Biocompatibility of borosilicate glass-ceramics based LTCC materials for microfluidic biosensor application

Three kinds of borosilicate glass-ceramics Low temperature co-fired ceramics (LTCC) substrate materials, Ca-B-Si-O (CBS), Ca-Al-B-Si-O (CABS), and Ca-Mg-B-Si-O (CMBS), have been prepared, and the biocompatibility of these materials was evaluated. Compared with CBS and CMBS samples, the CABS sample presented the lowest crystallinity and dissolution in the bioleaching experiments. The direct and indirect cell culturing results showed that the CABS sample also possessed the best biocompatibility to the bone mesenchymal stem cells (BMSCs) due to its good bio-stability and surface micro-pore structure. The effects of surface topography and released ions on cytocompatibility were analyzed. These results were expected to offer some guideline information for developing LTCC substrate materials used in the microfluidic biosensors for the future biological and medical application.     

Intrinsic Elastic, Dielectric, and Piezoelectric Losses in Lead Zirconate Titanate Ceramics Determined by an Immittance-Fitting Method

The material coefficients of "soft" and "hard" lead zirconate titanate (PZT) ceramics were determined as complex values by the nonlinear least-squares-fitting of immittance data measured for length-extensional bar resonators. The piezoelectric d -constant should be a complex value to obtain a best fitting between observed and calculated results. Because the elastic, dielectric, and piezoelectric losses determined in this process were not "intrinsic" losses, a calculation process to evaluate the "intrinsic" losses was proposed. It was confirmed that the intrinsic losses were smaller than the corresponding extrinsic losses. The intrinsic piezoelectric loss existed in both soft and hard PZTs; ∼50% of the loss of piezoelectric d -constant was derived from the elastic and dielectric losses. The most notable difference between the soft and hard PZTs was observed in their elastic losses.     

Effect of dopant precursors on the optical properties of rare-earths doped oxyfluoride glass-ceramics

The crystallization of fluoride nanocrystals (NCs) in chemically and mechanically stable aluminosilicate glasses has shown interesting optical properties even for small crystal fractions (10-15 wt%). When rare-earth (RE) ions are used as dopants, crystal-like features can be reproduced and an increase in the emission and/or energy transfer processes, with respect to the starting glasses, is observed. A crucial point for these materials is the study of the local surrounding of RE ions and their incorporation in the NCs. In fact, the effective concentration in the NCs can be much higher than the nominal concentration, up to one order of magnitude or even higher. The knowledge of RE ions incorporation in the NCs permits choosing proper doping levels to optimize both linear and nonlinear optical properties. In this work, transparent oxyfluoride glass-ceramics with LaF₃ NCs, doped with Nd³⁺ and Er³⁺ using oxide and fluoride precursors, were prepared using the melt-quenching method and controlled crystallization. The local surrounding of the RE ions was studied using X-ray absorption spectroscopy, electron paramagnetic resonance and photoluminiscence. The results show that most RE ions are already in a fluorine-rich amorphous environment even in the initial glass. The crystallization process provokes the RE ion redistribution and incorporation in the fluoride NCs. The different RE precursors, used as oxides or fluorides, have an influence on the incorporation of the RE in the NCs and, as a consequence, on the final optical properties.     

Control of Crystal Orientation and Piezoelectric Response of Lead Zirconate Titanate Thin Films Near the Morphotropic Phase Boundary

PbZr_0.53Ti_0.47O₃ (PZT) thin films with various preferred crystallographic orientations were synthesized on various substrates using pulsed laser deposition techniques. Larger piezoelectric displacement, which involved the bending vibration of the PZT film/substrate, was observed in randomly oriented PZT thin film than that in (100)- and (111)-preferred texture films. This result was discussed by correlation with the number of effective spontaneous polarization axes in the morphotropic phase boundary of the PZT system. Moreover, polarization fatigue was found to lower the electric-field-induced displacement significantly, indicating a large contribution of ferroelectric domain motion to the piezoelectric response of PZT thin films under bipolar drive.     

Fabrication and Evaluation of Porous Piezoelectric Ceramics and Porosity–Graded Piezoelectric Actuators

Porous ceramics of lead zirconate titanate (PZT) were prepared by sintering powder compacts consisting of PZT and stearic acid powders in an air atmosphere; stearic acid was added as a pore-forming agent (PFA). The dielectric, elastic and piezoelectric properties of uniformly porous PZT ceramics were investigated as a function of the porosity volume fraction. Furthermore, a beam-shaped PZT actuator sample with a graded porosity content across its thickness was fabricated by sintering PFA-graded powder compacts. The electric-field-induced bending displacement characteristics of the actuator samples were measured by using strain gauges and were found to be in good agreement with the theoretical predication based on a classical lamination theory.     

Cement-Based 0-3 Piezoelectric Composites

To meet the requirements of development for smart or intelligent structures in civil engineering, new functional materials that have good compatibility with civil engineering structural materials are needed. In this study, for the first time in the field of piezoelectric materials, cement-based 0-3 piezoelectric (PZT) composites were fabricated by the normal mixing and spreading method. The new materials have very good compatibility with portland cement concrete. The cement-based 0-3 piezoelectric composites were shown to have a slightly higher piezoelectric factor and electromechanical coefficient than those of 0-3 PZT/polymer composites with a similar content of PZT particles; thus, they are adequate for sensor application. There is potential for the application of cement-based 0-3 PZT composites in civil engineering because of their better piezoelectric properties and good compatibility with portland cement concrete.     

Strength Evaluation of Piezoelectric Ceramics under Transient Thermal Environments

The strength of piezoelectric ceramics is analyzed for a plate suddenly exposed to an environmental medium of different temperatures. The admissible temperature jump the material can sustain is studied using the stress- and fracture-toughness-based failure criteria. The critical parameters governing the level of the transient thermal stress in piezoelectric ceramics are identified. Solutions are obtained for the maximum thermal shock that the plate can sustain without failure, under the conditions that (i) maximum local tensile stress equals the tensile strength of the ceramic, and (ii) maximum stress intensity factor for representative pre-existing cracks equals the fracture toughness of the ceramic.     

Crystallization control in Ni2+-doped glass-ceramics for broadband near-infrared luminesce

The research of doped photonic glass has recently attracted much attention owning to the significant applications in various fields, including lasers, photovoltaics, and optical amplification. In this work, we present the design, fabrication, and experimental implementation of a novel fluorosilicate photonic glass-ceramics with broadband luminescence. We demonstrate that precipitated nanocrystals can be tuned by changing the heat-treatment temperature. This proposal offers an excellent opportunity for controlling the local environment around Ni²⁺ dopant. Consequently, the broadband and flat emission covering a waveband from 1200 to 2400 nm with a bandwidth of 605 nm can be realized. The possible physical mechanism, which can be attributed to the gradual change of nanocrystals from K₂SiF₆ to KCdF₃ with the enhancement of the heat-treatment temperature, is also discussed.     

Dielectric, Piezoelectric, and Pyroelectric Properties of Lead Zirconate—Lead Zinc Niobate Ceramics

New piezoelectric and pyroelectric ceramics consisting of antiferroelectric lead zirconate (PZ) and relaxor ferroelectric lead zinc niobate (PZN) are studied from an application view-point of the field-induced antiferroelectric-to-ferroelectric phase transition. An antiferroelectric-ferroelectric phase boundary exists in PbZr_x(Zn_1/3Nb_2/3)_1−xO₃ (PZZN-1000x) close to x = 0.93 to 0.94 at room temperature. A new ferroelectric rhombohedral phase change, F_α–F'_α, at low temperature is found and studied by the temperature dependence of the pyroelectric coefficient. Electrical poling in these ceramics is easy, and the coercive field E_c∼8 to kV/cm is rather low. Samples with compositions in the range PZZN-86 to PZZN-92 have a large electromechanical coupling constant, k (k_t and k₁₅∼50% to 60%), and a low dielectric constant, ɛ_s (ɛ^T₃₃/ɛ₀= 260 to 320, ɛ^T₁₁/ɛ₀= 380). PZZN ceramics appear to be potential candidates for high-frequency ultrasonic transducers used in the thickness shear mode. The pyroelectric figure of merit (F_v) of these ceramics is comparable to the values published for the PZT-based or PbTiO₃-based materials.     

Antiferroelectrics: History,fundamentals, crystal chemistry,crystal structures,size effects,and applications

Antiferroelectric (AFE) materials are of great interest owing to their scientific richness and their utility in high-energy density capacitors. Here, the history of AFEs is reviewed, and the characteristics of antiferroelectricity and the phase transition of an AFE material are described. AFEs are energetically close to ferroelectric (FE) phases, and thus both the electric field strength and applied stress (pressure) influence the nature of the transition. With the comparable energetics between the AFE and FE phases, there can be a competition and frustration of these phases, and either incommensurate and/or a glassy (relaxor) structures may be observed. The phase transition in AFEs can also be influenced by the crystal/grain size, particularly at nanometric dimensions, and may be tuned through the formation of solid solutions. There have been extensive studies on the perovskite family of AFE materials, but many other crystal structures host AFE behavior, such as CuBiP₂Se₆. AFE applications include DC-link capacitors for power electronics, defibrillator capacitors, pulse power devices, and electromechanical actuators. The paper concludes with a perspective on the future needs and opportunities with respect to discovery, science, and applications of AFE.     

Piezoelectric softening by Nb substitution in (Ba,Pb)ZrO3 ceramics

Donor doping is commonly applied for softening of the piezoelectric and dielectric properties and facilitation of polarization switching in the ubiquitous Pb(Zr,Ti)O₃ [PZT] ceramics. The origin of the donor‐dopant effects is not entirely clear. (Pb,Ba)ZrO₃ [PBZ] is a related ferroelectric material, its perovskite A‐site being partially occupied by the larger Ba⁺² cation, less prone to evaporation than Pb⁺², and the B‐site is occupied entirely by the valency‐stable Zr⁺⁴. Here we report on our studies of Nb⁺⁵ doping effects in (Pb,Ba)ZrO₃. Similarly, to past observations on La⁺³ and Nb⁺⁵ doped PZT, we find a strong reduction in relative density of PBZ when the doping is <0.5 atomic %. This is accompanied by lattice parameter reduction, enhanced PbO loss, smaller grain size and deterioration of dielectric, piezoelectric and polarization switching properties, the latter being opposite of expected softening effect. All those observations can be interpreted in terms of the Nb entering A‐site at small concentrations. This is supported by ab‐inito calculations and analysis of the possible defect reaction equations. The structure and microstructure of PBZ with Nb>0.2% are consistent with Nb⁺⁵ entering the B‐site and softening effects are observed. The study supports the scenario of hardening due to domain walls pinning by V_Pb‐V_O divacancies and softening upon decrease in their concentration.     

Toughening of Glass by a Piezoelectric Secondary Phase

A toughening concept for glass, based on exploiting the ferroelastic effect of piezoelectric particles embedded in a glass matrix, is described. It is hypothesized that the domains within a piezoelectric phase will align themselves in the direction of the stress field around an advancing crack, thus absorbing energy and contributing to toughening. A powder technology route was optimized to fabricate lead-containing glass-matrix composites with up to 30 wt% of a lead zirconate titanate (PZT) particulate phase. An increase in fracture toughness of >50% was achieved via the addition of 30 wt% of PZT particles. Although other toughening mechanisms could be excluded in the present composites, the actual contribution of piezoelectric toughening remains under investigation.     

Method for Obtaining the Full Set of Linear Electric, Mechanical, and Electromechanical Coefficients and All Related Losses of a Piezoelectric Ceramic

A method based on the use of four piezoelectric resonances for three sample geometries is presented that allows one to obtain all the dielectric permittivities, compliances, and piezoelectric coefficients of a piezoelectric ceramic in complex form and, therefore, all related losses. Piezoelectric losses are responsible for heat generation and hysteresis in actuators. The method is applied to a Navy type II PZT-based piezoelectric ceramic (PZT = lead zirconate titanate), for which the full set of linear electric, mechanical, and electromechanical coefficients is given in complex form. Full sets of coefficients for the available piezoceramics are required for exploiting all the possibilities of finite element analysis, both in fundamental research (mechanisms of degradation) and in development (element design). This numerical technique is necessary to explore arbitrary shapes provided by solid free-form-fabrication technologies.     

Fabrication of Piezoelectric Ceramic/Polymer Composite Transducers Using Fused Deposition of Ceramics

The fused deposition of ceramics (FDC) technique was used to fabricate piezoelectric ceramic skeletons for the development of piezoelectric composite transducers with 2–2 connectivity for medical imaging. The green parts were designed to have 30 vol% lead zirconate titanate ceramic (PZT-5H) in the final composites. Physical characterization of the sintered samples revealed that 96% of the theoretical density was achieved. Optical microscopy showed that defects due to the FDC mode of deposition, such as small roads and bubbles, were eliminated, because of improvements in powder processing. The electromechanical properties of the final composites were similar to the properties that were obtained for conventionally made composites. A matching layer and a backing layer, as well as wires and an inductor, were added to each FDC composite to fabricate a functional medical imaging transducer. The devices were tested in water using a steel target 3.5 cm thick. Echoes from the target could be detected with all the transducers that were fabricated using FDC. The sensitivities of the transducers were similar to that of a commercial transducer. However, the ringing was much longer than that for a commercial transducer, because the backing layer was not optimized in the transducers that were fabricated using FDC.     

High Piezoelectric Voltage Coefficient in Structured Lead‐Free (K,Na,Li)NbO3 Particulate—Epoxy Composites

A high‐voltage coefficient has been found in lead‐free piezoelectric particulate composites based on epoxy with lead‐free (K_0.50Na_0.50)_0.94Li_0.06NbO₃ (KNLN) piezoceramic particles with a natural cubic morphology. The KNLN powder used in the composites has been prepared using a new solid‐state double calcination processing route. These particles were subsequently used to create random and structured KNLN‐epoxy composites. Using dielectrophoresis, these natural cubical KNLN particles were structured into one‐dimensional chains inside the epoxy matrix. Composites produced with these powders showed piezoelectric properties about a factor of 2 higher than those of composites processed with conventionally calcined KNLN powders. The dielectrophoretically structured KNLN‐epoxy composites with optimized particle size and morphology showed excellent piezoelectric properties, which can replace lead containing piezoelectric composites for sensor and energy harvesting applications in future.     

Diffusion of 110mAg Tracer in Polycrystalline and Single-Crystal Lead-Containing Piezoelectric Ceramics

We have conducted diffusion measurements of radioactive ^110mAg tracer in single-crystal PbMgNbO₃–PbTiO₃ (PMN-PT) and in polycrystalline 50Pb(Ni_1/3Nb_2/3)O₃·35PbTiO₃·15PbZrO₃ (PNN-PT-PZ) piezoelectric ceramics. Both materials measured belong to the perovskite family. Diffusion in PMN-PT is characterized by an activation energy of 277 kJ/mol and pre-exponential factor of 0.0034 m²/s and compares well with cation diffusion in high-temperature superconducting YBa₂Cu₃O_7–δ. Diffusion in polycrystalline PNN-PT-PZ, on the other hand, is many orders of magnitude faster and is attributed to grain boundaries. PNN-PT-PZ has a lower activation energy, 168 kJ/mol, and a combined pre-exponential factor ( s δ( D _b)_o, where s is the segregation factor of silver, δ the thickness, and ( D _b)_o the pre-exponential factor for grain boundaries) of 3.7 × 10⁻⁹ m³/s. The unusually large combined pre-exponential factor infers large segregation of silver at the grain boundaries and small solid solubility within the grains. It is possible, using a semiempirical model, to compute metal– (silver–) ceramic interface energies as a function of temperature, from which values of 90 kJ/mol and 0.9 R are obtained for enthalpy and entropy, respectively, for grain-boundary segregation.     

Improvement in Time-Dependent Displacement Degradation of Piezoelectric Ceramics by Manganese/Indium Addition

High-durability lead zirconate titanate (PZT) ceramics were developed in the present study to prevent time-dependent deterioration of displacement, as well as failure under operation. Current leakage in PZT was decreased by adding elemental manganese, changing the zirconium content from 54.0 to 54.2 mol%, and decreasing the antimony content. Displacement was improved by adding both manganese and indium to the PZT. The present investigation resulted in the development of PZT compositions with high displacement and low time-dependent displacement degradation. These results were confirmed by analyzing stack actuators made from enhanced PZT compositions.     

Large Electrostrain in K(Nb1−xMnx)O3 Lead‐Free Piezoelectric Ceramics

K(Nb_1?xMn_x)O₃ (KN_1?xM_x) ceramics with 0.005 ≤ x ≤ 0.015 were sintered at 1020°C through a normal sintering process without the formation of a liquid phase. They exhibited double polarization versus electric field (P–E) hysteresis and sprout‐shaped strain versus electric field (S–E) curves owing to the presence of a defect dipole (P_D), which was formed between the acceptor Mn³⁺ ion and the oxygen vacancy. Moreover, the aging process was not required to develop the P_D. The KN_1?xM_x ceramics exhibited a large strain of ~0.2% at 6.0 kV/mm. For the KN_0.985M_0.015 ceramic, this large strain was maintained after 10⁴ cycles of an electric field of 6.0 kV/mm. This ceramic also maintained a double hysteresis curve at 200°C. Therefore, the KN_0.985M_0.015 ceramic has a large electric field‐induced strain, along with good thermal and fatigue properties for multilayer piezoelectric actuators.     

Effects of Octahedral Tilting on the Piezoelectric Properties of Strontium/Barium/Niobium-Doped Soft Lead Zirconate Titanate Ceramics

(Pb_1−x−ySr_xBa_y)(Zr_0.976−zTi_zNb_0.024)O₃ solid solutions have been investigated to understand the relationship between structural changes caused by isovalent strontium and barium substitution on the A-site and dielectric and piezoelectric properties. As strontium and barium were substituted for lead, the zirconium:titanium (Zr:Ti) ratio was modified so that all compositions had an optimized piezoelectric coefficient (d₃₃). The value of d₃₃ was at a maximum in the tetragonal phase near, but not at, the morphotropic-phase boundary (MPB). The real MPB was taken as the Zr:Ti ratio at which X-ray diffraction patterns appeared either pseudocubic or a mixture of rhombohedral and tetragonal. As strontium content increased, optimized d₃₃ also increased from 410 pC/N (x= 0) to 640 pC/N (x= 0.12), commensurate with a decrease in the paraelectric-to-ferroelectric phase transition temperature (T_C) from 350°C (x= 0) to 175°C (x= 0.12). However, for ceramics where x > 0.12, optimized d₃₃ decreased even though the phase-transition temperature was ∼150°C. Low strontium concentration ceramics (x= 0–0.08) contained 80 nm ferrroelectric domains typical of PZT, but high strontium concentration ceramics (x= 0.12–0.16) contained fine-scale domains (20 nm) in some regions of the microstructure. In addition, [110] pseudocubic electron diffraction patterns revealed superlattice reflections at 1/2{hkl} positions associated with rotations of the octahedra in antiphase. Co-doping ceramics with strontium (x= 0.06) and barium (y= 0.06) resulted in the disappearance of the 1/2{hkl} reflections. Optimized d₃₃ (∼520 pC/N, T_C∼ 205°C) for this composition was similar to that of ceramics where x= 0.08, y= 0, which had a T_C of ∼250°C.     

Movers,shakers, and storers of charge: The legacy of ferroelectricians L. Eric Cross and Robert E. Newnham

The last 100 years has seen the burgeoning of the field of ferroelectrics from a scientific curiosity to the basis of major industries in capacitors, piezoelectrics, and electro‐optics. This paper will discuss the history of the field, with an emphasis on the contributions made by Professors Robert E. Newnham and L. Eric Cross of the Pennsylvania State University. Their scientific contributions encompassed many key areas in ferroelectrics, including phenomenology, structure determination, relaxor ferroelectrics, composite piezoelectrics, structure‐property relations, and flexoelectricity. Scientific advances were often motivated by and closely coupled with application needs. Finally, their impact on global academic communities is discussed.