Two novel silver(I) complexes {[Ag(OTf)(PPh3)(4,4'-bipy)]}∞(1) and {[Ag2-(OTf)2(dppb)3](CH3CN)4}∞(2)(OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4'-bipy = 4,4'-bipyridine, dppb = bis(diphenylphosphino)butane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259(2), b = 9.85070(12), c = 16.3827(17) ?, V = 3108.0(5) ?3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F(000) = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections(I > 2σ(I)). Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370(11), b = 13.5261(13), c = 16.4539(15) ?, α = 106.7120(10), β = 97.3830(10), γ = 113.027(2)?, V = 2441.2(4)?3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F(000) = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections(I > 2σ(I)). Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4'-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.
Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In present study, we have developed an effective route to obtain recycled sintered magnets from Nd-Fe-B sintered magnet sludges by calcium reduction-diffusion(RD) process. Compared to conventional recycling process, our research is focused on recovering most of the useful elements, including Nd, Pr, Dy, Co, and Fe together instead of just rare earth elements. To improve the recycling efficiency and reduce pollution, the co-precipitating parameters were simulated and calculated using MATLAB software. Most of useful elements were recovered by a co-precipitation method, and the obtained composite powders were then directly fabricated as recycled Nd-Fe-B powders by a calcium reduction-diffusion(RD) method. The recovery rates are 98%, 99%, 99%, 93%, and 99%, for Nd, Pr, Dy, Co, and Fe, respectively. The amount of useful elements contained in the recovered composite powders is greater than99.71 wt%. The process of RD for synthesizing Nd_2 Fe_(14)B and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of1053 kA/m, and an energy product of 235.6 kJ/m^3, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.
Nd-Fe-B permanent magnets doped with CuZn_5 powders were prepared via conventional sintered method. The effects of CuZn_5 contents on magnetic properties and corrosion resistance of the magnets were systematically studied. It shows that the remanence,coercivity, and maximum energy product decrease gradually with the increase in CuZn_5 doping content. The magnet's corrosion kinetics in autoclaves environment and its electrochemical properties in electrolytes were also examined. It is interesting to see that the weight loss of3.5 wt% and 4.5 wt% CuZn5 powders doping magnets is only 1 and 0 mg·cm^(-2) after autoclaves test at 121℃,2 ×10~5 Pa for 500 h, respectively, which is much lower than that of the magnets without CuZn_5 doping. Electrochemical results show that the CuZn_5 powders doping magnets display more positive corrosion potential(E_(corr))and lower corrosion current density(I_(corr)) than those of the original magnets without CuZn_5 doping in sulphuric acid electrolyte and distilled water. It is, therefore, concluded that doping CuZn_5 powders is a promising way to enhance the corrosion resistance of sintered Nd-Fe-B magnets.
Zhuang WangWei-Qiang LiuDong-Tao ZhangMing YueXiu-Lian HuangXu-Liang Li
Recycling of waste sintered Nd-Fe-B permanent magnets by doping DyH 3 nanoparticles was investigated. The effect of the Dy H3 nanoparticles on the microstructure and magnetic properties of the recycled magnets was studied. As the DyH 3 nanoparticles additive increased, the coercivity of recycled magnet increased gradually. The recycled magnets with Dy H3 nanoparticle content between 0.0 wt.% and 1.0 wt.% maintained the remanence(Br), but, with higher additions, the Br began to decrease rapidly. The best recycled magnet produced contained 1.0 wt.% of DyH 3 nanoparticles when compared to the properties of the starting waste sintering magnet. The Hcj, Br and(BH)max values of 101.7%, 95.4%, and 88.58%, respectively, were recovered.
Grain boundary diffusion technique with TbH_3 nanoparticles was applied to fabricate Tb-less sintered NdFe-B permanent magnets with high coercivity. The magnetic properties and microstructure of magnets were systematically studied. The coercivity and remanence of grain boundary diffusion magnet are improved by 112% and reduced by 26% compared with those of the original magnet, respectively. Meanwhile, both the remanence temperature coefficient(α) and the coercivity temperature coefficient(β) of the magnets are improved after diffusion treatment. Microstructure shows that Tb element enriches in the surface region of Nd_2Fe_(14)B grains and is expected to exist as(Nd,Tb)_2Fe_(14)B phase. Thus, the magneto-crystalline anisotropy field of the magnet improves remarkably. As a result, the sintered Nd-FeB magnets by grain boundary diffusion with TbH_3 nanoparticles exhibit enhanced coercivity.
Wei-Qiang LiuCheng ChangMing YueJing-Shan YangDong-Tao ZhangJiu-Xing ZhangYan-Qin Liu
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℃,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^-4T),and a coercivity of 14.6 kOe(1 Oe=79.6A·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.
Nd-Fe-B permanent magnets with a small amount of Cu nano-particles doping have been prepared by conventional sintered method.Effects of Cu content on magnetic properties,corrosion resistance,and oxidation properties of the magnets have been studied.It shows that the coercivity rises gradually,while the remanence decreases simultaneously with increasing Cu doping amount.Microstructure observation reveals that Cu element enriches mainly the Nd-rich phase.Autoclave test results show that the corrosion rate of the magnets decreases with increasing Cu content.After oxidation,the maximum energy product loss of the magnets with 0 and 0.2 wt% Cu nano-particles doping are 6.13% and 0.99%,respectively.Therefore,it is concluded that Cu nano-particles doping is a promising way to enhance the coercivity and corrosion resistance of sintered Nd-Fe-B magnets.
