Phase transition,microstructure and electrical properties of Fe doped Ba0.70Ca0.30TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of Ba_0.70Ca_0.30Ti_1?xFe_xO₃ (x=0–0.03) have been synthesized by a conventional solid state reaction method. The influence of Fe content on the microstructure, phase transition, dielectric, ferroelectric, and piezoelectric properties is investigated systematically. The ceramics with x≤0.02 are diphasic composites of tetragonal Ba_0.80Ca_0.20TiO₃:Fe and orthorhombic Ba_0.07Ca_0.93TiO₃:Fe solid solutions. The tetragonal phase is gradually suppressed as x increases, the ceramic with x=0.03 is found to have diphasic pseudocubic and orthorhombic phases. And the grain size is dependent on Fe content significantly. Introduction of Fe at B-sites improves the densification and decreases the sintering temperature. As x increases from 0 to 0.03, the room temperature relative dielectric permittivity enhances, dielectric loss decreases, and the Curie temperature decreases monotonically from 128 °C to 58 °C. However, the ferroelectricity enhances slightly and reaches the maximum near x=0.005, and then weakens with increasing x. On the other hand, the piezoelectric coefficient (d₃₃) and the electromechanical coupling coefficient (k_p) decrease simultaneously with increasing x, whereas the mechanical quality factor (Q_m) increases significantly. The structure–electrical properties relationship is discussed intensively to give more information on (Ba,Ca)TiO₃-based lead-free piezoelectric ceramics.     

Preparation of diamond/SiC composites by the liquid silicon infiltration method and their microstructure and properties

Diamond/SiC composites have long been recognized as advanced materials for thermal management as they exhibit excellent thermal and mechanical properties. The objective was to investigate and understand the phase composition, diamond graphitization behavior, microstructure, and properties of diamond/SiC composites developed following the liquid silicon infiltration process. The results revealed that the incorporation of α-SiC particles increased the degree of uniformity of the microstructure of the diamond/SiC composites. The acoustic mismatch model was used to analyze the samples before and after diamond graphitization to evaluate the interfacial thermal resistance of the composites. The results indicated that the interfacial thermal resistance of the graphitized composites was 11.9 times higher than the interfacial thermal resistance of the un-graphitized composites. Finally, the correlation between the diamond content of the composites and their thermal and mechanical properties was investigated.     

Piezoelectric properties of polypeptide-PMMA molecular composites fabricated by contact charging

The most common piezoelectric materials (PM) in use today are ceramic crystals which are heavy and brittle despite high piezoelectricity. Polymer-based PM is an alternative to ceramic crystals but they have lower piezoelectric coupling constants which deteriorates quickly at high temperature. In an effort to develop non-brittle and light PM with stable piezoelectric properties, we explored fabrication of composite materials comprising piezoelectric α-helical poly(α-amino acids), poly(γ-benzyl α,l-glutamate) (PBLG) and matrix polymer, poly(methylmethacrylate) (PMMA). Thick composite disks were created by contact charging of PBLG-MMA solution mixture followed by curing the MMA matrix in a designed mold. Compared to our prior method of corona discharge, this new method allowed the application of predefined electrical fields to the PMMA solution with little MMA evaporation. This communication presents the fabrication and characterization of a series of PBLG-PMMA composite disks with various PBLG compositions prepared under different poling conditions. The results show for the first time that all PBLGs can be poled in the direction normal to the disk surface and that the poled PBLGs within the PMMA matrix are directly responsible for the piezoelectricity of the composite materials. The two-polymer composite system allows independent modulation of film’s mechanical properties and piezoelectricity at a molecular level.     

Piezoelectric and mechanical properties of hydroxyapatite/titanium oxide composites

Hydroxyapatite (HAp) is the most common bioactive ceramic used to replace hard tissue in the body. Because of its low resistance and fragile nature, more attention is being given to composites based on HAp such as HAp/TiO₂ composites. This study aims at reporting the synthesis of HAp/TiO₂ composites (hereafter named HT composite) by sol-gel and co-precipitation methods assisted by ultrasonic radiation. The structural characterization was carried out by X-ray Diffraction (XRD) and Scanning Transmission X-ray Microscopy (STXM) techniques using synchrotron radiation, which allowed a mixture of phases to be identified separately in the two materials once the composite was formed. A Rietveld refinement for XRD data determined the phase percentage and structural parameters obtained for each material. In addition, crystallite size using the modified Scherrer equation was determined. A piezoelectric character of the two materials was confirmed by Piezoresponse Force Microscopy (PFM) to determine the piezoelectric coefficient (d_eff). Finally, PinPoint-AFM force curves confirmed an increase in the Young's modulus value for the HT composite.     

Piezoelectric and Dielectric Properties of Acrylonitrile Butadiene Rubber/Lead Magnesio-Niobate Piezoelectric Ceram

A new composite with special piezoelectric property was prepared by using lead magnesio-niobate piezoelectric ceram powders (PMN) as dispersing phase in acrylonitrile butadiene rubber (NBR) matrix. The dielectric and piezoelectric properties of the composite were studied. The result shows that the particle size of 80% of PMN ceram powders was 0.5–2 µm. The piezoelectric constant (d₃₃) of the composite increased with increasing volume fraction of PMN, and the max piezoelectric constant is 33 when the PMN volume fraction is 85%. Appropriate delay of polarizing time with increasing polarizing voltage could be helpful to improve the d₃₃ value. The optional polarizing condition is 25 min, 7–8 kv/mm, and 80°C. The dielectric constant increased with the increasing of the PMN volume fraction. Polarized time, polarized voltage, and polarized temperature have no effect on the dielectric constant.     

Processing,microstructure and piezoelectric properties of Li-doped BCZT ceramics

Li₂CO₃ is a promising additive to reduce the sintering temperature for (Ba_0.85Ca_0.15) (Zr_0.1Ti_0.9)O₃ (BCZT) ceramics, however, the solubility of Li₂CO₃ in water and the high volatility of Li₂O at elevated temperatures make the processing and densification of BCZT-Li₂CO₃ ceramics (known as BCZT-L) challenging. In our work, an optimized processing route was developed to obtain dense and flat BCZT-L ceramics made with 0–10 mol% of Li₂CO₃ and involving sintering at 1300 °C–1400 °C. The chemical and structural evolution of BCZT-L ceramics during sintering with and without a BCZT powder bed are comprehensively documented and the distribution of Li in the matrix has been observed through TOF-SIMS to explain the effects of Li doping on the piezoelectric properties. The d₃₃ and k_p of BCZT-L initially increased with Li content, but then decreased with excess Li. The decreased d₃₃ and k_p with excess Li is associated with Li aggregation in the BCZT matrix.     

The effect of nano-sized BNBT on microstructure and dielectric/piezoelectric properties

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (abbreviated as BNBT6) ceramic of near MPB composition was synthesized by two different processes. The first one is the addition of pre-synthesized BaTiO₃ and pre-milled Bi₂O₃, Na₂CO₃, BaCO₃ powders and calcination powder milled with a high energy milling machine in order to obtain a nano-particle size. The second one is a conventional one to compare with the former process. The pre-milling and the pre-synthesis process of raw materials lowered the calcination temperature to the extent of 59 °C as compared with conventionally fabricated BNBT6. The particle size of the powder exposed to heavy high energy milling reduced to 50–70 nm, whereas that of the conventionally ball-milled powder without the pre-milling and the pre-synthesis process had a larger size of 280 nm. To investigate the effects of the modified process on the characteristic of BNBT6 ceramics, the dielectric and the piezoelectric properties of sintered specimens fabricated by the two different processes were evaluated. It was found that the properties of the nano-sized BNBT6 ceramic near the MPB composition were increased by the modified mixing and milling method, showing superior characteristics in terms of the piezoelectric/dielectric constant and sintering density compared with those of the conventional process. The modified mixing and milling method was considered to be a new and promising process for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties.     

Influence of lightweight aggregate on the microstructure and durability of mortar

The results of an investigation on the effect of dry and prewetted lightweight aggregates on the microstructure and durability of mortar are presented in this paper. The results are compared with those obtained for normal aggregate mortar. There appears to be only a small difference in the microstructure of the interfacial transition zone (ITZ) between dry and prewetted lightweight aggregate mortars. The porous ITZ surrounding lightweight aggregate appears to extend for about 10 and 15 μm from the aggregate surface for dry and prewetted lightweight aggregates, respectively. The ITZ for dry and prewetted lightweight aggregates seems to be surrounded by dense paste that extends from 10 to about 50 μm from the aggregate surface. This dense paste has lower porosity than that observed in the bulk paste located 50 μm and farther from aggregate surface. The normal aggregate mortar prepared with the same water/cement ratio appears to have porous ITZ that extends beyond 35 μm from the aggregate surface. The dry and prewetted lightweight aggregate mortars seem to have a lower sorptivity and electrical conductivity than does the normal aggregate mortar. Lightweight aggregate mortars also appear to have excellent resistance to sulfate attack as compared with normal aggregate mortar.     

Effect of polyvinylidene fluoride on the fracture microstructure characteristics and piezoelectric and mechanical properties of 0-3 barium zirconate titanate ceramic-cement composites

Barium zirconate titanate (40−60 vol.%; BZT), Portland cement (PC) and polyvinylidene fluoride (0−7 vol.%; PVDF) were used as raw materials to produce 0–3 piezoelectric cement-based composites. The highest piezoelectric charge coefficient (d₃₃∼26-27 pC/N) was found at 50−60 vol.% BZT with 5 vol.% PVDF. Moreover, the composite with 50 vol.% BZT and 5 vol.% PVDF had the highest piezoelectric voltage coefficient (g₃₃ = 16.0 × 10⁻³ V·m/N). Scanning electron microscopy was used to investigate the morphology of the fracture surface of the composite. When PVDF was used in the composite, it was observed to fill some pores at the interface zone and within the cement phase. The elastic behaviour of PVDF could also be seen in the fracture surface, where it appeared as a stretched material different from both the BZT ceramic and cement, which are brittle materials. In addition, increasing the PVDF content led to increased fracture toughness.     

Temperature-insensitive dielectric and piezoelectric properties in (1-x)K0.5Na0.5Nb0.997Cu0.0075O3-xSrZrO3 ceramics

Systematic investigation on phase transition, dielectric and piezoelectric properties of (1-x)K_0.5Na_0.5Nb_0.997Cu_0.0075O₃-xSrZrO₃ (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15, abbreviated as KNNC-100xSZ) ceramics was carried out. Due to the coexistence of orthorhombic and tetragonal phase in a wide temperature range, a diffused polymorphic phase transition (PPT) region was achieved in KNNC with x ≥ 0.06. KNNC-12SZ ceramics exhibited high dielectric permittivity (∼1679), low dielectric loss (∼0.02) and small variation (Δe'/ε'_25 °C ≤ 15%) in dielectric permittivity from −78 °C to 237.3 °C. KNNC-6SZ ceramic possessed a high level of unipolar strain (∼0.15%) and maintained a smaller variation of ±12% under the corresponding electric field of 60 kV cm⁻¹ at 10 Hz from 25 °C to 175 °C. d₃₃^*, which was calculated according to the unipolar strain at 60 kV cm⁻¹, was 230 pm V⁻¹ and remained stable below 100 °C. Therefore, our work provided a new promising candidate for temperature-insensitive capacitors and piezoelectric actuators.     

ITZ microstructure of concrete containing GGBS

The interfacial transition zone (ITZ) of aggregate-cement paste and the morphology of hydrates in concrete containing ground granulated blast-furnace slag (GGBS) have been investigated using XRD, SEM and microhardness measurements. The experimental results demonstrated that GGBS significantly decreases both the quantity and the orientating arrangement of CH crystals at the ITZ. The CH crystal size becomes smaller because of the addition of GGBS. The weak ITZ between aggregate and cement paste was strengthened as a result of the pozzolanic reaction of GGBS. The above improvements become much more significant with the decrease of particle sizes of GGBS.     

Effect of entrained air voids on the microstructure and mass transport properties of concrete

The effects of entrained air on microstructure and transport properties of concrete with up to 11.5% air at different w/c ratios, curing and conditioning regimes were investigated. It was found that air voids disrupt the packing of cement and increase the heterogeneity of the microstructure. The width of the affected interface is around 30 μm. Gaseous diffusivity and permeability are increased by up to a factor of 2–3 at the highest air contents. This effect is similar to that due to increasing w/c ratio from 0.35 to 0.50 when samples are conditioned at 52% r.h or 50 °C. The effect on sorptivity is less consistent, while the effect on electrical conductivity is influenced by the moisture condition of the air voids. It is estimated that every 1% increase in air content increases transport by 10% or decreases it by 4%, depending on whether the air voids act as conductors or insulators.     

Influence of aggregate size, water cement ratio and age on the microstructure of the interfacial transition zone

This paper presents the results of an investigation on the effect of water-cement ratio (w/c), aggregate size, and age on the microstructure of the interfacial transition zone (ITZ) between normal weight aggregate and the bulk cement paste. Backscattered electron images (BSE) obtained by scanning electron microscope were used to characterize the ITZ microstructure. The results suggest that the w/c plays an important role in controlling the microstructure of the ITZ and its thickness. Reducing w/c from 0.55 to 0.40 resulted in an ITZ with characteristics that are not distinguishable from those of the bulk paste as demonstrated by BSE images. Aggregate size appears to have an important influence on the ITZ characteristics. Reducing the aggregate size tends to reduce the ITZ porosity. The evolution of the ITZ microstructure relative to that of the bulk paste appears to depend on the initial content of the unhydrated cement grains (UH). The results suggest that the presence of a relatively low amount of UH in the ITZ at early age may cause the porosity of the ITZ, relative to that of the bulk paste, to increase with time. The presence of relatively large amount of UH in the ITZ at early ages may cause its porosity, relative to that of the bulk paste, to decrease with time.     

Water-cement ratio gradients in mortars and corresponding effective elastic properties

Water-cement ratio gradients are modeled through the interfacial transition zone (ITZ) of a mortar with spherical inclusions. The model is a function of the over-all water-cement ratio, volume fraction and radius of sand, specific gravity of cement and thickness of ITZ. Based on experimental data from the literature, the dependence of saturated, homogeneous cement paste is modeled as a function of water-cement ratio. Subsequently, the effective bulk and shear moduli for mortars are determined using a generalized self-consistent method. Finally, application of the model to data in the literature pertaining to elastic wave speeds in saturated mortars composed of 20-30 screened sand with an overall water-cement ratio of 0.3 yielded a mean ITZ thickness of 48.3 μm.     

Synchronous improvement of piezoelectric property and temperature stability in PSN-PMN-PT ceramics by forming composites with ZnO

Relaxor ferroelectric materials with high piezoelectric properties always suffer from low phase transition temperature, making them difficult to satisfy the demands for high-temperature environment applications. In this work, we proposed a composite approach to improve the piezoelectricity and temperature stability of PSN-PMN-PT ceramics at the same time. The ZnO nanoparticles as a second phase were introduced into the PSN-PMN-PT matrix to form composite ceramics. When the ZnO content reaches 5 mol%, the piezoelectric constant d₃₃ increases from 529 pC/N for pure PSN-PMN-PT ceramic to 590 pC/N. Meanwhile, the retained d₃₃ after annealing at 200 °C keeps 92% of the value before annealing, indicating the thermal depolarization behavior is suppressed by the composite method. The synchronous improvement of the d₃₃ and thermal depolarization behavior for PSN-PMN-PT/ZnO composite ceramics is related to the local electric field and stress field caused by the addition of ZnO particles. Our results pave a simple and effective way to develop next-generation PT-based relaxor ferroelectric ceramics.     

Interfacial microstructure and mechanical properties of zirconia ceramic and niobium joints vacuum brazed with two Ag-based active filler metals

Reliable brazing of a zirconia ceramic and pure niobium was achieved by using two Ag-based active filler metals, Ag-Cu-Ti and Ag-Cu-Ti+Mo. The effects of brazing temperature, holding time, and Mo content on the interfacial microstructure and mechanical properties of ZrO₂/Nb joints were investigated. Double reaction layers of TiO and Ti₃Cu₃O formed adjacent to the ZrO₂ ceramic, whereas TiCu₄+Ti₂Cu₃+TiCu compounds appeared in the brazing interlayer. With increasing brazing temperature and time, the thickness of the Ti₃Cu₃O layer increased with consumption of the TiO layer, and the total thickness of the reaction layers increased slightly. Meanwhile, the blocky Ti-Cu compounds in the brazing interlayer tended to accumulate and grow. This microstructural evolution and its formation mechanism are discussed. The maximum shear strength was 157 MPa when the joints were brazed with Ag-Cu-Ti at 900 °C for 10 min. The microstructure and bonding properties of the brazed joints were significantly improved when Mo particles were added into the Ag-Cu-Ti. The shear strength reached 310 MPa for joints brazed with 8.0 wt% Mo additive, which was 97% higher than that of joints brazed with single Ag-Cu-Ti filler metal.     

Effects of atmospheric powder on microstructure and piezoelectric properties of PMZN-PZT quaternary ceramics

The effects of atmospheric powder on microstructure and piezoelectric properties of Pb(Mn_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMZN-PZT) quaternary ceramics were investigated. Specimens with various contents of Pb(Mn_1/3Nb_2/3)O₃ from 0 to 20 mol% were prepared by columbite two-stage process with and without atmospheric powder of PbZrO₃. The results revealed that the atmospheric powder is favored to the liquid-state sintering process in PbO vapor pressure equilibrium. The specimen sintered with atmospheric powder is homogenous and the fracture is intergranular. However, the specimen sintered without atmospheric powder is less homogenous and the fracture is essentially transgranular. On the other hand, the pyrochlore phase was formed along with the perovskite phase for the specimens sintered without atmospheric powder and the second phase was seriously detrimental to the electromechanical properties. The superior piezoelectric properties were observed for the specimens sintered with atmospheric powder. By optimizing the specimen composition, excellent piezoelectric, and dielectric properties (Q_m=2528, K_p=0.55, tan δ=0.003) were obtained at 10 mol% Pb(Mn_1/3Nb_2/3)O₃.     

Aggregate-cement paste transition zone properties affecting the salt-frost damage of high-performance concretes

The influence of the cement paste-aggregate interfacial transition zone (ITZ) on the frost durability of high-performance silica fume concrete (HPSFC) has been studied. Investigation was carried out on eight non-air-entrained concretes having water-to-binder (W/B) ratios of 0.3, 0.35 and 0.42 and different additions of condensed silica fume. Studies on the microstructure and composition of the cement paste have been made by means of environmental scanning electron microscope (ESEM)-BSE, ESEM-EDX and mercury intrusion porosimetry (MIP) analysis. The results showed that the transition zone initiates and accelerates damaging mechanisms by enhancing movement of the pore solution within the concrete during freezing and thawing cycles. Cracks filled with ettringite were primarily formed in the ITZ. The test concretes having good frost-deicing salt durability featured a narrow transition zone and a decreased Ca/Si atomic ratio in the transition zone compared to the bulk cement paste. Moderate additions of silica fume seemed to densify the microstructure of the ITZ.