放电等离子烧结-热变形各向异性Nd-Fe-B磁体的微观组织及磁性能

采用放电等离子烧结及后续热变形技术制备各向异性Nd-Fe-B磁体,研究烧结温度对放电等离子烧结Nd-Fe-B磁体微观组织和磁性能的影响。随着烧结温度在650~900°C范围内的升高,烧结态Nd-Fe-B磁体的剩磁、内禀矫顽力及最大磁能积呈现先升后降的趋势。在800°C下烧结所获得磁体的磁性能最佳。随后,对800°C烧结后具有最佳磁性能的磁体采用放电等离子烧结技术进行后续热变形处理。与初始吸氢-歧化-脱氢-再复合粉末和烧结态磁体相比,热变形磁体拥有更显著的各向异性和更好的磁性能。当热变形温度为800°C且压缩比为50%时,热变形磁体中的Nd2Fe14B晶粒呈扁平片状且不发生异常长大;磁体沿热压方向具有最佳的磁性能：Br、Hcj和（BH）max分别为1.16 T、449 k A/m和178 k J/m3。     

Synthesis and electrochemical performance of LiMnPO4/C composites cathode materials

LiMnPO4/C composites were synthesized via solid-state reaction with different carbon sources:sucrose,citric acid and oxalic acid.The samples were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM) and electrochemical performance test.The results of XRD reveal that carbon coating has no effect on the phase of LiMnPO4.The LiMnPO4/C synthesized at 600 ℃ with citric acid as carbon source shows an initial discharge capacity of 117.8 mAh·g-1 at 0.05 C rate.After 30 cycles,the capacity remains 98.2 mAh.g 1.The improved electrochemical properties of LiMnPO4/C is attributed to the decomposition of organic acid during the sintering process.     

SPS制备各向异性微米晶SmCo_5烧结磁体的研究

采用放电等离子烧结技术制备了各向异性微米晶SmCo_5磁体,研究了磁体的烧结工艺及添加Fe纳米粉对磁体结构和磁性能的影响。研究发现,SmCo_5烧结磁体的最佳烧结温度为830℃,此时磁体的室温磁性能最佳:B_r=8.19 kGs,H_(cj)=10.6 kOe,(BH)_(max)=13 MGOe;而添加Fe纳米粉的烧结磁体,饱和磁化强度升高,但剩磁和矫顽力降低。XRD结果表明,未添加Fe纳米粉的烧结磁体具有单相CaCu_5结构,而添加Fe纳米粉的烧结磁体出现了2∶17相和Fe-Co软磁相。SEM及能谱分析发现,添加的Fe纳米粉扩散进入了1∶5相,形成Sm(Fe,Co)_5和Sm_2(Fe,Co)_(17))。     

Possible methods of recycling NdFeB-type sintered magnets using the HD/degassing process

With the rapid growth in the use of NdFeB-type magnets and with the growing environmental need to conserve both energy and raw materials, the recycling of these magnets is becoming an ever important issue. In this paper it is demonstrated that hydrogen could play a vital role in this process. Fully dense sintered NdFeB-type magnets have been subjected to the hydrogen decrepitation (HD) process. The resultant powder has been subsequently processed in one of two ways in order to produce permanent magnets. Firstly, the powder was subjected to a vacuum degassing treatment over a range of temperatures up to 1000 °C in order to produce powder that would be suitable for the production of anisotropic bonded or hot pressed magnets. Secondly, the HD-powder has been used to produce fully dense sintered magnets; in which case optimisation of the milling time, sintering temperature and time was carried out. The optimum degassing temperature for coercive powder was found to be 700 °C, giving powder with a remanence (Br) of 1350 mT (±50 mT) and an intrinsic coercivity (Hcj) of 750 kA m⁻¹ (±50 kA m⁻¹). The best sintered magnet was produced by very lightly milling the powder (30 min, roller ball mill), aligning, pressing and vacuum sintering at 1080 °C for 1 h. The magnetic properties of this magnet were: (BH)_max = 290 kJ m⁻³ (±5 kJ m⁻³), Br = 1240 mT (±50 mT) and Hcj = 830 kA m⁻¹ (±50 kA m⁻¹); representing decreases of 15%, 10% and 20%, respectively, from the properties of the initial magnet.     

等离子喷涂La2(Zr0.7Ce0.3)2O7热障涂层的抗热震性能

采用等离子喷涂制备了La₂(Zr_0.7Ce_0.3)₂O₇（LZ7C3）热障涂层,并对涂层的微观组织、相结构、成分、相稳定性、涂层热导率以及抗热震性能进行了研究.结果表明,LZ7C3涂层由单相烧绿石结构物质组成,高温稳定性较好;涂层的热导率较块材下降约20%,这是由于涂层具有较高的孔隙率所致:涂层在不同温度范围的热震寿命和失效机制不同,在室温至约1000℃间的热震寿命为116 cyc,涂层失效方式以片状剥落为主:在室温至1100℃间的热震寿命为53 cyc,涂层失效方式为片状剥落和层状撕裂;在室温至1200℃间的热震寿命为3 cyc,涂层失效方式以层状撕裂为主.     

Effect of Heat Treatment Time on Dy–Cu Alloy Diffusion Process in Dy-Containing Commercial Nd–Fe–B Sintered Magnets

In this paper, the grain boundary diffusion process(GBDP) using a Dy_(70)Cu_(30)(at.%) alloy as the diffusion source was performed in a commercial sintered Nd–Fe–B magnet, and the effect of heat treatment time on the microstructure and magnetic properties of the magnet was investigated in detail. For the processed magnets heat-treated at 860℃, as heat treatment time increased, the coercivity and the depth of(Nd,Dy)_2Fe_(14)B core–shell structure increased first and then decreased. However, when the heat treatment time was more than 2 h, the diffusion path of Dy from the Dy-rich shell phase into the Nd_2Fe_(14)B grains was revealed, and a nearly homogeneous(Nd,Dy)_2Fe_(14)B phase was formed, which brought on the decrease in both the depth of visible core–shell structure and the coercivity of Nd–Fe–B magnet.     

CuO掺杂Ni0.4Zn0.6Fe2O4铁氧体的组织与性能探讨

采用传统球磨法制备了Ni0.4-xCu_xZn0.6Fe₂O₄（x＝0,0.12,0.20,0.28）铁氧体,并通过扫描电镜（SEM）、X-ray衍射（XRD）、综合热分析（TG-DSC）和振动样品磁强计（VSM）等手段研究掺杂CuO对Ni-Zn铁氧体的显微组织、相组成和磁性能。结果表明,随着CuO含量的增加,第二相Ni-Cu-Zn相生成,且 Ni-Cu-Zn铁氧体衍射峰强度逐渐增强;从显微组织形貌和能谱可以看出,Cu ^2＋参与了铁氧体的反应,CuO含量增加得越多,样品烧结性能越好,并促使Ni-Cu-Zn铁氧体的晶化温度降低;磁滞回线显示了Ni0.4-xCu_xZn0.6Fe₂O₄（x＝0,0.12,0.20,0.28）铁氧体的软磁特性,CuO原子分数x为0.2时的铁氧体的饱和磁化强度（Ms）最高,且具有较低的矫顽力（Hc）。     

放电等离子烧结制备纳米晶双相耦合(NdDy)11.5(FeCoNb)82.4B6.1致密磁体

使用放电等离子烧结(SPS)制备致密的纳米晶交换耦合Nd_2Fe_(14)B/α-Fe永磁合金.研究烧结温度、时间、压力对合金磁性能和显微组织的影响.结果表明,随温度、压力的升高,密度增大,磁能积增加;但温度过高或时间过长,使得晶粒长大,导致矫顽力降低.在烧结压力为500 MPa,烧结温度为700 ℃保温3 min后,得到密度为7.6 g/cm~3,晶粒细小的致密块体,其磁性能为:B_r=0.81 T,H_(ci) =856 kA·m~(-1),(BH)_m =106 kJ·m~(-3),其晶粒大小约20 nm.     

Structure and magnetic properties of Mn1.2Fe0.8P0.76Ge0.24 annealed alloy

Bulk Mn_1.2Fe_0.8P_0.76Ge_0.24 alloy was prepared by mechanical milling and subsequent spark plasma sintering technique.Effect of annealing on the structure and magneto-caloric properties of the alloy was investigated.XRD results show that both sintered and annealed samples possess a hexagonal Fe₂P-type crystal structure.After annealing,ferromagnetic impurity Fe₃Mn₄Ge₆,which exists in the sintered sample,was eliminated from the alloy.Furthermore,the lattice constants a and c change noticeably,leading to a decrease in c/a ratio,while the cell volume almost remains invariable.As a result,the Curie temperature of the alloy increases from 253 K to 298 K,but the maximum magnetic entropy change decreases from 37.5 to 11.7 J·kg·K^-1 for 2 T magnetic field change.On the other hand,the thermal hysteresis of M-T curves around T_C upon heating and cooling is 14 and 8 K for the as-sintered and the annealed sample,respectively,showing evident change.     

Mechanical properties and fracture mechanism study of sintered Nd–Fe–B alloy

The mechanical properties including bending strength (σ_bb) and fracture toughness (K_IC) of sintered Nd–Fe–B magnets have been examined in this paper. Alloyed magnet with Dy, Co, Nb additions shows the higher magnetic properties and bending strength but the lower fracture toughness than the ternary magnet. The zero plastic energy in bending procedure presents the purely brittle nature of Nd–Fe–B magnet. Fracture mechanism has been discussed on the base of the in situ SEM observation of micro-crack nucleation and FE-SEM (field emission scanning electron microscope) observation of indentation cracks. The fracture mechanism of sintered Nd–Fe–B alloy is concluded as two stages: the damage-accumulating stage and the crack-propagating stage. Some suggestions for improving toughness of sintered Nd–Fe–B magnets are mentioned.     

Behavior of residual carbon in Sm(Co, Fe, Cu, Zr)z permanent magnets

When sintered Sm(Co, Fe, Cu, Zr)_z permanent magnets are prepared by metal injection molding, some organic binders are added in alloy powder, which leads to much residual carbon in the magnets. The residual carbon decreases magnetic properties and destroys the microstructure of the magnets. In this paper, the behavior of carbon in Sm(Co, Fe, Cu, Zr)_z permanent magnets has been studied. The results indicate that Sm(Co, Fe, Cu, Zr)_z magnets can keep excellent magnetic properties when the carbon content is below 0.1 wt.%: Br ≥ 10 kGs, H_cj ≥ 22 kOe, BH_max ≥ 25 MGOe. When the carbon content is above 0.1 wt.%, Br, H_cj and BH_max decrease with increasing carbon content evidently. Carbon consumes Zr content and forms ZrC, which reduces the volume fraction of the lamella and Sm(Co, Cu)₅ phases. Thus, the cell size increases and the cellular microstructure deteriorates. When the carbon content reaches 0.43 wt.%, there is not enough Sm(Co, Cu)₅ phase to form a uniform cellular microstructure. Br, H_cj and BH_max are approximate to zero. Since carbon has little influence on the content of Sm₂(Co, Fe)₁₇ phase, Ms can keep a high value (≥100 emu/g). ZrC has high melting point (3420 °C) and acts as dispersion particle in the magnets, which prevents the grains of SEM structure growing and reduces the liquid content of green compacts during sintering. Therefore, the density of the magnets decreases.     

B effects on crystallization and magnetic properties of Pr_（9.44）Fe_（90.56-x）B_x（x=7.16, 4.76） nanocomposite magnets

Magnetic properties, phase evolution and microstructures of Pr_9.44Fe_90.56-xB_x (x=7.16 and 4.76) nanocomposite magnets have been investigated. Both as-spun ribbons exhibit two-step demagnetization curves, indicating the feature of partial crystallization. By using differential scanning calorimeter (DSC) measurements, remained amorphous phase of ribbon with x=7.16 shows a higher crystallization temperature. At optimum annealing temperature of 650 ℃for 10 min, better magnetic properties, M_r=1.01 T, _jH_c=796 kA/m and (BH)_max=136 kJ/m³ were obtained in the sample with x=4.76. Transmission electron microscopy (TEM) observation confirms that the sample with x=4.76 possesses much finer grain size, which causing a better exchange coupling between soft and hard magnetic grains.     

Sm0.5Sr0.5CoO3 cathode material from glycine-nitrate process: Formation, characterization, and application in LaGaO3-based solid oxide fuel cells

Cathode material Sm_0.5Sr_0.5CoO₃ (SSC) with perovskite structure for intermediate temperature solid oxide fuel cell was synthesized using glycine-nitrate process (GNP). The phase evolution and the properties of Sm_0.5Sr_0.5CoO₃ were investigated. The single cell performance was also tested using La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) as electrolyte and SSC as cathode. The results show that the formation of perovskite phase from synthesized precursor obtained by GNP begins at a calcining temperature of 600 °C. The single perovskite phase is formed completely after sintering at a temperature of 1000 °C. The phase formation temperature for SSC with complete single perovskite phase is from 1000 to 1100 °C. The SrSm₂O₄ phase appeared in the sample sintered at 1200 °C. It is also found that the sample sintered at 1200 °C has a higher conductivity. The electrical conductivity of sample is higher than 1000 S/cm at all temperature examined from 250 to 850 °C, and the highest conductivity reaches 2514 S/cm at 250 °C. The thermal expansion coefficient of sample SSC is 22.8 × 10⁻⁶ K⁻¹ from 30 to 1000 °C in air. The maximum output power density of LSGM electrolyte single cell attains 222 and 293 mW/cm² at 800 and 850 °C, respectively.     

Magnetoresistance enhancement and temperature stability of magnetoresistance in La1-x(Sr1-yNay)xMnO3

A series of the samples La1-x(Sr1-yNay)xMnO3(y=0.0,0.2,0.4,0.6,0.8,1.0)were prepared by the solid-state reaction method.Magnetoresistance enhancement and temperature stability of magnetoresistance in the system La1-x(Sr1-yNay)xMnO3 with unchanged Mn3+/Mn4+ ratio through the doping of both monovalent and divalent elements at A site were studied through the measurements of X-ray diffraction(XRD)patterns,resistivity-temperature(p-T)curves and magnetoresistance-temperature(MR-T)curves.The results indicate that with the increase of Na doping amount,the peak value of MR increases,and it increases from 12.4％ for y=0.2 to 50.6％ for y=1.0 in the magnetic field B=0.8 T;p-T curves exhibit the double-peak phenomenon,which comes from the competition between the resistivity of surface phase and that of body phase; for the sample of y=0.8,MR increases slowly from 8.3％ to 9.4％ in the temperature range from 259 to 179 K,and MR is so stable in such a wide temperature range,which provides reference for the research on the temperature stability of MR.     

Two-phase microstructure in Pr-(Fe, Co, Ni)-B sintered magnets

A search was carried out for a two-phase sintered magnet comprising Pr₂TM₁₄B and PrTM, where TM stands for Fe, Co and Ni. Specimens were prepared by a powder metallurgical method using alloys with compositions Pr₁₇(Fe_0.6Co_0.3Ni_0.1)₈₃−_χB_χ (x = 4, 5 and 6). X-Ray diffraction and scanning electron microscopy—energy-dispersive X-ray studies have revealed that two-phase magnets are realized for Pr₁₇(Fe_0.6Co_0.3Ni_0.1)₇₈B₅. The microstructures of these sintered magnets are characterized by Pr₂TM₁₄B grains surrounded by an intergranular Ni-rich PrTM phase whose thickness is less than about 3 μ.     

Sintering of alumina-niobium carbide composite

Several studies have been focused on particulate-dispersed Al₂O₃ composites in order to improve both room and high temperature mechanical properties and wear resistance. In the present work Al₂O₃-NbC composites have been pressureless sintered and their microstructures analysed as a function of NbC and Y₂O₃ concentration, the latter added as sintering aid. The compositions used in this study were Al₂O₃-xNbC and (Al₂O₃ 3%Y₂O₃)-xNbC, (x = 10, 20 and 40 wt%) and the sintering was performed at 1650 °C/30 min and 1750 °C/15 min. A density greater than 96% of the theoretical density was reached even for those materials sintered at 1650 °C. The observed microstructure was more homogeneous for the samples with Y₂O₃ addition and the Y₃Al₅O₁₂ phase was detected. The Al₂O₃ grain growth restraining due to the NbC concentration was more pronouncedly in samples sintered at 1750 °C.     

放电等离子烧结NdFeB的晶界结构与矫顽力

选取Nd11Dy2Gd2FebalAl4.0Nb0.8Zr0.8B6/Dy2O3磁粉采用放电等离子烧结技术制备各向异性磁体。微观组织和磁性能研究表明,烧结温度对磁体中晶界相的分布形态起决定作用。样品经870 ℃,12 min (40 MPa)放电等离子烧结及后续970 ℃, 2 h + 600 ℃, 1 h二级回火后,致密度达到7.39 g/cm3,剩磁达到1.08 T,矫顽力达到1181 kA·m-1。与同成分的传统烧结磁体相比较,放电等离子烧结磁体中晶界相分布不连续、晶界相中的稀土元素相对含量因烧损而显著下降以及晶界结构存在一定程度的不平衡等问题,都导致磁体的矫顽力较低。     

Microstructural evolution of Fe3B/Nd2Fe14B nanocomposite magnets microalloyed with Cu and Nb

The microalloying effect of Cu and Nb on the microstructure and magnetic properties of an Fe₃B/Nd₂Fe₁₄B nanocomposite permanent magnet has been studied by transmission electron microscopy (TEM) and atom probe field ion microscopy (APFIM). Additions of Cu are effective in refining the nanocomposite microstructure and the temperature range of the heat treatment to optimize the hard magnetic properties is significantly extended compared with that of the ternary alloy. Combined addition of Cu and Nb is further effective in reducing the grain size. Optimum magnetic properties obtained by annealing a melt-spun Nd_4.5Fe_75.8B_18.5Cu_0.2Nb₁ amorphous ribbon at 660°C for 6 min are B_r=1.25 T, H_cJ=273 kA/m and (BH)_max=125 kJ/m³. The soft magnetic Fe₂₃B₆ phase coexists with the Fe₃B and Nd₂Fe₁₄B phases in the optimum microstructure of the Cu and Nb containing quinternary alloy. Three-dimensional atom probe (3DAP) results show that the finer microstructure is due to the formation of a high number density of Cu clusters prior to the crystallization reaction, which promote the nucleation of the Fe₃B phase. The Nb atoms appear to induce the formation of the Fe₂₃B₆ phase when the remaining amorphous phase is crystallized.     

导电银浆在铝合金表面的烧结性能分析

制备一种用于铝合金表面烧结银厚膜的低温烧结型导电银浆,以解决铝合金的软钎焊问题. 采用熔融淬火方法制备玻璃化转变温度(T_g)为360 ℃的Bi₂O₃-B₂O₃-ZnO玻璃粉. 将玻璃粉、亚微米银粉和有机载体混合制成无铅低温烧结型银浆,将该银浆涂覆在6061铝合金表面,并在440,470,500,530 ℃的温度下进行烧结. 研究烧结温度对银厚膜的电阻率、可焊性及与基板结合强度的影响. 当玻璃粉与银粉重量比为1∶9,烧结温度为530 ℃时,烧结银厚膜的电阻率为2.2 μΩ·cm,抗剪强度为56.0 MPa;同时Al,Mg和Bi₂O₃发生氧化还原反应在银厚膜与铝基板界面产生纳米级Bi单质,进而实现冶金结合. 结果表明,提高烧结温度可以有效促进玻璃的润湿铺展、Ag颗粒之间的颈缩和Ag颗粒的生长,进而明显改善银厚膜软钎焊可焊性.     

Ni/Ti(C,N)包覆粉及其金属陶瓷的制备

采用非均相沉淀-热还原法制备Ni/Ti(C,N)包覆粉,并用该包覆粉经真空烧结制得金属陶瓷。利用扫描电镜、电子能谱、X-射线衍射等手段研究包覆粉的结构形貌及烧结后的微观组织与性能。结果表明:非均相沉淀过程中,非晶态的NiCO3·2Ni(OH)2·2H2O在Ti(C,N)颗粒表面成核并生长;经热还原过程后,NiCO3·2Ni(OH)2·2H2O分解并完全还原成Ni,Ni的平均晶粒尺寸约为50nm;采用包覆粉为原料制备金属陶瓷,有效改善了硬质相和粘结相的分布均匀性,但包覆粉烧结过程中存在晶粒长大现象;金属陶瓷的相成分为纯净的Ti(C,N)与Ni两相;金属陶瓷的综合性能相对于传统工艺制得的金属陶瓷有一定提高。