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.     

Magnetic and conducting Fe3O4–polypyrrole nanoparticles with core‐shell structure

Magnetic and conducting Fe₃O₄–polypyrrole nanoparticles with core‐shell structure were prepared in the presence of Fe₃O₄ magnetic fluid in aqueous solution containing sodium dodecylbenzenesulfonate (NaDS) as a surfactant and dopant. Both the conductivity and magnetization of the composites depend strongly on the Fe₃O₄ content and the doping degree. With increase of Fe₃O₄ content in the composite, the conductivity at room temperature decreases, but the saturated magnetization and coercive force increase. Transmission electron microscopy (TEM) images of Fe₃O₄ and Fe₃O₄–polypyrrole particles show almost spherical particles with diameters ranging from 20 to 30 and 30 to 40 nm, respectively. The thermal stability of Fe₃O₄–polypyrrole composites is higher than that of pure polypyrrole. Studies of IR, UV–visible and X‐ray photoelectron spectroscopy (XPS) spectra suggest that the increased thermal stability may be due to interactions between Fe₃O₄ particles and polypyrrole backbone. Copyright © 2003 Society of Chemical Industry     

Polypyrrole‐Fe3O4 Magnetic Nanocomposite Prepared by Ultrasonic Irradiation

Summary: Ultrasonic irradiation was employed to prepare polypyrrole (PPY)/Fe₃O₄ magnetic nanocomposite by chemical oxidative polymerization of pyrrole in the presence of Fe₃O₄ nanoparticles. This approach can solve the problem in the dispersion and stabilization of inorganic nanoparticles in polymer. The structure and properties of PPY/Fe₃O₄ nanocomposite were characterized by TEM, XPS, FT‐IR, TG, and XRD. PPY deposits on the surface of Fe₃O₄ nanoparticles while Fe₃O₄ nanoparticles are dispersed at the nanoscale by ultrasonic irradiation, which leads to the formation of polypyrrole‐encapsulated Fe₃O₄ composite particles. The doping level of PPY in PPY/Fe₃O₄ nanocomposite is higher than that of neat PPY. The composites possess good electrical and magnetic properties. With the increase in the Fe₃O₄ content, the magnetization increases and the conductivity first increases and then decreases. When the Fe₃O₄ content is 40 wt.‐%, the conductivity reaches a maximum value of 11.26 S · cm^?1, about nine times higher than that of neat PPY, and the saturation magnetization is 23 emu · g^?1. Also, the introduction of Fe₃O₄ nanoparticles enhances the thermal stability of PPY/Fe₃O₄ composite.

Conductivity of PPY/Fe₃O₄ composite at different Fe₃O₄ content.     

Enhanced Electrocaloric Effects in Spark Plasma‐Sintered Ba0.65Sr0.35TiO3‐Based Ceramics at Room Temperature

Improvement of electrocaloric effect was investigated in the lead‐free undoped and Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics prepared by spark plasma sintering process. Owing to the merit of spark plasma sintering process, a fully dense undoped and Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics with fine grain sizes could be obtained. The electrocaloric (EC) effect can be significantly enhanced from 0.83 K for conventional sintered Ba_0.65Sr_0.35TiO₃ to 3.08 K for spark plasma‐sintered Mn‐doped Ba_0.65Sr_0.35TiO₃ ceramics since the dielectric strength was dramatically increased. This work indicated an effective way to achieve the significantly enhanced EC effect in a lead‐free system at room temperature.     

Preparation of Fe3Si‐Al2O3 Nanocomposite Powders by Mechanochemical Reaction of Fe3O4‐Si‐Al Powder Mixtures

Phase evolution and morphology of Fe₃O₄‐Si‐Al powder mixtures during ball milling from 30 min to 20 h were investigated. A 3‐h critical milling was necessary for the occurrence of mechanically activated combustion reaction. The reaction results in the formation of Fe (Si), Fe₃Si, and α‐Al₂O₃. During ball milling from 3 to 20 h, Fe (Si) and Fe₃Si were combined into disordered Fe₃Si intermetallic and Fe₃Si‐Al₂O₃ composite powder was formed. The presence of in situ formed alumina leads to a decrease in crystallite and particle sizes. The Fe₃Si‐Al₂O₃ particles after milling for 20 h had a crystalline size of 10~12 nm.     

醇-水共热法制备Fe3O4磁流体

报道了采用醇-水共热法制备稳定Fe3O4磁流体的工艺条件。应用透射电镜。X射线衍射仪。古埃磁天平对所制备的磁流体中的磁性颗粒的粒径。形貌，磁性等进行了表征。并分析了试验条件对制备的影响。     

磁性纳米粒子Fe3O4的制备方法

随着纳米科技不断的发展,磁性材料也逐渐的进入了纳米材料的新纪元。由于纳米粒子具有小尺寸效应、表面效应、量子尺寸效应以及宏观量子隧道效应,导致了磁性纳米材料的磁学性能有了很大的变化,扩展了其应用前景。文章介绍了Fe3O4磁性纳米粒子的四种制备方法:共沉淀合成法,水热合成法,微乳合成法和微乳-凝胶合成法。     

Poly(Caprolactone)‐Poly(N‐Isopropyl Acrylamide)‐Fe3O4 Magnetic Nanofibrous Structure with Stimuli Responsive Drug Release

Poly(caprolactone; PCL)—poly(N‐isopropylacrylamie; PNIPAAm)—Fe₃O₄ fiber, that can be magnetically actuated, is reported. Here, a structure is engineered that can be utilized as a smart carrier for the release of chemotherapeutic drug via magneto‐thermal activation, with the aid of magnetic nanoparticles (MNPs). The magnetic measurement of the fibers revealed saturation magnetization values within the range of 1.2–2.2 emu g^?1. The magnetic PCL‐PNIPAAm‐Fe₃O₄ scaffold shows a specific loss power value of 4.19 W g^?1 at 20 wt% MNPs. A temperature increase of 40 °C led to a 600% swelling after only 3 h. Doxorubicin (DOX) as a model drug, demonstrates a controllable drug release profile. 39% ± 0.92 of the total drug loaded is released after 96 h at 37 °C, while 25% drug release in 3 h at 40 °C is detected. Cytotoxicity results show no significant difference in cell attachment efficiency between the MNP‐loaded fibers and control while the DOX‐loaded fibers effectively inhibited cell proliferation at 24 h matching the drug release profile. The noncytotoxic effect, coupled with the magneto‐thermal property and controlled drug release, renders excellent potential for these fibers to be used as a smart drug‐release agent for localized cancer therapy.     

Bio‐Based Hybrid Magnetic Latex Particles Containing Encapsulated γ ‐Fe2O3 by Miniemulsion Copolymerization of Soybean Oil‐Acrylated Methyl Ester and Styrene

This work reports the use of acrylated fatty acid methyl ester (AFAME) as a biomonomer for the synthesis of bio‐based hybrid magnetic particles poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ produced by miniemulsion polymerization. Poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ can be tailored for use in various fields by varying the content of AFAME. The strategy employed is to encapsulate superparamagnetic iron oxide nanoparticles (SPIONs) as γ‐Fe₂O₃ into a styrene/AFAME‐based copolymer matrix. Raman spectroscopy is employed to ensure the formation of the SPIONs (γ‐Fe₂O₃) obtained by a co‐precipitation technique followed by oxidation of Fe₃O₄. The functionalization of SPIONs with oleic acid (OA) is carried out to increase the SPIONs–monomer affinity. The presence of OA on the surface of γ‐Fe₂O₃ is certified by identification of main absorption bands by fourier‐transform infrared spectroscopy (FTIR). Thermal analysis (differential thermogravimetry/differential thermo analysis and differential scanning calorimetry) results of poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ show an increase in AFAME content leading to a lower copolymer glass transition temperature (T _g). Dynamic light scattering (DLS) measurements result in poly(styrene‐co‐AFAME)/γ‐Fe₂O₃ particles with diameter in the range of 100–150 nm. It is also observed by transmission electron microscopy (TEM) and cryo‐TEM techniques that γ‐Fe₂O₃ particles are successfully encapsulated into the poly(styrene‐co‐AFAME) matrix.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Oxygen Migration in Dense Spark Plasma Sintered Aluminum‐Doped Neodymium Silicate Apatite Electrolytes

Neodymium silicate apatites are promising intermediate temperature (500°C–700°C) electrolytes for solid oxide fuel cells. The introduction of Al promotes isotropic percolation of O^2?, and at low levels (0.83–2.0 wt% Al) enhances bulk conductivity. To better understand the effect of Al‐doping on intrinsic conductivity, and the impact of grain boundaries on the transport, dense Nd_9.33+x/3Al_xSi_6?xO₂₆ (0 ≤ x ≤ 2) pellets were prepared by spark plasma sintering. Phase purity of the products was established by powder X‐ray diffraction and the microstructure examined by scanning electron microscopy. The ionic conductivity measured by AC impedance spectroscopy for the spark plasma sintered ceramics were compared with transport in single crystals of similar composition. Intermediate Al‐doping (0.5 ≤ x ≤ 1.5) delivered superior overall conductivity for both the polycrystalline and single crystal specimens.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Nanocrystalline/Nanosized Ni1−γFe2+γO4 Ferrite Obtained by Contamination with Fe During Milling of NiO–Fe2O3 Mixture. Structural and Magnetic Characterization

The nanocrystalline nickel ferrite (NiFe₂O₄) was synthesized by reactive milling starting from equimolar mixture of oxides. The iron contamination during milling leads to a solid state reaction between Fe and NiFe₂O₄ spinel. This reaction starts for a milling time longer than 30 h. A mixed nickel–iron ferrite (Ni_1?γFe_2+γO₄) and elemental Ni are obtained. The evolution of the nickel–iron mixed ferrite during milling and its properties were investigated using X‐ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Laser Particles Size Analyzer and magnetic measurements. Annealing treatment (350°C/4 h in vacuum) is favorable to the reaction between phases. Replacement of Ni²⁺ cations by iron cations provided by contamination leads to the increase of lattice parameter value of the spinel structure. The magnetization of the nickel–iron mixed ferrite newly formed is larger than the nickel ferrite magnetization (13.6 μ_B/f.u. and 6.22 μ_B/f.u., respectively), due to the magnetic moment of Fe²⁺ cation which is double as compared to the Ni²⁺ cation. Magnetization of the milled samples decreases during milling due to the structural changes induced by milling in the nickel–iron mixed ferrite. The annealing induces a reordering of the cations which leads to a larger magnetization.     

Influence of two structural phases of Fe3O4 and γ‐Fe2O3 on the properties of polyimide/iron oxide composites

Partially aliphatic polyimide/iron oxide composites based on the poly(amic acid) from 5‐(2,5‐dioxotetrahydro‐3‐furyl)‐3‐methyl‐3‐cyclohexene‐1,2‐dicarboxylic acid anhydride and 4,4′‐oxydianiline with iron oxide in different weight percentages were obtained. The structural phases of the transition of magnetite to maghemite occurring in these composites, at different temperatures, are discussed. The physical characteristics, including magnetic, thermal, structural and morphological properties, evaluated using X‐ray diffraction, scanning electron microscopy and thermal analysis, are influenced by the interplay of the filler content and the structural changes of the composite. The X‐ray diffraction patterns of all samples show a cubic structure indexed as magnetite (Fe₃O₄) or maghemite (γ‐Fe₂O₃). Quantification of these two phases was evidenced by the Rietveld method. The electrical properties analysed under different humidity conditions evidence the potential applicability of these polyimide/iron oxide materials as humidity sensors. © 2015 Society of Chemical Industry     

Enhanced O2 Flux of CaTi0.85Fe0.15O3−δ Based Membranes by Mn Doping

Dense symmetric membranes of CaTi_0.85?xFe_0.15Mn_xO_3?δ (x = 0.1, 0.15, 0.25, 0.4) are investigated in order to determine the optimal Mn dopant content with respect to highest O₂ flux. O₂ permeation measurements are performed as function of temperature between 700°C–1000°C and as function of the feed side ranging between 0.01 and 1 bar. X‐ray photoelectron spectroscopy is utilized to elucidate the charge state of Mn, and synchrotron radiation X‐ray powder diffraction (SR‐XPD) is employed to investigate the structure symmetry and cell volume of the perovskite phase at temperatures up to 800°C. The highest O₂ permeability is found for x = 0.25 over the whole temperature and ranges, followed by x = 0.4 above 850°C. The O₂ permeability for x = 0.25 reaches 0.01 mL(STP) min^?1 cm^?1 at 925°C with 0.21 bar feed side and Ar sweep gas. X‐ray photoelectron spectroscopy indicates that the charge state of Mn changes from approx. +3 to +4 when x > 0.1, which implies that Mn mainly improves electronic conductivity for x > 0.1. The cell volume is found to decrease linearly with Mn content, which coincides with an increase in the activation energy of O₂ permeability. These results are consistent with the interpretation of the temperature and dependency of O₂ permeation. The sintering behavior and thermal expansion properties are investigated by dilatometry, which show improved sinterability with increasing Mn content and that the thermal expansion coefficient decreases from 12.4 to 11.9 × 10^?6 K^?1 for x = 0 and x = 0.25, respectively.     

Biodegradable magnetic‐sensitive shape memory poly(ɛ‐caprolactone)/Fe3O4 nanocomposites

A novel biodegradable magnetic‐sensitive shape memory poly(?‐caprolactone) nanocomposites, which were crosslinked with functionalized Fe₃O₄ magnetic nanoparticles (MNPs), were synthesized via in situ polymerization method. Fe₃O₄ MNPs pretreated with γ‐(methacryloyloxy) propyl trimethoxy silane (KH570) were used as crosslinking agents. Because of the crosslinking of functionalized Fe₃O₄ MNPs with poly(?‐caprolactone) prepolymer, the properties of the nanocomposites with different content of functionalized Fe₃O₄ MNPs, especially the mechanical properties, were significantly improved. The nanocomposites also showed excellent shape memory properties in both 60 °C hot water and alternating magnetic field (f = 60, 90 kHz, H = 38.7, 59.8 kA m^?1). In hot water bath, all the samples had shape recovery rate (R_r) higher than 98% and shape fixed rate (R_f) nearly 100%. In alternating magnetic field, the R_r of composites was over 85% with the highest at 95.3%. In addition, the nanocomposites also have good biodegradability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45652.     

Preparation of polyethylene oxide/LixV2‐δO4‐δ nanocomposites

Polyethylene oxide (PEO)/LixV_2‐δO_4‐δ nanocomposites were prepared in aqueous solution. Characterization of the nanocomposites using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), powder X‐ray diffraction (XRD), and Fourier transform infrared spectrum (FTIR) shows that polymer chains intercalate inorganic host lamella and exhibit lattice expansion along the stacking direction of 4.2 Å. A possible model for the structure of the nanocomposite is also provided. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2162–2166, 2001     

超细Fe_3O_4磁性行为的Preisach模拟

Fe3O4具有类似尖晶石的结构,是目前使用极广泛的磁性材料。近年来的研究使其在磁记录等方面的应用取得了显著的进展。Preisach模型对材料的模拟,主要从自发磁矩的先后翻转顺序出发对材料磁化结构有一个详细的数值解释,考察了材料Barkhausen跳跃的实质问题。本文用改进的Preisach模型对Fe3O4各种磁性行为进行了模拟,如零场冷却(ZFC)磁化强度和加场冷却(FC)磁化强度,以及不同温度下的磁滞回线等实验结果进行了分析模拟。通过对实验拟合得到巴克豪森跳跃谱的相关参数,这些参数很好的反映了材料磁化的物理本质。     

磁性四氧化三铁纳米粒子的合成及改性

Fe3O4由于有磁性且原料易得、价格低廉而被大量应用于涂料和油墨等领域;纳米Fe3O4粒子还被广泛用作磁记录材料、固定化酶、免疫诊断、靶向药物、催化剂载体、磁性微球和生物探针等。近年来有关磁性Fe3O4纳米粒子的合成和改性已引起人们的广泛关注。