of the modified-KNN ceramic in piezoelectric sensors.

A Theoretical and Empirical Investigation of Design Characteristics in a Pb(Zr,Ti)O3-Based Piezoelectric Accelerometer.

A theoretical and experimental study on the design-to-performance characteristics of a compression-mode Pb(Zr,Ti)O3-based piezoelectric accelerometer is presented. Using the metamodeling to approximate the relationship between the design variables and the performances, the constituent components were optimized so that the generated electric voltage, representing sensitivity, could be maximized at different set values of the resonant frequency (25-40 kHz). Four kinds of optimized designs were created and fabricated into the accelerometer modules for empirical validation. The accelerometer modules fabricated according to the optimized designs were highly reliable with a broad range of resonant frequency as well as sufficiently high values of charge sensitivity. The fixed (or mounted) resonant frequency was between 16.1-30.1 kHz based on the impedance measurement. The charge sensitivity decreased from 296.8 to 79.4 pC/g with an increase of the resonant frequency, showing an inverse relation with respect to the resonant frequency. The design-dependent behaviors of the sensitivity and resonant frequency were almost identical in both numerical analysis and experimental investigation. This work shows that the piezoelectric accelerometer can be selectively prepared with best outcomes according to the requirements for the sensitivity and resonant frequency, fundamentally associated with trade-off relation.

Piezoelectric Energy Harvesting from Two-Dimensional Boron Nitride Nanoflakes.

Two-dimensional (2D) piezoelectric hexagonal boron nitride nanoflakes (h-BN NFs) were synthesized by a mechanochemical exfoliation process and transferred onto an electrode line-patterned plastic substrate to characterize the energy harvesting ability of individual NFs by external stress. A single BN NF produced alternate piezoelectric output sources of ∼50 mV and ∼30 pA when deformed by mechanical bendings. The piezoelectric voltage coefficient (g11) of a single BN NF was experimentally determined to be 2.35 × 10-3 V·m·N-1. The piezoelectric composite composed of BN NFs and an elastomer was spin-coated onto a bulk Si substrate and then transferred onto the electrode-coated plastic substrates to fabricate a BN NFs-based flexible piezoelectric energy harvester (f-PEH) which converted a piezoelectric voltage of ∼9 V, a current of ∼200 nA, and an effective output power of ∼0.3 µW. This result provides a new strategy for precisely characterizing the energy generation ability of piezoelectric nanostructures and for demonstrating f-PEH based on 2D piezomaterials.

Design Optimization of Bulk Piezoelectric Acceleration Sensor for Enhanced Performance.

While seeking to achieve high performances of a bulk piezoelectric acceleration sensor, we investigated the behavior of the design variables of the sensor components and optimized the sensor design using a numerical simulation based on piezoelectric analysis and metamodeling. The optimized results demonstrated that there was an exponential dependency in the trade-off relation between two performance indicators, the electric voltage and the resonant frequency, as induced by the design characteristics of the sensor. Among the design variables, a decrease in the base height and epoxy thickness and an increase in the piezo element's inner diameter had a positive effect on two performances, while the head dimensions (diameter and height) exhibited the opposite effect on them. The optimal sensor designs are proposed within the valid range of resonant frequency (25-47.5 kHz). Our redesign of a commercial reference sensor improved the resonant frequency by 13.2% and the electric voltage by 46.1%.

Proposal of a rhombohedral-tetragonal phase composition for maximizing piezoelectricity of (K,Na)NbO3 ceramics.

Great progress in the field of piezoelectricity of (K,Na)NbO3 (KNN) lead-free ceramics, driven by emerging rhombohedral-tetragonal (R-T) phase boundary, has instigated research activity regarding elaborate controls of the phase boundary structure. Through phase-microstructure-property mapping in KNN ceramics doped with Bi-containing perovskite oxides, in this study we for the first time report the existence of a certain R-T phase boundary state by which to create maximum piezoelectric response in KNN systems. This phase boundary condition is usually comprised of approximately 15% R phase and 85% T phase, regardless of the choice of dopant material. Any deviation from this phase composition, either by inclusion of orthorhombic (O) phase or by enrichment of R phase, has a negative effect on the value of d33. These findings can provide useful guidance for chemical doping control associated with the type of phase boundary and the phase composition for advanced KNN-based materials.

Aging-resistant nanofluids containing covalent functionalized boron nitride nanosheets.

Developing a thermally stable nanofluid that can maintain good thermo-conductive and flow performance at moderate or elevated temperatures for prolonged periods of time is a great challenge in heat transfer applications. Here, the thermal conductivity and rheological properties as well as their thermal stability characteristics of a nanofluid containing two-dimensional (2D) hexagonal boron nitride nanosheets (h-BNNSs) in ethylene glycol (EG) are presented, in comparison with those for a graphene oxide (GO) nanofluid as a counterpart. In place of a surfactant, hydroxyl functional groups covalently bound to the BNNS surface provided excellent compatibility and stable dispersion of the particles within EG at temperatures up to 90 °C. Owing to the percolation effect of the 2D sheets, the thermal conductivity of the EG base fluid was significantly enhanced by 80% at 5 vol% of BNNS, superior to that of the GO fluid. Moreover, the BNNS fluids exhibited excellent long-term stability at 90 °C for 5 d without loss of their high thermal conductivity, low viscosity and electrical insulating property, whereas the GO fluids underwent thermal degradation with irreversible particle aggregation and increasing viscosity due to the selective chemical reduction of the surface functional groups (i.e., C-O groups) of the GO.

Rapid and direct synthesis of complex perovskite oxides through a highly energetic planetary milling.

The search for a new and facile synthetic route that is simple, economical and environmentally safe is one of the most challenging issues related to the synthesis of functional complex oxides. Herein, we report the expeditious synthesis of single-phase perovskite oxides by a high-rate mechanochemical reaction, which is generally difficult through conventional milling methods. With the help of a highly energetic planetary ball mill, lead-free piezoelectric perovskite oxides of (Bi, Na)TiO3, (K, Na)NbO3 and their modified complex compositions were directly synthesized with low contamination. The reaction time necessary to fully convert the micron-sized reactant powder mixture into a single-phase perovskite structure was markedly short at only 30-40 min regardless of the chemical composition. The cumulative kinetic energy required to overtake the activation period necessary for predominant formation of perovskite products was ca. 387 kJ/g for (Bi, Na)TiO3 and ca. 580 kJ/g for (K, Na)NbO3. The mechanochemically derived powders, when sintered, showed piezoelectric performance capabilities comparable to those of powders obtained by conventional solid-state reaction processes. The observed mechanochemical synthetic route may lead to the realization of a rapid, one-step preparation method by which to create other promising functional oxides without time-consuming homogenization and high-temperature calcination powder procedures.

Nanogenerators consisting of direct-grown piezoelectrics on multi-walled carbon nanotubes using flexoelectric effects.

We report the first attempt to prepare a flexoelectric nanogenerator consisting of direct-grown piezoelectrics on multi-walled carbon nanotubes (mwCNT). Direct-grown piezoelectrics on mwCNTs are formed by a stirring and heating method using a Pb(Zr0.52Ti0.48)O3 (PZT)-mwCNT precursor solution. We studied the unit cell mismatch and strain distribution of epitaxial PZT nanoparticles, and found that lattice strain is relaxed along the growth direction. A PZT-mwCNT nanogenerator was found to produce a peak output voltage of 8.6 V and an output current of 47 nA when a force of 20 N is applied. Direct-grown piezoelectric nanogenerators generate a higher voltage and current than simple mixtures of PZT and CNTs resulting from the stronger connection between PZT crystals and mwCNTs and an enhanced flexoelectric effect caused by the strain gradient. These experiments represent a significant step toward the application of nanogenerators using piezoelectric nanocomposite materials.

Precisely Determining Ultralow level UO2(2+) in Natural Water with Plasmonic Nanowire Interstice Sensor.

Uranium is an essential raw material in nuclear energy generation; however, its use raises concerns about the possibility of severe damage to human health and the natural environment. In this work, we report an ultrasensitive uranyl ion (UO2(2+)) detection method in natural water that uses a plasmonic nanowire interstice (PNI) sensor combined with a DNAzyme-cleaved reaction. UO2(2+) induces the cleavage of DNAzymes into enzyme strands and released strands, which include Raman-active molecules. A PNI sensor can capture the released strands, providing strong surface-enhanced Raman scattering signal. The combination of a PNI sensor and a DNAzyme-cleaved reaction significantly improves the UO2(2+) detection performance, resulting in a detection limit of 1 pM and high selectivity. More importantly, the PNI sensor operates perfectly, even in UO2(2+)-contaminated natural water samples. This suggests the potential usefulness of a PNI sensor in practical UO2(2+)-sensing applications. We anticipate that diverse toxic metal ions can be detected by applying various ion-specific DNA-based ligands to PNI sensors.

The role of hand-assisted laparoscopic surgery in a right hemicolectomy for right-sided colon cancer.

PURPOSE: The purpose of this study is to evaluate the perioperative and long-term oncologic outcomes of hand-assisted laparoscopic surgery (HALS) and standard laparoscopic surgery (SLS) and assess the role of HALS in the management of right-sided colon cancer. METHODS: The study group included 53 patients who underwent HALS and 45 patients who underwent SLS for right-sided colon cancer between April 2002 and December 2008. RESULTS: The patients in each group were similar in age, American Society of Anesthesiologist (ASA) score, body mass index, and history of previous abdominal surgeries. Eight patients in the HALS group and no patient in the SLS group exhibited signs of tumor invasion into adjacent structures. No differences were noted in the time to return of normal bowel function, time to toleration of diet, lengths of hospital stay and narcotic usage, and rate of postoperative complications. The median incision length was longer in the HALS group (HALS: 7.0 cm vs. SLS: 4.8 cm, P < 0.001). The HALS group had a significantly higher pathologic TNM stage and significantly larger tumor size (HALS: 6.0 cm vs. SLS: 3.3 cm, P < 0.001). The 5-year overall, disease-free, and cancer-specific survival rates of the HALS and the SLS groups were 87.3%, 75.2%, and 93.9% and 86.4%, 78.0%, and 90.7%, respectively (P = 0.826, P = 0.574, and P = 0.826). CONCLUSION: Although patients in the HALS group had more advanced disease and underwent more complex procedures than those in the SLS group, the short-term benefits and the oncologic outcomes between the two groups were comparable. HALS can, therefore, be considered an alternative to SLS for bulky and fixed right-sided colon cancer.

Effects of sintering temperature on the pyrochlore phase in PZT nanotubes and their transformation to the perovskite phase by coating with PbO multilayers.

We report the phase evolution of Pb(Zr0.52Ti0.48)O3 nanotubes (PZT-NTs), from the pyrochlore to perovskite phase, with an outer diameter of about 420 nm and a wall thickness of about 10 nm. The PZT-NTs were fabricated in pores of porous anodic alumina membrane (PAM) using a spin coating of PZT sol-gel solution and subsequent annealing at 500-700 degrees C in oxygen gas. The pyrochlore phase was found to be formed at 500 degrees C, and also found not to be transformed into the perovskite phase, even though annealing was performed at higher temperatures to 700 degrees C. Elementary distribution analysis of PZT-NTs embedded in PAM reveal that Pb diffusion from nanotubes into pore walls of PAM is one of the main reasons. By employing firstly an additional PbO coating on the pyrochlore nanotubes and then subsequent annealing at 700 degrees C, we have successfully achieved an almost pure perovskite phase in nanotubes. These results suggest that PbO acts as a Pb-compensation agent in the Pb- deficient PZT-NTs. Moreover, our method can be used in the synthesis of all metal-oxide materials, including volatile elements.

Phototoxic effect of blue light on the planktonic and biofilm state of anaerobic periodontal pathogens.

PURPOSE: The purpose of this study was to compare the phototoxic effects of blue light exposure on periodontal pathogens in both planktonic and biofilm cultures. METHODS: Strains of Aggregatibacter actinomycetemcomitans, Fusobacterium nucleatum, and Porphyromonas gingivalis, in planktonic or biofilm states, were exposed to visible light at wavelengths of 400.520 nm. A quartz-tungsten-halogen lamp at a power density of 500 mW/cm(2) was used for the light source. Each sample was exposed to 15, 30, 60, 90, or 120 seconds of each bacterial strain in the planktonic or biofilm state. Confocal scanning laser microscopy (CSLM) was used to observe the distribution of live/dead bacterial cells in biofilms. After light exposure, the bacterial killing rates were calculated from colony forming unit (CFU) counts. RESULTS: CLSM images that were obtained from biofilms showed a mixture of dead and live bacterial cells extending to a depth of 30-45 µm. Obvious differences in the live-to-dead bacterial cell ratio were found in P. gingivalis biofilm according to light exposure time. In the planktonic state, almost all bacteria were killed with 60 seconds of light exposure to F. nucleatum (99.1%) and with 15 seconds to P. gingivalis (100%). In the biofilm state, however, only the CFU of P. gingivalis demonstrated a decreasing tendency with increasing light exposure time, and there was a lower efficacy of phototoxicity to P. gingivalis as biofilm than in the planktonic state. CONCLUSIONS: Blue light exposure using a dental halogen curing unit is effective in reducing periodontal pathogens in the planktonic state. It is recommended that an adjunctive exogenous photosensitizer be used and that pathogens be exposed to visible light for clinical antimicrobial periodontal therapy.

Reliability evaluation of nano-bi/silver paste sensor electrode for detecting trace metals.

The reliability of sensor characteristics for a nano-bismuth (Bi)/silver (Ag) paste electrode has been investigated by comparison with Hg/Bi film electrodes in terms of accuracy and precision. Using Ag paste instead of carbon paste as a conducting layer, the sensitivity and detection limit of the sensor electrode were more enhanced due to a lower electrical conductivity of Ag. For the evaluation of detecting ability, the Zn, Cd, and Pb ion concentrations of the prepared standard solutions were experimentally measured on Hg film, Bi film, and nano-Bi electrodes using anodic stripping voltammetry. A nano-Bi electrode can detect Zn, Cd, and Pb ions at 0.1 ppb with higher precision and accuracy compared with Hg film and Bi film electrodes. From the trace analyses of Zn, Cd, and Pb ions in commercial drinking water and river water using a nano-Bi electrode and inductively coupled plasma (ICP) technique, it was concluded that the nano-Bi electrode exhibited excellent sensing characteristics with high reliability, and could detect even traces of Zn, Cd, and Pb ions that were not detected by the ICP method.

The effect of implant shape and bone preparation on primary stability.

PURPOSE: The purpose of this study was to evaluate the effects of implant shape and bone preparation on the primary stability of the implants using resonance frequency analysis. METHODS: Sixty bovine rib blocks were used for soft and hard bone models. Each rib block received two types of dental implant fixtures; a straight-screw type and tapered-screw type. Final drilling was done at three different depths for each implant type; 1 mm under-preparation, standard preparation, and 1 mm over-preparation. Immediately after fixture insertion, the implant stability quotient (ISQ) was measured for each implant. RESULTS: Regardless of the bone type, the ISQ values of the straight-screw type and tapered-screw type implants were not significantly different (P > 0.05). Depth of bone preparation had no significant effect on the ISQ value of straight-screw type implants (P > 0.05). For the tapered-screw type implants, under-preparation significantly increased the ISQ value (P < 0.05), whereas overpreparation significantly decreased the ISQ value (P < 0.05). CONCLUSIONS: Within the limitations of this study, it is concluded that bone density seemed to have a prevailing effect over implant shape on primary stability. The primary stability of the tapered-screw type implants might be enhanced by delicate surgical techniques.

Marginal bony changes in relation to different vertical positions of dental implants.

PURPOSE: The purpose of this study was to radiographically evaluate marginal bony changes in relation to different vertical positions of dental implants. METHODS: Two hundred implants placed in 107 patients were examined. The implants were classified by the vertical positions of the fixture-abutment connection (microgap): 'bone level,' 'above bone level,' or 'below bone level.' Marginal bone levels were examined in the radiographs taken immediately after fixture insertion, immediately after second-stage surgery, 6 months after prosthesis insertion, and 1 year after prosthesis insertion. Radiographic evaluation was carried out by measuring the distance between the microgap and the most coronal bone-to-implant contact (BIC). RESULTS: Immediately after fixture insertion, the distance between the microgap and most coronal BIC was 0.06 ± 0.68 mm; at second surgery, 0.43 ± 0.83 mm; 6 months after loading, 1.36 ± 0.56 mm; and 1 year after loading, 1.53 ± 0.51 mm (mean ± SD). All bony changes were statistically significant but the difference between the second surgery and the 6-month loading was greater than between other periods. In the 'below bone level' group, the marginal bony change between fixture insertion and 1 year after loading was about 2.25 mm, and in the 'bone level' group, 1.47 mm, and in 'above bone level' group, 0.89 mm. Therefore, the marginal bony change was smaller than other groups in the 'above bone level' group and larger than other groups in the 'below bone level' group. CONCLUSIONS: Our results demonstrated that marginal bony changes occur during the early phase of healing after implant placement. These changes are dependent on the vertical positions of implants.

Effect of phase stability degradation of bismuth on sensor characteristics of nano-bismuth fixed electrode.

Effect of phase stability degradation of bismuth on sensor characteristics of nano-bismuth fixed electrode has been investigated using square-wave anodic stripping voltammetry technique, scanning electron microscopy (SEM) and X-ray diffraction (XRD) spectroscopy. From the analyses of square-wave anodic stripping voltammograms (SWASV) repetitively measured on the nano-bismuth fixed electrode, it was found that the oxidation peak currents dropped by 81%, 68% and 59% for zinc, cadmium and lead, respectively, after the 100th measurement (about 400 min of operation time). The sphere bismuth nanoparticles gradually changed to the agglomerates with petal shape as the operation time increased. From the analyses of SEM images and XRD patterns, it is confirmed that the oxidation of Bi into BiOCl/Bi(2)O(2)CO(3) and the agglomeration of bismuth nanoparticles caused by the phase change decrease a reproducibility of the stripping voltammetric response. Moreover, most of the bismuth becomes BiOCl at pH 3.0 and bismuth hydroxide, Bi(OH)(3) at pH 7.0, which results in a significant decrease in sensitivity of the nano-bismuth fixed electrode.

Homogeneous dispersion of TiC nano particles in a cast carbon steel matrix.

Metal matrix nano-composites (MMNCs) (metal matrix with nano-sized ceramic particles) can be of great significance because of their high performance and thus it would be advantageous to produce as-cast bulk MMNCs. However, it is so difficult to disperse nano-sized ceramic particles uniformly in molten metal. In this study, carbon steel matrix composites with a homogeneous dispersion of TiC nano particles were fabricated by conventional liquid metal casting method. In order to get highly wettable nano-sized TiC ceramic particles, the micro-sized (approximately 10 m) TiC particles were first mechanically milled (MMed) by Cu in a high-energy ball mill machine (MMed TiC/Cu), and then mixed with Sn powders to obtain better wettability, as this lowered the surface tension of the carbon steel melt. According to OM images, an addition of MMed TiC/Cu-Sn mixed powders favorably disperses the TiC nano particles in the carbon steel matrix. SEM and EDS images revealed that spherical particles with several hundreds of nanometers were distributed uniformly in the carbon steel matrix. It was also found that the grain size refinement of the cast matrix is achieved remarkably when TiC nano particles were added due to the fact that TiC nano particles act as nucleation sites during the solidification process.

Synthesis of nanocrystalline bismuth and its application to the detection of trace metals.

Surface modified carbon strip electrode with Bi nanopowder was suggested for a simultaneous analysis of Zn, Cd, and Pb ions by a square wave anodic stripping voltammetry, and the influence of the modifying Bi mass and particle size on the trace metal response was investigated. The Bi nanopowders with various particle size distributions were synthesized by an optimization of the gas condensation condition, in which a refractory crucible was applied for the evaporation of volatile Bi, and then immobilized on the surface of a working electrode. The result of the stripping measurements shows that when the modifying mass and the particle size of the Bi powder were in the range of 2 to 5 microg/cm2 and less than 300 nm, respectively, a well-developed and reproducible stripping response was obtained. The proposed "mercury-free" carbon strip electrode, modified with Bi nanopowder, is conveniently usable and directly applicable to a trace metal analysis without a pre-deposition of Bi and complicated surface polishing steps.