Superior corrosion resistance and corrosion mechanism of dual-main-phase (Ce15Nd85)30FebalB1M magnets in different solutions

The electrochemical corrosion behavior of both(Ce₁₅Nd₈₅)₃₀Fe_balB₁ M sintered magnets prepared with dual-main-phase method and N45-type magnets was studied in 3.5 wt% NaCl,1.1 wt% NaH₂ PO₄,and2.5 wt% NaOH solutions,respectively.The(Ce₁₅Nd₈₅)₃₀Fe_balB₁ M sintered magnets perform superior corrosion resistance than N45-type magnets in the tested solutions.In general,two ...     

高Ce 含量的速凝带及其磁性能

近年来,Nd-Fe-B磁体需求量的与日俱增间接地造成了稀土Ce 金属的大量积压,为提高稀土Ce 的利 用率,并降低Nd-Fe-B磁体的生产成本,可采取双主相合金法制备（Nd, Ce）-Fe-B磁体,为解决上述难题提供 了一种有效途径。通过对高Ce 含量速凝带的成分及速凝工艺的探索,成功制备出了具有较好枝晶且几乎 不含α-Fe 相的Ce-Fe-B 和（Nd, Ce）-Fe-B 速凝带。在制备的烧结磁体中,（Nd, Ce）-Fe-B 磁体的剩磁达到了 11.33 kGs,Ce-Fe-B磁体的剩磁达到了8.037 kGs,为后期制定制备高Ce 含量的高性能双主相磁体的热处理工 艺提供了数据参考。     

Effects of grain boundary ternary alloy doping on corrosion resistance of(Ce,Pr,Nd)-Fe-B permanent magnets

To satisfy the application of different environments,grain boundary doping is commonly used in the preparation of sintered magnets to improve the coercivity and the corrosion resistance.In this paper,the alloys were prepared by mixing different ratios of the master alloy(Ce,Pr,Nd)-Fe-B and the sintering aid(Pr,Nd)-Al.The coercivity of sintered(Ce,Pr,Nd)-Fe-B magnet is substantially enhanced by doping 2 wt%of(Pr,Nd)-Al,while the maximum energy product decreases slightly.We systematically investigated the corrosion behavior and micro structure of the sintered magnets in order to determine the mechanism of the degradation.The sintered(Ce,Pr,Nd)-Fe-B magnets with 2 wt% of(Pr,Nd)-Al addition exhibit the decreasing corrosion rate compared with others,due to the distribution of intergranular phases.The electrode potential difference between the main phase and the RE-rich phase is reduced by the addition of Al,improving the potential and stability of RE-rich phase due to the higher electrode potential of Al than that of Nd,Pr or Ce.In addition,the element distribution of the magnets doped by(Pr,Nd)-Al indicates that the Al-rich shell formed at the marginal area of the Ce-rich phase improves its stability.Therefo re,intergranular adding te rnary(Pr,Nd)-Al alloy powders results in both high coe rcivity and good corrosion resistance synchronously.     

液相扩散对钕铁硼磁体性能和组织结构的影响

用双合金工艺在Nd13.05Dy0.23Fe80.12B6.5铸片主合金中分别添加质量分数为3％～20％的富稀土铸锭辅合金Nd38.2Cc11.8Fe44.88Al4.12B,研究在钕铁硼永磁体中用Ce部分地取代Nd时对永磁体的磁性能的变化规律.实验结果表明,在一定的烧结及热处理工艺条件下,辅合金加入量介于8％ ～ 12％(质量分数)时,磁体的内禀矫顽力和磁能积相对较高,对剩磁的影响不大.显微成分分析表明,采用双合金法,使组织中细小的颗粒状富稀土相增多,形成了更多的对矫顽力有贡献的富稀土相,并且富稀土相分布于晶界上.     

Nd取代对Pr-Nd-Fe-B烧结磁体耐腐蚀性的影响

以HAST加速寿命试验后磁体失重,以及在不同腐蚀介质中磁体动电位极化曲线为表征,研究稀土元素Nd取代Pr对烧结Pr-Nd-Fe-B磁体耐腐蚀性的影响.结果表明:用Nd完全取代Pr后,磁体失重减小,室温下在0.1 mol/L HCl溶液、3.0 % NaOH溶液、3.5 % NaCl溶液中腐蚀电位不同程度地正移,表明磁体耐腐蚀性得到改善.通过场发射扫描电子显微镜观察HAST试验后磁体的微观组织形貌发现,Nd取代Pr后,晶界分布变得更加连续、清晰,且晶界交隅处的富稀土相含量减少,从而延缓了晶界腐蚀速率,使磁体的总体耐腐蚀性得到提升.      

Microstructure and corrosion resistance of sintered NdFeB magnet modified by intergranular additions of MgO and ZnO

Microstructure and corrosion resistance of sintered Nd15Dy1.2Fe77Al0.8B6 and Nd22Fe71B7 magnets modified by intergranular addition of MgO and ZnO were investigated. Both the remanence and sintering density of the magnets increased slightly with intergranular additions of MgO and ZnO. There was a remarkable increase in coercivity of Nd22Fe71B7 after addition. Besides, the effects on magnetic properties and an improved corrosion resistance were observed. Compared with the native magnets without addition, corrosion potential of the magnets with MgO and ZnO additives was more positive and the current density in the anodic branch of the polarization curve was reduced. Corrosion resistance resulting from autoclave testing （2×10^5 Pa of steam pressure, 120 ℃） showed that the corrosion rate of NdFeB magnets reduced with the increase of additive amount. Microstructure observation revealed that MgO and ZnO additives were incorporated into the intergranular phases in the magnets. With the introduction of MgO and ZnO, more intergranular phase with high oxygen content was formed while keeping the volume fraction of all the intergranular phases almost unchanged, which may contribute to improved corrosion resistance. Furthermore, addition of MgO and ZnO refined the grain size of Nd22Fe71B7.     

Corrosion resistance and mechanical properties of (Ho,Nd)FeB magnets

(Ho,Nd)FeB magnets with different Ho contents were prepared by Ho substitution for part of Nd during the casting process. Effects of Ho contents on the corrosion resistance and mechanical properties of (Ho,Nd)FeB magnets were analyzed by a highly accelerated aging tester, an electrochemical workstation, a microhardness tester, a bending tester, a scanning electron microscope and an X-ray diffractometer. Results show that the addition of Ho can change the main phase structure, optimize the distribution of rare-earth rich (RE-rich) phases in grain boundary, and improve the corrosion resistance and mechanical properties of NdFeB magnets. When the content of Ho increases from 0 to 21.0 wt%, the weight loss of magnets decreases from 2.672 to 0.933 mg/cm², and the microhardness and bending strength increase from 528.74 HV and 374.92 MPa to 633.84 HV and 459.80 MPa, respectively.     

Pitting corrosion behavior of cerium treated HSLA steel induced by sulfide inclusions in 3.5 wt% NaCl solution

Pitting corrosion behavior of Ce treated HSLA steels induced by sulfide inclusions in 3.5 wt% NaCl solution was investigated with potentiodynamic polarization and immersion corrosion test.The results show that Ce added steels exhibit better pitting corrosion resistance with lower corrosion current density and bigger pitting potential compared with steel without Ce,which is mainly attributed to optimized characteristics of spherical Ce-oxysulfide inclusions with less number density,smaller average size and lower pitting corrosion susceptibility.The spherical Ce₂O₂ S inclusions precipitated on the surface of CeAlO₃ inclusions in the Ce added steels induce pits with bigger opening mouth and shallow depth,reducing their tendency of extension to go deeper due to occlusion corrosion battery in the pitting holes.Furthermore,corrosion inhibitor Ce(OH)₃ generated by Ce₂O₂ S hydration can weaken electrochemical corrosion of the matrix micro-region around the pits.To avoid harmful bigger inclusions,Ce content in steels should be regulated within reasonable range,0.015 wt% Ce in present steels effectively modified inclusions to acquire the best pitting corrosion resistance of the steels.     

Coercivity enhancement of nanocrystalline hot-deformed Nd-Fe-B magnets by low-melting eutectic MM-Cu(MM=La,Ce,Pr,Nd) alloys addition

MM_(85)Cu_(15)(MM = La,Ce,Pr,Nd) eutectic alloys were added into the hot-deformed Nd-Fe-B magnets to enhance the coercivity.It is found that three endothermic peaks occur on the differential scanning calorimetry curve of the MM-Cu melt-spun ribbons at 432.2,451.1 and 516.5℃.The peaks substantially correspond to three types of MM-Cu low-melting eutectic phase.The coercivity of magnets increases when the MM-Cu content is lower than 4 wt%,and then keeps almost no change with the content further increasing to 5 wt%.The coercivity of the hot-deformed magnets with 4 wt% and without MM-Cu addition is 948 and 683 kA/m,respectively.Nearly all the platelet-shaped grains are isolated by the thickened intergranular phase after MM-Cu addition.Moreover,the average grain size of the magnets with MM-Cu addition decreases compared with that of the magnet without MM-Cu addition.Scanning electron microscopy images show that the areal fraction of the RE-rich grain boundary phase increases from 8.6% to 15.1% after MM-Cu addition.The La,Ce together with Cu and Ga aggregate at the grain boundary regions separating neighboring grains and smoothing the grain boundaries.Therefore,both the thickened grain boundary and decreased mean grain size result in the enhancement of coercivity after MM-Cu eutectic alloy addition.     

(Nd,Pr,Ce)-Fe-B磁体的组织与磁学性能

为开发低成本烧结钕铁硼磁体,用30% Ce替代(Nd_0.75Pr_0.25)_32.69Fe_66.25B_1.06磁体中的Nd和Pr,研究了磁体在烧结及回火过程中的组织结构和磁学性能变化.结果表明,取向压坯在1030~1080℃烧结2 h后,随烧结温度升高,磁学性能下降,烧结温度为1030℃时综合磁学性能均最好.烧结态Ce替代磁体的综合磁学性能优于未替代磁体.一级回火后,相组成和晶粒尺寸基本不变,边界结构也未发生明显变化,磁体性能基本不变,或有少量下降.二级回火后,晶界明显改善,获得较清晰且平直的晶界,磁体矫顽力均得到大幅提高.Ce替代磁体的剩磁、矫顽力和磁能积均稍低于未替代磁体.     

Influence of Nd and Y additions on the corrosion behaviour of extruded Mg-Zn-Zr alloys

To improve the corrosion resistance of wrought magnesium alloys through rare earth (RE) additions, the corrosion behaviour of Mg-5Zn-0.3Zr-xNd (x=0, 1, and 2; wt%) and Mg-5Zn-0.3Zr-2Nd-yY (y=0.5 and 1; wt%) alloys in a 5wt% NaCl solution was investigated using immersion test and electrochemical measurements. The results of immersion test show that Mg-5Zn-0.3Zr-2Nd alloy exhibits the best corrosion resistance among the tested alloys. Electrochemical measurements show that secondary phases in RE-containing Mg-5Zn-0.3Zr alloys behave as less noble cathodes in micro-galvanic corrosion and suppress the cathodic process. The additions of Nd and Y into Mg-5Zn-0.3Zr alloy also improve the compactness of the corrosion product film and are beneficial to the corrosion resistance.     

Preparation of Sintered (Ce1-xNdx) 30FebalCU0.1B1 Magnets by Blending Powder Method

Magnets with nominal compositions of(Nd1-xCex)30FebalCu0.1B1(x=0,0.15,0.3and 0.4,mass%)have been fabricated by blending powder method.The remanence(Br),intrinsic coercivity(Hc)and maximum energy product(BH)maxof the RE2Fe14 B type magnets deteriorated when Nd was replaced by Ce.The chemical composition and crystal structure of magnet were investigated systemically.Backscattered electron(BSE)and energy dispersive spectroscopy(EDS)results revealed that Ce-rich and Ce-lean matrix grains coexisted in the magnets.The magnetic coupling mechanism among the double hard magnetic phases was discussed.Low melting point RE-Cu phase was in favor of the formation of uniform continuous grain boundary.Transmission electron microscopy(TEM)investigation showed the presence of fcc(Nd,Ce)Oxphase in the grain boundary.When the Ce content was 15% of the total amounts of all the rare earth,the maximum energy product of the sintered magnet was 359.8kJ/m3.     

Anisotropic corrosion behavior of sintered (Ce0.15Nd0.85)30FebalB permanent magnets

In this work, the corrosion behavior of the surface parallel to the oriented c-axis(c‖) and perpendicular to c-axis(c⊥)in the(Ce_(0.15)Nd_(0.85))_(30)Fe_(bal)B dual main phase magnet was studied. With the addition of Ce,the volume fraction of RE-rich phase shown in the backscattered electron(BSE) images is basically approximate on the two surfaces. The free corrosion potential(E_(corr)) of the c‖ surface is more negative,which shows the worse corrosion resistance from the perspective of thermodynamics. While the reaction kinetics parameters with the smaller free corrosion current(i_(corr)) and the larger transfer resistance(R_(ct)) react the opposite conclusion in 3.5 wt% NaCl solution. Moreover, the c‖ surface performs smaller ions concentration of corrosion product and less damaged corrosion morphology compared to c⊥ surface after the free corrosion. The inconformity is not affected by the RE-rich phase, but by the anisotropy of the grains that the c‖ surface has larger density of the atoms and the lower ratio of(Nd, Ce)/Fe.     

NdFeB-CeFeB互扩散对其组织和磁性能的影响

近年来由于Ce元素的价格优势和特殊性能,Ce掺杂NdFeB永磁体受到越来越广泛的关注。通过900℃均匀化处理、真空扩散焊接和900℃扩散处理制备了NdFeB-CeFeB扩散偶,探究了NdFeB和CeFeB互扩散对各自微观结构和磁性能的影响。扫描电子显微镜(SEM)和能谱分析(EDS)结果发现,随着900℃保温处理时间增长,组织中的第二相和孔洞逐渐消失。互扩散后Ce原子不能置换Nd2Fe14B中的Nd原子,而是主要被富Nd相捕获。而Nd原子扩散后置换Ce2Fe14B中的Ce原子,形成了(Nd0.615Ce0.385)2Fe14B和(Nd0.165Ce0.835)2Fe14B两相,证明(Nd1-xCex)2Fe14B化合物存在溶解间隙。两相区(Ce,Nd)FeB样品中Ce平均原子数约占总稀土原子数的69%,饱和磁化强度μ0MS约为1.46T,各向异性场μ0HA约为7.37T,其磁性能未因高Ce含量而大幅下降主要归功于两相组织的"核壳"结构和Nd对Ce价态的影响。     

Improved corrosion resistance and thermal stability of sintered Nd-Fe-B magnets with holmium substitution

The effects of Ho substitution for Nd on the microstructure, corrosion resistance and thermal stability of the Nd-Fe-B magnets were investigated. The(Nd,Ho)-O phase was formed with increasing Ho substitution. The results of potentiodynamic polarization and highly accelerated stress test show improved corrosion resistance with increasing Ho substitution. The optimum mass loss 0.29 mg/cm~2 is achieved.Moreover, the average temperature coefficients for remanence and coercivity in the range of 25-150℃are both closer to zero, indicating improved thermal stability. The mechanisms for the improved corrosion resistance and thermal stability are discussed in relation to the microstructure featuring the(Nd,Ho)-O phase.     

(Ce_(20)Nd_(80))_(31)Fe_(bal)B_1M磁体腐蚀产物多样性的研究

对双主相粉末烧结工艺制备的(Ce_(20)Nd_(80))_(31)Fe_(bal)B_1M磁体进行高压加速腐蚀实验,观察其腐蚀形貌并进行EDS能谱分析。结果表明:腐蚀24 h后,腐蚀产物呈绒球状和圆球状。绒球状腐蚀产物主要是稀土相氧化物,随着腐蚀时间的增加,绒球状腐蚀产物演变为团絮状;圆球状腐蚀产物主要是铁的氧化物,随着腐蚀时间的延长,圆球状腐蚀产物部分脱落,没有脱落的被腐蚀颗粒缔结到基体上,一定程度上可以阻碍腐蚀的进一步进行。     

烧结温度对Nd24.38Ce0.52Gd6.65Febal.TM1.76B0.95磁体组织与性能的影响

采用双合金法制备Nd24.38Ce0.52Gd6.65Febal.TM1.76B0.95（质量分数,%）永磁体,通过扫描电镜及能谱、AMT-4磁测试仪、电子万能力学试验机等手段研究烧结温度对磁体组织和性能的影响.结果表明：随烧结温度从1060℃升高到1100℃,在烧结温度为1080℃时,晶粒均匀且结合致密,富稀土相分布均匀,能获得较好的组织形态;富稀土相中稀土总含量从84.98%增加到98.04%,烧结过程中铈从主相显著扩散到富稀土相;磁体剩磁Br、矫顽力Hcj、磁能积（BH）max 先升后降,在1080℃烧结时获得较好的磁性能,分别为1.22 T、964 kA/m 和293 kJ/m3,同时磁体抗弯强度也达到最大值为257 MPa.     

高丰度稀土永磁材料的研究现状与展望

随着稀土永磁材料应用领域的扩大及需求量的猛增,导致关键稀土元素(Pr、Nd、Dy、Tb)的过度使用,而高丰度稀土元素(La、Ce、Y)却不断积压.高丰度稀土永磁材料不仅可以降低成本,还可实现稀土资源综合平衡利用,出于国家战略安全和原材料成本角度考虑,高性价比的高丰度稀土永磁材料的研究与开发势在必行.近年来,大量学者对高丰度稀土永磁材料的高值化利用展开了广泛研究.然而,在不同成分合金中,其主相热稳定性、第二相种类、相析出行为、价态、微量元素的偏聚冶金行为等方面均与目前广泛使用的Nd基商业磁体存在较大差异.综述了高丰度稀土永磁材料的相结构、磁性能、微观结构和耐蚀性能等研究现状,并为其进一步开发与利用提出了建议.      

Preparation and characterization of sodium silicate/epoxy resin composite bonded Nd-Fe-B magnets with high performance

As an organic binder for bonded Nd-Fe-B magnets, epoxy resin(EP) has poor heat resistance but good moisture resistance, while sodium silicate(SS) has poor moisture absorption but better heat resistance and corrosion resistance. In order to improve high temperature stability and decrease moisture absorption of bonded Nd-Fe-B magnets, EP/SS composites were applied as the binder to prepare bonded Nd-Fe-B magnets. The magnetic properties, moisture absorption, corrosion resistance, compressive strength and microstructure of composite bonded magnets were investigated. The results show that EP/SS bonded magnets can obtain excellent magnetic properties at room temperature, and even useable magnetic properties a thigh temperature environments at 200°C. EP/SS composite binder effectively improves heat resistance and corrosion resistance of bonded Nd-Fe-B magnets, and reduces the hygroscopic properties. The molecule of sodium silicateis rigid and keeps it original shape at high temperature environments. In addition, SS in composite binder improves the mobility of the magnetic powders during the pre-pressing process, which makes the magnetic powders attain a more regular structure. These two factors will increase the mechanical properties. Moreover, sodium silicate in the composite binder can also cover the surfaces protecting the magnetic powders from oxidation and corrosion. EP in composite binder can cover SS surface to reduce the water absorption of SS as epoxy is a hydrophobic material. The EDX analysis shows that the composite binder has accumulated in the gaps of the magnet powders, which not only improves heat resistance and corrosion resistance, but also increases the mechanical properties. Therefore, EP/SS composite binder endows bonded Nd-Fe-B magnets excellent comprehensive properties.     

Structure and intrinsic magnetic properties of MM_2Fe_(14)B(MM=La,Ce, Pr,Nd) alloys

MM_(33)Fe_(66)B(MM=La, Ce, Pr, Nd) alloys(mass ratio) were prepared by induction melting and heat-treated at 1353 K for 24 h to produce homogeneous MM_2Fe_(14) B phase. The phase structure and element distribution of the alloys were analyzed by X-ray diffraction(XRD) and scanning electron microscope(SEM). The alloys were applied ball milling to obtain powders with good size distribution and then magnetic aligned in a static magnetic field of 2 T for 4 h, in order to achieve the intrinsic magnetic properties by vibrating sample magnetometer(VSM). XRD results showed that the alloys were composed of the single 2:14:1 main phase and RE-rich phase, which was similar to Nd_2Fe_(14)B structure. Magnetic measurements showed that the saturation magnetization(Ms) and anisotropy field(HA) of the MM_(33)Fe_(66)B alloy were 11.3 k Gs and 48.4 k Oe, respectively, demonstrating its good potential as permanent magnets. The Curie temperature of the MM_(33)Fe_(66)B alloy was determined as 502.9 K by magnetization-temperature curves. Microstructure observation showed that Nd and Pr were mainly in the 2:14:1 ferromagnetic phase, while La and Ce prefered to aggregate in the RE-rich grain boundary phase, which is beneficial to fabricating(Pr, Nd, MM)_2Fe_(14)B magnets with good magnetic properties.