Multifunctional Properties of Multistage Spark Plasma Sintered HA–BaTiO3‐Based Piezobiocomposites for Bone Replacement Applications

This work reports the processing–microstructure–property correlation of novel HA–BaTiO₃‐based piezobiocomposites, which demonstrated the bone‐mimicking functional properties. A series of composites of hydroxyapatite (HA) with varying amounts of piezoelectric BaTiO₃ (BT) were optimally processed using uniquely designed multistage spark plasma sintering (SPS) route. Transmission electron microscopy imaging during in situ heating provides complementary information on the real‐time observation of sintering behavior. Ultrafine grains (≤0.50 μm) of HA and BT phases were predominantly retained in the SPSed samples. The experimental results revealed that dielectric constant, AC conductivity, piezoelectric strain coefficient, compressive strength, and modulus values of HA‐40 wt% BT closely resembles with that of the natural bone. The addition of 40 wt% BT enhances the long‐crack fracture toughness, compressive strength, and modulus by 132%, 200%, and 165%, respectively, with respect to HA. The above‐mentioned exceptional combination of functional properties potentially establishes HA‐40 wt% BT piezocomposite as a new‐generation composite for orthopedic implant applications.     

Spark Plasma Sintered HA‐Fe3O4‐Based Multifunctional Magnetic Biocomposites

Although HA is highly biocompatible, one of the major disadvantages of HA include the lack of antibacterial property. In an earlier study, we demonstrated the potential role of magnetic field stimulation on bactericidal property in vitro. Following this, it was hypothesized that antibacterial property can be realized if bacteria are grown on magnetic biocomposites in vitro. In addressing this issue, this study demonstrates the development of HA‐Fe₃O₄‐based magnetic substrate with multifunctional properties. For this purpose, HA‐xFe₃O₄ (x: 10, 20 and 40 wt%) powder compositions were sintered using uniquely designed spark plasma sintering conditions (three stage sintering with final holding temperature of 1050°C for 5 min). A saturation magnetization of 24 emu/g is measured with HA‐40%Fe₃O₄. Importantly, all the HA‐Fe₃O₄ composites demonstrated bactericidal property by rupturing the membrane of Escherichia coli bacteria, while supporting cell growth of metabolically active human fetal osteoblast cells over 8 d culture. A systematic decrease in bacterial viability with Fe₃O₄ addition is consistent with a commensurate increase in reactive oxygen species (ROS).     

Pulsed Electrical Stimulation and Surface Charge Induced Cell Growth on Multistage Spark Plasma Sintered Hydroxyapatite‐Barium Titanate Piezobiocomposite

The primary purpose of the present work was to illustrate whether cell proliferation can be enhanced on electroactive bioceramic composite, when the cells are cultured in the presence of external electrical stimulation. The two different aspects of the influence of electric field (E‐field) application toward stimulating the growth/proliferation of bone/connective tissue cells in vitro, (a) intermittent delivery of extremely low strength pulsed electrical stimulation (0.5–4 V/cm, 400 μs DC pulse) and (b) surface charge generated by electrical poling (10 kV/cm) of hydroxyapatite (HA)‐BaTiO₃ piezobiocomposite have been demonstrated. The experimental results establish that the cell growth can be enhanced using the new culture protocol of the intermittent delivery of electrical pulses within a narrow range of stimulation parameters. The optimal E‐field strength for enhanced cellular response for mouse fibroblast L929 and osteogenic cells is in the range of 0.5–1 V/cm. The MTT [3‐(4, 5‐dimethylthiazol‐2‐yl)‐2, 5‐diphenyl tetrazolium bromide] assay results suggested the increased viability of E‐field treated cells over 7 d in culture, implicating the positive impact of electrical pulses on proliferation behavior. The alizarin red assay results showed noticeable increase in Ca‐deposition on the E‐field treated samples in comparison to their untreated counterparts. The negatively charged surfaces of developed piezocomposite stimulated the cell growth in a statistically noticeable manner as compared with the uncharged or positively charged surfaces of similar composition.     

Phase‐dependent radiation‐resistant behavior of BaTiO3: An in situ X‐ray diffraction study

The radiation‐resistant response of BaTiO₃ in the tetragonal and rhombohedral phases on exposure to 100 MeV Ag⁷⁺ ion irradiation was investigated by in situ X‐ray diffraction (XRD) at room temperature (300 K) and low temperature (25 K), respectively. This study revealed that the BaTiO₃ in rhombohedral phase retained crystallinity up to an ion fluence of 1×10¹⁴ ions/cm², whereas tetragonal phase amorphized at much lower fluence viz. 1×10¹³ ions/cm². The in situ XRD along with Raman spectroscopy studies revealed that BaTiO₃ in rhombohedral phase is more radiation resistant than that of tetragonal phase. The density functional theory (DFT) calculations confirmed higher bond strength of rhombohedral phase as compared to tetragonal phase, which supported the experimental result of higher radiation stability of rhombohedral phase. The theoretical predictions on high‐temperature phase will be of relevance to the nuclear waste applications.     

TiO2–BaTiO3 nanocomposite for electron capture in dye‐sensitized solar cells

Different compositions of TiO₂–BaTiO₃ nanocomposites are synthesized with various weight ratios for dye‐sensitized solar cell (DSSC) applications. TiO₂ and BaTiO₃ nanoparticles (NPs) are synthesized by sol‐gel and solvothermal methods, respectively and are employed as the photoanode electrodes. BaTiO₃ NPs have pure cubic perovskite crystal structure with an average size of 20‐40 nm, while TiO₂ NPs show pure anatase phase with 15‐30 nm size. The power conversion efficiency (PCE) enhancement of the cells is first attained by controlling the thickness of the films for light harvesting improvement. The fabricated DSSC composed of pure BaTiO₃ NPs with an optimal thickness of 25 μm shows efficiency of 6.83%, whereas that made of pure TiO₂ NPs with 14 μm thickness has cell efficiency of 7.24%. Further improvement of cell efficiency is achieved by preparation of binary oxide nanocomposites using TiO₂ and BaTiO₃ NPs with various weight ratios. The highest PCE of 9.40% is obtained for the nanocomposite with TiO₂:BaTiO₃=85:15 (wt%). The enhancement is assigned to less recombination of photo‐generated electrons and higher incident photon to current conversion yield as a result of rapid charge collection and higher dye sensitization.     

Barium titanate‐based nanodielectrics of two chemically recyclable thermosets

In this work was investigated the effect of the addition of barium titanate (BaTiO₃) on electrical properties of two chemically recyclable thermosets, polyhemiaminal (PHA) and polyhexahydro‐s‐triazine (PHT), both fabricated from 4,4′‐oxydianiline (ODA), an ether derivative of aniline and paraformaldehyde. Thermal and mechanical properties as well as chemical recyclability of the two polymers and their nanocomposites/nanodielectrics were also investigated. In addition, a quantitative analysis was conducted of the nanoparticle dispersion in the PHA‐/PHT‐based BaTiO₃‐containing nanocomposites using transmission electron microscopy imaging and the nearest‐neighbor distance index and this index was used to analyze the investigated properties in connection with the proper mechanisms. Regarding the electrical properties for both neat polymers, conductivity values of the order of 10^?8 S m^?1 at 100 Hz were observed and dielectric constant values close to 2.80 for both polymers at 1 kHz. The addition of 0.5 wt% of BaTiO₃ ferroelectric nanoparticles increased by about 44% the dielectric constant (1 kHz) and conductivity (10² Hz) of the PHA‐based nanocomposite. PHA and PHT exhibited glass transition temperature (T_g) values in the range 125–180 °C. An increase of 7 °C in T_g was observed after the incorporation of 0.5 wt% of BaTiO₃ into PHA. Concerning the mechanical properties, values in the range 4.00–4.45 GPa for reduced modulus and 0.30–0.43 GPa for nanohardness for PHA and PHT polymers were observed. Independently of filler content or polymer matrix, both mechanical properties were enhanced after the addition of BaTiO₃. The chemical recycling of PHA/PHT and all nanocomposites in the initial ODA reagent after sulfuric acid treatment was successfully characterized using the NMR and Fourier transform infrared spectroscopic techniques. © 2018 Society of Chemical Industry     

Comparative In Vitro Osteoinductivity Study of HA and α‐TCP/HA Bicalcium Phosphate

A bicalcium phosphate (BCP) bioceramic comprising α‐tricalcium phosphate (α‐TCP) and hydroxyapatite (HA) was prepared by a two‐step sintering. The microstructure of the BCP bioceramic was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray diffraction. The in vitro osteoinductivity was evaluated by culturing MG63 osteoblast‐like cells on the BCP bioceramic. Results showed that the BCP bioceramic comprising α‐TCP and HA in a moderate ratio possessed a hardness of 93.7 Hv. The cells spread faster on the BCP bioceramic than those on the commercial HA. It suggested that the BCP bioceramic can enhance osteoinductivity in vivo.     

Temperature‐insensitive piezoelectricity in lead‐free NaNbO3‐based ceramics

In this work, we report a lead‐free piezoelectric ceramic of (0.9‐x)NaNbO₃‐0.1BaTiO₃‐xBaZrO₃, and the effects of BaZrO₃ on the phase structure, microstructure, electrical properties and temperature stability are investigated. A morphotropic phase boundary‐like region consisting of rhombohedral (R) and tetragonal (T) phases is constructed in the compositions with x = 0.035‐0.04. More importantly, in situ temperature independence of the piezoelectric effect {piezoelectric constant (d₃₃) and strain} can be achieved below the Curie temperature (T_c). Intriguingly, the electric field‐induced strain is still observed at T ≥ T_c due to the combined actions of the electrostrictive effect and the electric field‐induced phase transition. We believe that NaNbO₃‐based ceramics of this type have potential for applications in actuators and sensors.     

Large electric‐field‐induced strain and enhanced piezoelectric constant in CuO‐modified BiFeO3‐BaTiO3 ceramics

In this work, we fabricated the (1‐x)BiFeO₃‐xBaTiO₃+y‰ mol CuO ceramics by the modified thermal quenching technique. The pure perovskite phase was formed and a morphotropic phase boundary (MPB) was observed in the ceramics with x = 0.30‐0.33. The addition of CuO can significantly enhance the density of the BiFeO₃‐BaTiO₃ material. Importantly, an enhanced piezoelectric constant (d₃₃=165 pC/N), a large electric‐field‐induced strain (?S = 0.54%: peak to peak strain) and a large piezoelectric actuator constant (d₃₃*=449 pm/V) together with a high Curie temperature (T_C) of 503°C were observed in the ceramics with x = 0.30 and y = 5. As a result, the enhanced piezoelectricity and large electric‐field‐induced strain could significantly stimulate further researches in BFO‐based ceramics.     

In Vitro Degradation and Conversion of Melt‐Derived Microfibrous Borate (13‐93B3) Bioactive Glass Doped with Metal Ions

Microfibrous melt‐derived bioactive glasses based on a borate 13‐93B3 composition are showing a considerable capacity to heal chronic soft tissue wounds in humans and animals. Metal ion dopants in borate 13‐93B3 microfibers can be beneficial for healing soft tissue wounds and bone defects but their role and delivery have received little attention. In this study, the effect of selected metal ion dopants on the degradation and conversion of 13‐93B3 microfibers in simulated body fluid at 37°C was investigated. Two groups of microfibers (diameter = 0.2–3 μm) composed of 13‐93B3 glass (composition 6 Na₂O, 12 K₂O, 5 MgO, 20 CaO, 4 P₂O₅, 53 B₂O₃, wt%) doped with (1) CuO (0.4 wt%) + ZnO (1.0 wt%); and (2) CuO (0.4 wt%) + ZnO (1.0 wt%) + Fe₂O₃ (0.4 wt%) + SrO (2.0 wt%) were studied. The metal ion dopants had little effect on the degradation of the parent 13‐93B3 glass microfibers and their conversion to an amorphous calcium phosphate (ACP) product but they inhibited the crystallization of the ACP to HA. The release of Cu and Sr ions from the glass into the medium was considerably higher than Zn and Fe ions which were retained mainly in the ACP or HA product. These results are pertinent to the design of borate bioactive glasses for optimum healing of soft tissue wounds and bone.     

Effects of Mg‐Doping and of Reinforcing Multiwalled Carbon Nanotubes Content on the Structure and Properties of Hydroxyapatite Nanocomposite Ceramics

Surfactant‐assisted hydrothermal synthesis of magnesium‐doped hydroxyapatite (Ca_10?xMg_x(PO₄)₆(OH)₂) with 0 ≤ x ≤ 1) was realized in aqueous solution at 90°C. β‐TCP phase was formed in the Mg_0.6‐HA sample after heat treatment at 1000°C. Magnesium was found to degrade the sintering ability of Mg_x‐HA ceramics. Flexural strength (σ_f) was found to decrease as a function of Mg‐doped HA. The using of carbon nanotubes as reinforcing agents mitigated the strength loss of Mg‐HA ceramics. The flexural strength of Mg_0.6‐HA was then increased by nearly 20% from approximately 33 to 39 MPa with an optimum addition of 3 wt% of multi‐walled nanotubes.     

Ultra‐Broad Temperature Stability Obtained with Ce‐Doped BaTiO3‐Based Ceramics

Ce‐doped BaTiO₃‐based ceramics were prepared and studied to satisfy ultra‐broad temperature stability (from ?55°C to 300°C, capacitance variation rate based on C_20°C is within ±15%). The sample with 0.6 mol% CeO₂ succeeds to achieve this performance with a remarkably high ceiling temperature of 300°C. Meanwhile, the sample has good dielectric and electrical properties at room temperature (ε_r = 1667, tanδ = 1.478%, ρ_V = 5.9 × 10¹² Ω·cm). Ce ion can substitute for Ti ion as Ce⁴⁺ or Ba ion as Ce³⁺. The substitution decreases the spontaneous polarization of BaTiO₃, and then weakens the ferroelectricity of BaTiO₃. As a result, the temperature stability of samples is improved obviously. Besides, CeO₂ addition promotes the formation of exaggerated grains, which are consisting of Ba₆Ti₁₇O₄₀.     

Improved Energy Storage Properties of Fine‐Crystalline BaTiO3 Ceramics by Coating Powders with Al2O3 and SiO2

The multilayer structure of capacitor demands for fine grain size of dielectric ceramics in devices, because the thinner layer which needs ceramics with fine grain size is helpful in enlarging the capacitance. In this paper, the aqueous chemical coating method was utilized to modify the BaTiO₃ particles. The fine‐crystalline BaTiO₃ ceramics with an average grain size below 200 nm without abnormal grain growth by co‐coating Al₂O₃ and SiO₂ has been prepared. The phase composition, microstructures of coated particles and ceramics, and dielectric properties were investigated. For samples containing 3 wt% of Al₂O₃ and 1 wt% of SiO₂, the energy storage density is 0.725 J/cm³ and the efficiency of the ceramic samples can keep above 80%. The breakdown strength was improved to about 190 kV/cm.     

Improved stability and tumor targeting of 5‐fluorouracil by conjugation with hyaluronan

To circumvent the rapid clearance in vivo and consequent low tumor targeting of 5‐fluorouracil (5‐Fu), hyaluronan‐5‐fluorouracil conjugate (HA‐5‐Fu) was firstly synthesized and characterized. The stability of HA‐5‐Fu in vitro was evaluated by incubation with phosphate buffered saline, hyaluronidase solution, and mice plasma, respectively. The tumor targeting was tested by in vitro cytotoxicity evaluation and in vivo pharmacokinetics study in plasma and tumor. HA‐5‐Fu with drug loading of 87.674 mg/g was successfully obtained and confirmed. HA‐5‐Fu showed high stability in acidic environment and moderate stability under enzymatic cleavage. The enhanced cytotoxicity of HA‐5‐Fu over 5‐Fu depended on drug concentration, incubation time, and cell lines type. The t_1/2 of HA‐5‐Fu in plasma after injection of prodrug was extended up to 10 times compared with that of 5‐Fu. Notably, AUC_0–t in tumors of HA‐5‐Fu was 3.6 times higher than 5‐Fu, demonstrating its excellent tumor targeting and quite promising prospect in anti‐cancer therapy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 927‐932, 2013     

Structural and Magnetoelectric Behavior of Lanthanum Manganite‐Based Multiferroic Heterostructures

The effect of fabrication method on the structure of (100 ? x) wt% BaTiO₃ + x wt% La_0.7Ba_0.3MnO₃ (BT + BLM) and (100 ? x) wt% Na, Bi, Sr‐doped PZT + x wt% La_0.65Pb_0.35MnO₃ (PZTNB‐1 + PLM) magnetoelectric ceramics was studied. Profound interdiffusion of two interacting phases occurs in nearly all cases. The BT + BLM and PZTNB‐1 + PLM ceramics exhibit low piezoelectric parameters even with small manganite contents (10–20 wt%). The increased content of the magnetostrictive phase complicates the polarization process due to the high conductivity of La_0.7Ba_0.3MnO₃ and La_0.65Pb_0.35MnO₃. Doping of BaTiO₃ and PZTNB‐1 with small additions of manganite components affects piezoelectric properties, thereby lowering efficiency of the resulting material.     

Processing of 0.7BaTiO3–0.3BiScO3 Solid‐Solution Coatings

Coatings with the 0.7BaTiO₃–0.3BiScO₃ solid‐solution composition were formed on palladium and single‐crystal (001) SrTiO₃ substrates using a polymeric metal citrate precursor. Solutions of TiOCl₂, Ba(NO₃)₂, Sc(NO₃)₃, and Bi(NO₃)₃ were mixed with citric acid and polymerized with ethylene glycol. Stable mixed‐metal citrate solutions were formed at pH > 9 and used for coatings. The phase and composition of powders and coatings were characterized using DTA, TGA, SEM, TEM, and X‐ray diffraction. Single‐phase cubic 0.7BaTiO₃–0.3BiScO₃ solid solutions formed at 600°C. Coatings on Pd using precursors doped with 5 wt% lithium nitrate were dense after sintering at 950°C/1 h. Coatings without lithium nitrate required 1050°C/50 h to densify. Coatings on SrTiO₃ heat‐treated at 1150°C were dense but formed a (Sc,Ti)‐rich second phase.     

Reduction of Ti4+ to Ti3+ in Boron‐Doped BaTiO3 at Very Low Temperature

Reduction of Ti⁴⁺ to Ti³⁺ was found in boron‐doped BaTiO₃ ceramics when we sintered the samples at very low temperature (>850°C) in 5%H₂/Ar. Such reduction did not occur in pristine BaTiO₃ ceramic. The methods such as UV–vis spectroscopy, luminescence spectroscopy, and X‐ray photoelectron spectroscopy confirmed the reduction by showing the presence of Ti³⁺. The results of Ti–K‐edge X‐ray absorption near‐edge structure measurement (XANES) indicated that boron doping changed the geometry of Ti‐oxygen in BaTiO₃ to some extent. It was likely that some boron ions stayed at interstitial sites of BaTiO₃ lattice and acted as donors, which might trigger the reduction. The reduced boron‐doped BaTiO₃ were semiconducting and had very low room‐temperature resistivity (<100 Ω m). However, different from the n‐type rare‐earth‐doped BaTiO₃ ceramics, they did not display positive temperature coefficient resistance (PTCR) behavior.     

Grain Size Effects on Piezoelectric Properties and Domain Structure of BaTiO3 Ceramics Prepared by Two‐Step Sintering

A series of highly dense barium titanate (BaTiO₃) ceramics with the average grain size (GS) from 0.29 to 8.61 μm are successfully prepared by two‐step sintering, and the GS effect on piezoelectric coefficient (d₃₃) is systematically discussed in this work. It is found that when GS above 1 μm, d₃₃ can be enhanced with decreasing GS, reaching a maximum value of 519 pC/N around 1 μm due to the high activity of domain wall mobility. Subsequently, d₃₃ rapidly drops with a further decrease in GS owing to the reduced domain density. The results suggest that it is possible to prepare high‐performance BaTiO₃ ceramics by controlling the GS and domain configuration properly, which brings great revitalization to the BaTiO₃‐based piezoceramics.     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.