Dy_2O_3掺杂对机械球磨Nd_2Fe_(14)B/α-Fe复合磁体矫顽力的影响

用机械球磨法制备Nd_2Fe_(14)B/α-Fe复合磁体,研究了Dy_2O_3掺杂对纳米复合磁体磁性能的影响。结果表明,掺入Dy_2O_3能显著提高复合磁体的矫顽力,且随着Dy_2O_3掺杂量的增大最大矫顽力对应的退火温度降低。X射线衍射分析结果表明,掺入Dy_2O_3使Nd_2Fe_(14)B的晶格常数减小,也即Dy部分替代Nd后生成了(Nd,Dy)_2Fe_(14)B硬磁相。因此,复合磁体矫顽力的增强主要归因于硬磁相磁晶各向异性的提高。但是,硬磁相磁晶各向异性的提高缩短了有效交换耦合长度,表现为过量掺杂Dy_2O_3使矫顽力降低。     

贫稀土钕铁硼合金与Nd_(67)Cu_(33)混粉热变形磁体组织演变过程及其对磁体矫顽力的影响

分别真空感应快淬贫稀土钕铁硼合金Nd_(11.5)Fe_(81.8)B_(6.0)Nb_(0.7)与Nd_(67)Cu_(33)薄带,然后制备Nd_(67)Cu_(33)含量0,3%,6%,9%,12%(质量分数)的混粉热变形磁体,分析讨论了贫稀土钕铁硼合金与Nd_(67)Cu_(33)混粉变形磁体中组织演变过程及其对磁体矫顽力的影响。研究结果表明,在热变形过程中当变形量由0增到30%时,混粉热变形磁体中Nd-Cu的扩散导致与之相邻区域的α-Fe晶粒尺寸减小、局部出现富稀土相、2∶14∶1相中稀土含量部分补偿性增加,整个磁体中α-Fe相体积分数减少、2∶14∶1相与软磁相α-Fe交换耦合作用增强,混粉热变形磁体的矫顽力随变形量的增加而增大;当变形量进一步增加,在双相磁体中富稀土相消失,2∶14∶1相和α-Fe相晶粒尺寸增大,一旦α-Fe晶粒尺寸超过交换耦合的临界尺寸将导致双相交换耦合作用恶化,2∶14∶1相晶粒尺寸增大导致其对磁体矫顽力的贡献降低,整个混粉热变形磁体的矫顽力随变形量的增加而大幅度下降;当变形量达到70%时,混粉热压热变形磁体随Nd_(67)Cu_(33)添加量的增加尽管2∶14∶1等效平均晶粒尺寸增大但磁体的矫顽力不断提高,原因在于随Nd_(67)Cu_(33)的增加磁体分别出现α-Fe消失、富稀土晶界相出现、且富稀土晶界相体积分数增大,富稀土晶界相的去磁耦合作用增强。     

SmCo_5/α-Fe双相复合纳米晶磁体的结构与磁性研究

超声波分解Fe（CO）5的产物Fe纳米颗粒,通过非均相沉淀获得包覆型SmCo5/α-Fe双相复合磁粉,采用放电等离子快速热压技术（Spark Plasma Sintering,SPS）制备出全致密的各向同性Sm-Co5/α-Fe双相复合纳米晶磁体,研究发现,软磁相α-Fe添加后,磁体的剩磁Mr有所提高,矫顽力Hci则有所减小,随后通过对各向同性磁体进行热变形制备出各向异性磁体,形成了较好的C轴晶体织构。软磁相α-Fe名义含量为10%时,磁体磁性能为：μ0Ms=1.01T、μ0Mr=0.86T、Hci=0.1708T。     

Nd2Fe14B/α-Fe纳米复合永磁的制备和性能

用超声化学法制备纳米Fe颗粒包覆的Nd2Fe14B复合粉体,将其在Ar气保护下经放电等离子烧结(SPS),得到Nd2Fe14B/α-Fe纳米晶复合磁体.Fe名义质量分数为5%的烧结磁体具有较高的磁性能:Br=0.86 T,Hci=683.8 kA/m,(BH)max=95.92 kJ/m3.烧结前对复合粉末进行适当的高能球磨,能促进显微组织进一步细化,增强软磁相与硬磁相之间的交换耦合,使相同Fe含量和烧结工艺的磁体Br和(BH)max分别提高到0.94 T和113.6 kJ/m3.     

Nd2Fe14B/α-Fe纳米复相永磁合金微结构的形成

研究了使用不同快淬速度制备的Nd3 6Pr5 4Fe83Co3B5合金中Nd2Fe14B/α-Fe复合纳米晶结构的形成.采用X射线(XRD)、透射显微(TEM)分析技术和振动样品磁强计(VSM)观测和测量了材料的微结构和磁性.结果表明,使用最佳淬速(20m/s)形成的Nd2Fe14B/α-Fe复合纳米晶结构晶粒细小,晶粒尺寸均匀Nd2Fe14B相和α-Fe相的平均晶粒尺寸分别为14nm、16nm.合金中α-Fe相的体积分数为48.6%.纳米晶合金的磁性能为Jr=1.108T,Hc=446.5kA/m,(BH)max=193.6kJ/m3,剩磁比Jr/Js=0.736.     

声化学法与放电等离子烧结制备Nd-Fe-B/α-Fe纳米晶复合磁体

采用声化学法制备Nd-Fe-B/α-Fe型双相包覆磁粉，再经放电等离子烧结（SPS）制备成致密块状磁体．研究了不同α-Fe包覆含量对复合磁体磁性能及微观结构的影响．结果表明，声化学法可以制备均匀混和的双相纳米磁粉，α-Fe纳米粉均匀的包覆在硬磁相颗粒周围．烧结后的各向同性磁体有明显的剩磁增强，具有较高的磁性能．当α-Fe包覆量为2％（体积分数）时，磁体性能最佳，其（BH）max值为148．64kJ/m^3．     

化学法制备Nd-Fe-B颗粒退火产物的物相调控

为了制备具有优良性能的Nd-Fe-B颗粒,在等时变温退火和等温变时退火的基础上,深入研究了温度和时间对Nd-Fe-B氧化物物相组成和百分含量变化的影响,然后对物相进行调控。最终确定了合理的退火温度和退火时间,成功制备出了以Nd_2Fe_(14)B为主相的Nd-Fe-B纳米颗粒。通过XRD、Rietveld精修拟合、SEM、TEM、VSM检测分析,结果显示Nd-Fe-B氧化物主要由FeNdO_3,NdBO_3和α-Fe组成,最佳的退火温度为750℃,最佳的退火时间为5 h,最终获得的Nd-Fe-B氧化物分别为54.619%的FeNdO_3,19.901%的α-Fe,11.760%的NdBO_3。利用该氧化物成功制备出含有88.457%的Nd_2Fe_(14)B和11.543%的Fe_3B纳米粒子的Nd-Fe-B颗粒,该颗粒的矫顽力约206.96 kA/m。     

La2Fe14B和Ce2Fe14B合金在快淬和热处理过程中相析出行为的比较

研究了溶体快淬三元La_2Fe_(14)B和Ce_2Fe_(14)B合金的相析出行为和磁性能,对不同快淬速度(10~50 m/s)和不同热处理温度下制备的样品进行了系统分析。结果表明,通过直接快淬,La_2Fe_(14)B合金中不能形成2∶14∶1硬磁相,而Ce_2Fe_(14)B合金可以获得2∶14∶1相。La_2Fe_(14)B合金在10m/s快淬时主要由La和α-Fe相组成,而Ce_2Fe_(14)B合金中2∶14∶1硬磁相在10m/s和20m/s快淬时析出。随着辊速的增加,非晶相逐渐增多并成为主相。在热处理过程中,La_2Fe_(14)B合金析出相以α-Fe和La相为主,并且高温下液态的富La相和α-Fe相可以共存;而Ce_2Fe_(14)B合金中先析出α-Fe,后析出2∶14∶1硬磁相,随后析出相长大。结果还表明,La_2Fe_(14)B比Ce_2Fe_(14)B有更高的非晶居里温度和更低的α-Fe相析出温度。由于硬磁相的析出,Ce_2Fe_(14)B合金可以获得较好的硬磁性能,包括一定的矫顽力。此研究对含La、Ce稀土永磁材料的生产具有一定的指导作用。     

保护气氛和样品状态对水热法制备Nd2Fe14B磁粉的影响

利用水热法,采用Nd(NO_3)_3·6H_2O、Fe(NO_3)_3·9H_2O和H_3BO_3为原料制备了Nd-Fe-B前驱体,再依次通过高温氧化退火,还原-扩散退火成功制备了主相为Nd_2Fe_(14)B的磁性粉体。利用X射线衍射(XRD)、振动样品磁强计(VSM)、扫描电子显微镜和透射电子显微镜(TEM)等表征手段,对产物的物相组成、磁性能及微观组织结构进行了分析,研究了还原-扩散退火过程中N_2、Ar和5%H_2/Ar混合气3种不同保护气氛以及片状和粉状两种不同样品状态对产物组成和性能的影响。结果表明,在N_2中反应无法合成Nd_2Fe_(14)B相,在Ar中虽能成功合成Nd_2Fe_(14)B相,但因软磁相和非磁相杂质的存在,磁性能较差。粉状样品也无法在还原-退火过程中合成Nd_2Fe_(14)B相。只有片状样品在5%H_2/Ar混合气的保护下进行还原-扩散退火,才可以成功合成杂质相少,磁性能高,颗粒尺寸为0.6～2μm,以Nd_2Fe_(14)B相为主相的磁粉。     

HDDR各向异性NdFeB及其各向异性形成机理研究

各向异性粘结NdFeB是目前稀土永磁研究的一个热点。本工作研究了NdFeB-M合金(M=Co、Ga、Zr)在吸氢-歧化-脱氢-复合过程(hydrogenation-disproportionation-desorption-recombination,简称HDDR)中各向异性形成的机理和HDDR各向异性NdFeB磁粉及粘结磁体制备技术。 首次发现合金元素M在歧化过程中富集在NdH_2/α-(Fe,Co)相界,形成Nd_2(Fe,M)_(14)B微结构,成为与母相Nd_2(Fe,M)_(14)B晶体位向一致的“记忆点”。在合适的再复合热力学和动力学条件下,仅发生‘记忆点’形核并具有足够高的形核率,最终得到具有晶体织构的细小晶粒组织,结果形成各向异性和实现磁硬化。 通过对HDDR工艺的实验研究,发现在从“氢化-歧化”阶段进入“脱氢-再复合”阶段的中间温度和氢压调整阶段对各向异性形成具有决定性影响。在此基础上提出了适合稳定制备HDDR各向异性NdFeB磁粉的“多阶段再复合工艺”,其典型磁粉的性能为Br=1.22T,Hci=930kA/m,BHm=248kJ/m~3。 研究了HDDR各向异性粘结NdFeB磁体的成型技术。发现静磁场温压成型、脉冲室温成型都适合制备HDDR各向异性粘结NdFeB磁体。所得粘结磁体的磁性能为Br=0.88T,Hci=930kA/m,BHm=128kJ/m~3。还设计和制造了适合于批量生产的全自动脉冲取向成型装置以及各向异性粘结磁体的注塑成     

Study of the formation of crystal texture in α-Fe/Nd2Fe14B nanocomposite magnets prepared by controlled melt-spinning

For further improving the magnetic properties of nanocomposite magnets, the study of the formation of crystal textures in the hard magnetic phase is of great significance. In the present study, a strong (00l) crystal texture with the c-axis perpendicular to the ribbon plane was obtained in Nd₂Fe₁₄B nanocrystals in the α-Fe/Nd₂Fe₁₄B nanocomposite magnets prepared by the controlled melt-spinning of NdPrFeCoB. The intensity of the texture weakens from the free surface layer of the ribbon to the layer attached with the wheel. The oriented Nd₂Fe₁₄B crystals have a fine equiaxed characteristic, d = 36 nm, in the layer attached with the wheel and a coarse columnar characteristic, d = 69 nm, in the layer near the free surface. The formation of the crystal texture in the Nd₂Fe₁₄B nanocrystals is attributed to a large temperature gradient normal to the ribbon plane during the melt-spinning process.     

Synthesis of high-energy-density Pr2Fe14−x Co x B,x⩽3, magnets for practical applications

Stable magnetic powders, of 1–2μm particle size, of partially Co-substituted, Pr₂Fe_14−x Co _x B,x⩽3, alloys together with 2–4 at% excess Pr were prepared by rapidly quenching the associated melts into thin ribbons and then mechanical attriting the ribbons in the refined particle sizes. The saturation magnetizationM _s, remanent magnetizationJ _r, intrinsic coercivityH _ci and Curie temperatureT _c were studied in characterizing the powders for fabricating into sintered or polymer bonded magnets. It is found that the smallx=0·4–0·8 substitution of the Co on Fe sites in this series sensitively leads to an increase in the value ofH _ci, by as much as 40%, with the optimum value of 21 kOe atx ∼ 0·55, together with an improvement in theT _c from 292°C to 325°C, without significantly diluting theM _s∼150 emu/g andJ _r∼8·0 kG values. The Co-substituted Pr₂Fe₁₄B alloy particles are better stable and corrosion resistant in ambient atmosphere. The results are discussed with the microstructure and comparison with the data for Nd₂Fe₁₄B powders processed under the same conditions. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Fe3Si nanodots epitaxially grown on Si(111) substrates using ultrathin SiO2 film technique

Ultrahigh density (> 10¹² cm⁻²) Fe₃Si nanodots (NDs) are epitaxially grown on Si(111) substrates by codeposition of Fe and Si on the ultrathin SiO₂ films with ultrahigh density nanovoids. We used two kinds of methods for epitaxial growth: molecular beam epitaxy (MBE) and solid phase epitaxy. For MBE, low temperature (< 300 °C) growth of the Fe₃Si NDs is needed to suppress the interdiffusion between Fe atoms deposited on the surfaces and Si atoms in the substrate. These epitaxial NDs exhibited the ferromagnetism at low temperatures, which were expected in terms of the application to the magnetic memory device materials.     

Self-controlled growth of Fe3BO6 crystallites in shape of nanorods from iron-borate glass of small templates

Fe₃BO₆ can be an ideal compound for devising functional magnetic and dielectric properties in a single material for multiple applications such as electrodes, gas sensors, or medical tools. Useful to tailor such properties, here we report on a self-controlled Fe₃BO₆ growth in a specific shape of nanorods from a supercooled liquid precursor (an inorganic polymeric liquid or glass) of an initial composition (100 − x)B₂O₃ − xFe₂O₃, x = 40–50 mol%. B₂O₃ as a strong glass former co-bridges the Fe³⁺ ions in oxygen polygons primarily in a 2-D interconnected polymer network so that it dictates preferably a 1-D directional growth on the reaction Fe³⁺ species in form of a compound Fe₃BO₆, a favorable phase to nucleate and grow when annealing a precursor at 500–800 °C in ambient air. Distinct nanorods with a diameter ∼200 nm and 40–100 μm length have been formed on 10–15 min annealing a sample in microwave at moderate temperature 550 °C. A bonded surface B₂O₃ layer (15–25 nm thickness) has grown on the Fe₃BO₆ of the nanorods in situ in a specific structure. XPS bands in the Fe³⁺, B³⁺ and O²⁻ species confer this model structure. A local BO₃ → BO₄ conversion has incurred in the boroxol (B₃O_4.5)_n, n → ∞, rings in the surface layer, showing three distinct IR bands at 1035, 1215 and 1425 cm⁻¹.     

Characteristics of NixFe100−x films deposited on SiO2/Si(1 0 0) by DC magnetron co-sputtering

Ni_xFe_100−x films with a thickness of about 200 nm were deposited on SiO₂/Si(1 0 0) substrates at room temperature by DC magnetron co-sputtering using both Fe and Ni₈₀Fe₂₀ targets. Compositional, structural, electrical and magnetic properties of the films were investigated. Ni₇₆Fe₂₄, Ni₆₅Fe₃₅, Ni₆₀Fe₄₀, Ni₅₅Fe₄₅, Ni₄₉Fe₅₁ films are obtained by increasing the sputtering power of the Fe target. All the films have a fcc structure. Ni₇₆Fe₂₄, Ni₆₅Fe₃₅, Ni₆₀Fe₄₀ and Ni₅₅Fe₄₅ films grow with crystalline orientations of [1 1 1] and [2 2 0] in the direction of the film growth while the Ni₄₉Fe₅₁ film has the [1 1 1] texture structure in the direction of the film growth. The lattice constant of the film increases linearly with increasing Fe content. All of the films grow with thin columnar grains and have void networks in the grain boundaries. The grain size does not change markedly with the composition of the film. The resistivity of the film increases with increasing Fe content and is one order of magnitude larger than that of the bulk. For all the films the magnetic hysteresis loop shows a hard magnetization. The Ni₇₆Fe₂₄ film has the lowest saturation magnetization of 6.75×10⁻² T and the lowest saturation field of 8.36×10⁴ A/m while the Ni₄₉Fe₅₁ film has a largest saturation magnetization of 9.25×10⁻² T and the largest saturation field of 1.43×10⁵ A/m.     

Epitaxial growth of Fe3Si/CaF2/Fe3Si magnetic tunnel junction structures on CaF2/Si(111) by molecular beam epitaxy

The Fe₃Si(24 nm)/CaF₂(2 nm)/Fe₃Si(12 nm) magnetic tunnel junction (MTJ) structures were grown epitaxially on CaF₂/Si(111) by molecular beam epitaxy (MBE). The 12-nm-thick Fe₃Si underlayer was grown epitaxially on CaF_2/Si(111) at approximately 400 °C; however, the surface of the Fe₃Si film was very rough, and thus a lot of pinholes are considered to exist in the 2-nm-thick CaF₂ barrier layer. The average roughness (Ra) of the CaF₂ barrier layer was 7.8 nm. This problem was overcome by low-temperature deposition of Fe and Si at 80 °C on CaF₂/Si(111), followed by annealing at 250 °C for 30 min to form the Fe₃Si layer. The Ra roughness was significantly reduced down to approximately 0.26 nm. A hysteresis loop with coercive field H_c of approximately 25 Oe was obtained in the magnetic field dependence of Kerr rotation at room temperature (RT).     

Synthesis and electrochemical properties of Ti doped Li3 − xFe2 − xTix(PO4)3/C cathode materials

Li_3 − xFe_2 − xTi_x(PO₄)₃/C (x = 0-0.4) cathodes designed with Fe doped by Ti was studied. Both Li₃Fe₂(PO₄)₃/C (x = 0) and Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C (x = 0.2) possess two plateau potentials of Fe³⁺/Fe²⁺ couple (around 2.8 V and 2.7 V vs. Li⁺/Li) upon discharge observed from galvanostatic charge/discharge and cyclic voltammetry. Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C has higher reversibility and better capacity retention than that of the undoped Li₃Fe₂(PO₄)₃/C. A much higher specific capacity of 122.3 mAh/g was obtained at C/20 in the first cycle, approaching the theoretical capacity of 128 mAh/g, and a capacity of 100.1 mAh/g was held at C/2 after the 20th cycle.     

Polymorphous Fe/FexOy composites: One-step oxidation preparation,composition control,and static magnetic and electromagnetic characteristics

Polymorphous Fe/Fe_xO_y core–shell and urchin-like composites were synthesized via a facile oxidation process at relatively low temperatures (100–300 °C) in the absence of surfactants or an external magnetic field. The oxidation temperature plays a key role in determining the morphology, crystal size, and composition of the resulting products. The static magnetic and electromagnetic (EM) properties of Fe/Fe_xO_y composites are influenced by their morphology, crystal size, and composition. In this study, excellent soft magnetic properties and enhanced permeability were obtained from core–shell Fe/Fe_xO_y composites with low Fe_xO_y shell contents and low surface anisotropy. In contrast, high coercivity and dielectric performance were exhibited by urchin-like Fe/Fe_xO_y composites with high shape and surface anisotropy. This work provides insights into the absorption mechanism of urchin-like complex absorption materials.     

An Efficient Process for Recycling Nd–Fe–B Sludge as High-Performance Sintered Magnets

Given the increasing concern regarding the global decline in rare earth reserves and the environmental burden from current wet-process recycling techniques, it is urgent to develop an efficient recycling technique for leftover sludge from the manufacturing process of neodymium–iron–boron (Nd–Fe–B) sintered magnets. In the present study, centerless grinding sludge from the Nd–Fe–B sintered magnet machining process was selected as the starting material. The sludge was subjected to a reduction–diffusion (RD) process in order to synthesize recycled neodymium magnet (Nd₂Fe₁₄B) powder; during this process, most of the valuable elements, including neodymium (Nd), praseodymium (Pr), gadolinium (Gd), dysprosium (Dy), holmium (Ho), and cobalt (Co), were recovered simultaneously. Calcium chloride (CaCl₂) powder with a lower melting point was introduced into the RD process to reduce recycling cost and improve recycling efficiency. The mechanism of the reactions was investigated systematically by adjusting the reaction temperature and calcium/sludge weight ratio. It was found that single-phase Nd₂Fe₁₄B particles with good crystallinity were obtained when the calcium weight ratio (calcium/sludge) and reaction temperature were 40 wt% and 1050 °C, respectively. The recovered Nd₂Fe₁₄B particles were blended with 37.7 wt% Nd₄Fe₁₄B powder to fabricate Nd–Fe–B sintered magnets with a remanence of 12.1 kG (1 G = 1 × 10⁻⁴ T), and a coercivity of 14.6 kOe (1 Oe = 79.6 A·m⁻¹), resulting in an energy product of 34.5 MGOe. This recycling route promises a great advantage in recycling efficiency as well as in cost.     

Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu₃Fe₂Sb₂O₁₂ is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe³⁺ in high spin state (S = 5/2). The coupling of Fe–Cu is antiferromagnetic, while that of Cu–Cu is ferromagnetic. The calculated total spin moment is 6.17 μ_B.