Influence of microstructure on dielectric properties of Nd-doped barium titanate synthesized by hydrothermal method

Nd-doped barium titanates were successfully synthesized via a hydrothermal route. The as-prepared barium titanate was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transformation infrared spectroscopy (FTIR), and Vis–NIR spectroscopy respectively. The results show that pure and Nd-doped barium titanate powders have cubic perovskite structure. After sintering at a temperature of 1,250 °C for 2 h, the phase compositions of all barium titanate are tetragonal phase structure. Vis–NIR spectra well confirmed that Nd³⁺ have been doped into barium titanate. The particle diameters of Nd-doped barium titanate powders and ceramics become samller with the increase of Nd³⁺ content. When Nd/Ba molar ratio is 0.02, the dielectric loss (0.0008) of the powder measured at 1 MHz and room temperature dramatically decreases by 99 % comparing with pure barium titanate (0.083) and shows frequency independence with the frequency increasing from 40 Hz to 1 MHz. The dielectric constant and dielectric loss are 436 and 0.09 after sintering. The Nd-doped BaTiO₃ show an improvement in the dielectric quality which possess a decreased sensitivity to frequency for both the dielectric constant and dielectric loss. Such improvements are of potential importance for high energy density and low loss.     

单相钡铁氧体磁性材料的制备及磁性能研究

以硝酸钡、硝酸铁和柠檬酸为原料,采用溶胶-凝胶法制备了单相钡铁氧体(BaFe12O19)纳米粉体,并进一步研究了n(Fe)/n(Ba)、热处理温度对产物组成、形貌以及磁性能的影响。用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和振动样品磁强计(VSM)分别对样品的组成、形貌和磁性能进行了表征。实验结果表明,当煅烧温度不变时,样品的晶粒尺寸随着n(Fe)/n(Ba)的增大而变大,磁性能随n(Fe)/n(Ba)的增大而增强;当n(Fe)/n(Ba)不变时,样品的晶粒尺寸随着煅烧温度的升高而变大。当n(Fe)/n(Ba)=12时,在800℃煅烧2h得到单一晶型的钡铁氧体粉体。1000℃时样品的磁性能最佳,饱和磁化强度(Ms)为70.88A.m2/kg,矫顽力(Hc)为372.89kA/m。     

Synthesis of nm-sized barium titanate crystallites using a new LTDS method and their characterization

A new LTDS method was established to synthesize nm-sized barium titanate crystallites with particle sizes around 10 nm. This LTDS method was the following two features, i.e., (1) a heat of neutralization in a neutralization reaction between strong acid and base can be used as a driving force for a formation of barium titanate, and (2) barium titanate crystallites can be directly synthesized from Ti and Ba ions, not via intermediates. Therefore, using the LTDS method, it can be expected that there is no minimum limit in particle sizes, and also no contamination in barium titanate crystallites. At first, optimum conditions for a formation of barium titanate were screened at various reaction temperatures and Ba/Ti atomic ratios in the starting materials. As a result, the formation of barium titanate was found at higher reaction temperatures than 50°C and higher Ba/Ti atomic ratios than 5. Under a constant temperature, particle sizes decreased with increasing Ba/Ti atomic ratios while under a constant Ba/Ti atomic ratio, particle sizes were independent of reaction temperatures. Finally, barium titanate crystallites with particle sizes below 10 nm were first prepared. These particles were also characterized using various methods.     

X-ray diffraction studies on aluminum-substituted barium hexaferrite

Effect of aluminum substitution in barium hexaferrite was studied following the hydrothermal precipitation–calcination techniques. It was attempted to prepare aluminum-substituted barium hexaferrites with compositions BaAl_xFe_12−xO₁₉ having x=2,4, 6, 8 and 10. The precursors were prepared by using stoichiometric amounts of Ba, Al and Fe³⁺ nitrate solutions with urea as the precipitating agent. The hydrothermally prepared precursors were calcined at temperatures in the range of 800–1200 °C. The detailed work carried out on identification of crystalline phases through XRD revealed that, after the hydrothermal treatment, the samples showed barium carbonate, hematite and boehmite as the crystalline phases (except that boehmite was not identified for Ba/Al/Fe ratio as 1:2:10). Irrespective of the Al content, none of the 1000 and 1200 °C calcined samples showed any crystalline phase of Al. The 1200 °C calcined samples showed that Al-substituted barium hexaferrite is formed only with the Ba/Al/Fe atomic ratio of 1:2:10. With increase in the Al content, formation of hexaferrite was not observed. BaCO₃ was found be present even at 1200 °C in all the samples except for the one having Fe/Al ratio 5. The normal decomposition temperature of BaCO₃ is between 950 and 1050 °C. It is difficult to explain the increased stability of BaCO₃, which is perhaps responsible for hindering the formation of aluminum-substituted barium ferrite having Fe/Al ratio ≤2. The Al substitution in barium hexaferrite was confirmed through magnetic measurements.     

热处理温度对M-Ba铁氧体微米纤维结构和磁性能的影响

以柠檬酸和金属盐为原料,采用有机凝胶先驱体转化法成功制备了直径为500～600nm的钡铁氧体(BaFe12O19)微米纤维。通过XRD、SEM和VSM等技术对所制备的目标纤维进行了表征。结果表明,经750℃焙烧2h后,可获得M-Ba铁氧体纯相。随着焙烧温度的升高,晶粒逐渐长大,经850℃焙烧2h后,纤维主要由比较规则的片状晶粒组成。钡铁氧体纤维的磁性能主要受晶粒尺寸和测试温度的影响。经950℃焙烧2h后,组成纤维的晶粒尺寸约为62nm,室温下测得的饱和磁化强度和矫顽力均取得最大值,分别约为67A.m2/kg和328kA/m。在液氮(77K)条件下,纤维的饱和磁化强度有显著提高,最大值约为87A.m2/kg,这主要是由于纳米晶的表面自旋有序程度提高造成的。     

Individual-specific transgenerational marking of fish populations based on a barium dual-isotope procedure

The present study focuses on the development and evaluation of an individual-specific transgenerational marking procedure using two enriched barium isotopes, (135)Ba and (137)Ba, mixed at a given and selectable molar ratio. The method is based on the deconvolution of the isotope patterns found in the sample into four molar contribution factors: natural xenon (Xe nat), natural barium (Ba nat), Ba135, and Ba137. The ratio of molar contributions between Ba137 and Ba135 is constant and independent of the contribution of natural barium in the sample. This procedure was tested in brown trout ( Salmo trutta ) kept in captivity. Trout were injected with three different Ba137/Ba135 isotopic signatures ca. 7 months and 7 days before spawning to compare the efficiency of the marking procedure at long and short term, respectively. The barium isotopic profiles were measured in the offspring by means of inductively coupled plasma mass spectrometry. Each of the three different isotopic signatures was unequivocally identified in the offspring in both whole eggs and larvae. For 9 month old offspring, the characteristic barium isotope signatures could also be detected in the otoliths even in the presence of a high and variable amount of barium of natural isotope abundance. In conclusion, it can be stated that the proposed dual-isotope marking is inheritable and can be detected after both long-term and short-term marking. Furthermore, the dual-isotope marking can be made individual-specific, so that it allows identification of offspring from a single individual or a group of individuals within a given fish group.     

Synthesis of barium hexaferrite by the co-precipitation method using acetate precursor

Fine particles of barium hexaferrite were synthesised by a chemical co-precipitation method using acetate-nitrate (barium acetate + iron nitrate) precursors. The thermal properties, phase composition and morphology of hexaferrite powders were studied. Simultaneous DTA/TG results confirmed by those obtained from XRD and VSM, indicated that the formation of barium hexaferrite occurs at a relatively low temperature of 710°C. This temperature is affected by the Fe³⁺/Ba²⁺ molar ratio. The SEM investigations revealed that the mean particle size of barium hexaferrite increases with increasing calcination temperature. In this system the Fe³⁺/Ba²⁺ molar ratio of 12 (stoichiometric ratio) is favourable.     

Preparation of M-Ba-ferrite fine powders by sugar-nitrates process

In this paper, fine M-type barium hexaferrite (M-Ba-ferrite) particles were synthesized from sugar and nitrates by simple route, which revealed the feasibility of using sugar as chelating agent in forming solid precursors of BaFe₁₂O₁₉. The effects of factors, such as the molar ratio of Fe/Ba, calcination temperature and time, on the morphology, the phase component and the magnetic properties of M-type barium hexaferrite particles were studied by means of X-ray diffraction, infrared spectroscopy, transmission electron microscopy and physical property measurement system. The results showed that the molar ratio of Ba²⁺ to Fe³⁺ influenced significantly on the formation of the single phase barium ferrite. The hexagonal platelet barium ferrite particles with a specific saturation magnetization of 64.48 emu/g, remanence magnetization (Mr) of 33.84 emu/g, and coercive force (Hc) of 1848.85 Oe were obtained when the molar ratio of Fe/Ba was 11.5 and the calcination temperature was 1100 °C for 2 h.     

偶氮氯膦——mA分光光度法测定钢样及食盐中钡

在pH9.0的NH_3—NH_4Cl缓冲溶液中,Ba(Ⅱ)与间乙酰基偶氮氯膦(CPAmA)生成紫蓝色络合物。络合物的最大吸收位于635nm。络合物的组成Ba(Ⅱ):CPAmA为1∶4,表现摩尔吸光系数ε_(max)=1.95×10~41·mol~(-1)·cm~(-1),钡(Ⅱ)含量在0-3.2×10~(-3)g/L范围内遵守比尔定律。本法用于测定钢样及食盐中的钡,结果满意。     

壳核型聚苯胺/钛酸钡复合电流变材料的制备及表征

采用溶液聚合的方法,在经过硅烷偶联剂表面修饰的钛酸钡微粉表面原位聚合聚苯胺,得到聚苯胺/钛酸钡壳核结构(BaTiO3/PAn)的有机-无机复合粒子.借助SEM、XRD、FT-IR、DSC-TG等分析手段研究了复合粒子的形貌、结构及热性能.利用改装后的旋转粘度计分别对钛酸钡和聚苯胺/钛酸钡复合颗粒的电流变性能进行研究.结果表明利用硅烷偶联剂成功地在钛酸钡粒子表面接枝合成聚苯胺,聚苯胺/钛酸钡复合颗粒电流变液的电流变性能明显比纯钛酸钡的电流变性能有所提高.     

纳米钛酸钡粉体的水热合成研究

采用氢氧化钡和四氯化钛作为钡源和钛源,氨水作矿化剂,在200～280℃保温4h条件下合成粒径为60～90nm钛酸钡粉体。TEM、XRD、钡/钛摩尔比(Ba/Ti)和比表面积的测试结果表明,在单一水介质中水热合成钛酸钡晶体的结晶过程遵循“溶解-结晶”机制,存在第II类聚集长大过程。前驱体浓度、合成温度和合成反应时间是影响粉体粒径的重要因素。粉体的Ba/Ti比过低会导致粉体中出现BaCO3杂质相,且Ba/Ti越低,钛酸钡晶体晶胞膨胀程度越大。     

Effect of Ultrasonic Processing on the Synthesis of Barium Titanyl Oxalate and the Characteristics of the BaTiO<Subscript>3</Subscript> Powder Prepared from It

Barium titanyl oxalate (BTO) with small deviations from stoichiometry has been synthesized by a chemical and a sonochemical method (under ultrasonication). Ultrasonic processing has been shown to reduce the particle size of the resultant BTO powder by about ten times and ensure a nearly spherical shape of the particles. The morphology of barium titanate powders prepared by decomposing the BTO at a temperature of 900°C is similar to that of the parent BTO and independent of stoichiometry. The powders have a barium to titanium ratio Ba/Ti = 1.002 and 0.987. The barium titanate powders synthesized using the sonochemical method contain a smaller amount of residual phases and have a larger specific surface area, smaller crystallite size (~100 nm), and smaller unit-cell parameters than do the powders prepared without ultrasonication.     

成分对烧结BAS(BaAl2Si2O8)凝胶玻璃形成的影响

采用XRD、SEM和拉曼光谱研究了溶胶一凝胶法制备的接近钡长石化学计量成分的Ba0．Al2O3-SiO2系烧结玻璃形成趋势。结果表明，在本实验条件下，SiO2含量高和BaO／Al2O3比值大，有助于形成玻璃。BaO／SiO2比值大，形成[AlO4]四配位结构的A12O3含量高。BaO／Al2O3与[AlO4]／Al^3 的关系近似线性关系。建立了一个烧结BAS凝胶玻璃形成的判别式，计算了在实验成分范围内，玻璃形成区与析晶区的边界线。根据判别式得到的计算结果与实验结果相符。     

Influence of synthesis variables on the properties of barium hexaferrite nanoparticles

Barium hexaferrite (BaFe₁₂O₁₉) nanoparticles were synthesized by sol–gel auto-combustion route. Prepared samples were sintered at 950 and 1100 °C with Fe³⁺/Ba²⁺ = 12 and 20 mol ratio. The formation mechanism of barium hexaferrite was investigated by using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses. In addition, the effect of temperature and Fe³⁺/Ba²⁺ mole ratio on BaFe₁₂O₁₉ formation and magnetic properties, and the effect of increasing the Fe³⁺/Ba²⁺ upon gel ignition and subsequent phase development were investigated. Finally the magnetic behavior was monitored with VSM. DSC studies showed that pure barium hexaferrite phase was formed from maghemite (γ-Fe₂O₃), without the formation of hematite (α-Fe₂O₃). Also, XRD results confirmed the formation of barium hexaferrite phase in non stoichiometric Fe/Ba ratio. VSM results showed that the saturation magnetization was decreased and coercivity increased with decreasing the grain size.     

Hydrothermal synthesis of barium ferrite fine particles from goethite

Barium ferrite fine particles were prepared from aqueous suspensions containing goethite (-FeOOH) and barium hydroxide by a hydrothermal method. Barium ferrite particles of thin hexagonal plate shape could be produced from commercially available goethite with an Fe: Ba molar ratio of 7.2, whereas barium ferrite particles could be produced from synthesized goethite with a molar ratio of unity. The effects on the size of hexagonal platelike particles of such reaction conditions as temperature, stirring speed and alkali concentration were investigated. Particles of 0.6 to 0.8 m mean size were prepared under the reaction conditions covered here.     

Homogeneous (co)precipitation of inorganic salts for synthesis of monodispersed barium titanate particles

Various processes of coprecipitation or crystallization of inorganicsalts of barium and titanium from homogeneous solutions were studiedin this work. In particular, barium hydroxide and barium chloridesalt as well as titanium tetrachloride were used as the startingmaterials for dielectric-tuning homogeneous precipitation in mixedsolvents of isopropanol and water. Hydroxypropylcellulose was used asa steric dispersant. Evaluations of size, shape, and composition ofsynthesized particles were made using scanning electron microscopy,high-temperature X-ray diffractometry, and differential thermalanalysis. Results show that salt concentration, pH, and reaction timeare important in determining the morphology and composition of thefinal powder. The titania particles from dielectric-tuningprecipitation are perfect microspheres with narrow size distribution(near monodispersed), while the particles from barium salts areflake-like, irregular in shape and size. Instead of particlescontaining uniform compositions of barium and titanium compounds,dielectric-tuning coprecipitation yielded powders of two separatedphases, i.e., monodispersed titania microspheres (1 m) coated onbarium chloride salt flakes. Titanium-rich barium titanate wasobtained after calcination of coprecipitated powders. However,preliminary results show that the titania particles obtained bydielectric-tuning precipitation can be hydrothermally converted toBaTiO₃ particles that are fully crystallized after calcination above950°C.     

Synthesis, characterization and dielectric properties of europium-doped barium titanate nanopowders

Europium-doped cubic barium titanate (BT) nanocrystals with % [Eu/Ti] mol ratio varying from 0.05 to 0.25 were prepared through hydrothermal route. The nano nature of these powders was confirmed by XRD and TEM studies. Pellets were prepared after calcining the powders at 1000 °C for 2 h. These pellets were annealed at 200, 500, 700 and 1000 °C for 2 h at each temperature and used for dielectric measurements. Raman spectra of two typical pellets with %[Eu/Ti] Eu/Ti mol ratios of 0.15 and 0.25 showed all the peaks characteristic of tetragonal BaTiO₃. Pure BT showed a low dielectric constant (DC) with a value of 398. Doping with small amounts of Eu resulted in many fold increase of DC values. A maximum value of 10576 at 1 KHz frequency was observed for the sample with % [Eu/Ti] mol ratio of 0.15. Lowering of Curie temperature T_c (95 to 110 °C) was observed for pure as well as Eu-doped barium titanate.     

钡铁氧体磁粉在液相中的分散性能

为了提高分散作用效果,选用聚乙二醇-20000(PEG-20000)、十二烷基硫酸钠(SDS)及二者组成的复配分散剂,利用机械球磨与添加分散剂相结合的分散方法制备了钡铁氧体浆料,通过考察分散剂的用量、浆料的pH值、zeta电位对分散性的影响,根据红外光谱分析,研究了分散剂的分散效果及作用机理,并测定了分散前后磁场成型各向异性钡铁氧体材料的磁性能。结果表明:加入分散剂可以改善钡铁氧体的分散效果,且SDS和PEG-20000的用量为钡铁氧体质量的1%和2%时,分散效果最好。SDS和PEG-20000均为静电和空间位阻稳定作用。分散后磁场成型各向异性钡铁氧体材料的磁性能得到提高。     

Microstructure and dielectric properties of Ba[Ti1 − x (Ln1/2Nb1/2) x ]O3 ceramics

We have studied the microstructure and dielectric properties of barium titanate-based ceramics containing niobium oxide and rare-earth (Nd, Sm, Gd, Dy, and Tm) oxide additions in a ratio needed for the formation of mixed perovskite solid solutions with the general formula Ba[Ti_{1 ? x} (Ln_1/2Nb_1/2) _x ]O₃. It was found that, after sintering at 1100–1120°C with the use of a zinc oxide-based sintering aid and manganese carbonate additions, the ceramics had a core-shell structure in which the core of the grains consisted of barium titanate and the shell consisted of a barium titanate-based solid solution. The average grain size of the major phase in the ceramics was within 0.7 μm. The ceramics contained additional phases in the form of inclusions which occasionally exceeded 5 μm in size. Their composition was determined. The Nd-, Sm-, and Gd-containing materials were shown to have the greatest potential as a base for the development of new engineering materials of stable groups with high dielectric permittivity for multilayer capacitors with electrodes containing 70% Ag and 30% Pd.     

Hexagonal ferrite particles for perpendicular recording prepared byion exchange

Particles of nonstoichiometric M-type barium hexaferrite with the chemical formula BaFe_10.5M_0.25O_17.05 (M=Mg, Cd, Co, Ni, Nd Zn) have been prepared by ion exchange in Ba containing molten salts from precursor ferrites with the β- or β"-alumina structure. The particles possess a plateletlike shape with diameters as low as 0.2 μm and as diameter-to-thickness ratio between 5 and 10. The Curie temperature is close to 470°C. Saturation magnetization values σ_s up to 64 emu g and coercive fields jH_c ranging from 0.5 to 1.5 kOe were found