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Engineering topics

Liu, Xubo

Publications and source records attributed to Liu, Xubo.

Recycling of additively printed anisotropic Nd-Fe-B bonded magnets

A high potential cost-effective and environmentally friendly method has been applied for recycling anisotropic Nd-Fe-B bonded magnets. Waste additively printed Hydrogenation-Disproportionation-Desorption-Recombination (HDDR) Nd-Fe-B anisotropic bonded magnet was pulverized into composite powder containing Nd-Fe-B particles and nylon binder through cryomilling at a liquid nitrogen temperature (~77 K) under Ar inert atmosphere. Then, the cryomilled composite powder was warm compacted into a bonded magnet. Further, the magnetic particles were aligned during post-compaction annealing under a magnetic field of 30 kOe. The recycled bonded magnets have a higher density (3% enhancement), but slightly inferior magnetic properties compared to the original magnets, i.e., the magnetic remanence, coercivity and maximum energy product are reduced by 2%, 3% and 8%, respectively. The scanning electron microscopy revealed that some HDDR Nd-Fe-B powder crumbled into fine particles during cryomilling. Powder X-ray diffraction showed a small amount of Nd-oxide impurity in the cryomilled powder. The slightly deteriorated magnetic properties are ascribed to the oxidation of Nd-Fe-B particles due to formation of fresh fracture surface during cryomilling. The approach enables the direct reuse of end-of-life bonded magnets in an economical and environmentally friendly way.

36 MATERIALS SCIENCE↗

Coercivity of (Fe 0.7 Co 0.3 ) 2 B Nanowire and Its Bonded Magnet

(Fe 0.7 Co 0.3 ) 2 B are potential permanent magnets material due to its large saturation magnetization and high Curie temperature. However, it has moderate magnetocrystalline anisotropy (MCA) and low coercivity. One way to improve its coercivity is to combine the contributions from magnetocrystalline- and magnetic-shape anisotropy by preparing (Fe 0.7 Co 0.3 ) 2 B nanowires. We study the effects of size, morphology, and surface defects on the hard magnetic properties of nanowires using micromagnetic simulation. The hard magnetic properties of (Fe 0.7 Co 0.3 ) 2 B nanowire-bonded magnets are estimated, including the role of inter-wire magnetostatic interaction. By considering the existence of local reductions in MCA energy of up to 30% on the surface layer of nanowires, the anisotropic bonded magnet with a 65% vol. of (Fe 0.7 Co 0.3 ) 2 B nanowires would have typical remanence, B r = 7.6–8.4 kG, coercivity, H ci = 9.6–9.9 kOe, and maximum energy product, (BH) m = 14–17.8 MGOe. Developing effective technology for synthesizing nanowires and fabricating corresponding bonded magnets is promising for manufacturing practical magnets based on the magnetic phase with a relatively low or moderate MCA, such as (Fe 0.7 Co 0.3 ) 2 B.

36 MATERIALS SCIENCE↗

Hot-Roll Fabrication of Anisotropic Nanograin Nd-Fe-B Magnet

Nd-Fe-B based magnets have the highest energy product among all permanent magnets, which is required for numerous clean energy technologies. For higher temperature applications (T > 150°C), additions of heavy rare earth elements (HREEs) such as Dy are required to maintain sufficient coercivity during operation. Additions of Dy are expensive. Thus, it is desirable to reduce the need for HREEs by reducing the grain size to the nanoscale, which increases the coercivity and decreases its temperature dependence. Here, we report a novel nanograin Nd-Fe-B magnet fabrication method that is continuous and inexpensive. The process uses mechanically milled Nd-Fe-B melt-spun flakes as feedstock powder that is packed into a metal vessel and then hot rolled to form a fully dense and highly textured strip magnet with tailored thicknesses, down to 800 µm. Finally, using this process, fully dense nanograin bulk magnets can be synthesized in minutes compared to the traditional multi-step processes that are typically low throughput.

36 MATERIALS SCIENCE↗

Site Occupancy Preference and Magnetic Properties in Nd 2 (Fe,Co) 14 B

Partial replacement of Fe by Co is an effective method to increase Curie temperature (T C ) , which improves the thermal stability of magnetic properties in Nd 2 Fe 14 B-based permanent magnets. The correlation between Fe substitution and magnetic properties has been studied in Nd 2 (Fe,Co) 14 B via a first-principles calculation. The calculated Fe substitution energies indicate that the Co atoms avoid the 8 j 2 site, which agrees with the experiments. The Co atoms are ferromagnetically coupled with Fe sublattice and show magnetic moments of about 1.2 to 1.7 μ B at different crystallographic sites, less than that of Fe (2.1–2.7 μ B ), resulting in the decrease in total magnetization at ground state (0 K) with increasing Co content. The effective exchange interaction parameter, derived from the energy difference between varied magnetic structures, increases from 7.8 meV to 17.0 meV with increasing Co content from x = 0 to x = 14 in Nd 2 Fe 14–x Co x B. This change in the effective exchange interaction parameter is responsible for the enhancement of T C in Nd 2 (Fe,Co) 14 B. The total magnetization at 300 K, derived from mean-field theory, shows a peak maximum value at x = 1 in Nd 2 Fe 14–x Co x B. The phenomenon results from the interplay between the reduction of the magnetic moment in the Fe(Co) sublattice and the enhancement of T C with increasing Co content.

36 MATERIALS SCIENCE↗

Effects of magnetic field annealing on the hard magnetic properties of milled Nd-Fe-B powders

In this study, we report the effect of magnetic field annealing (MA) in relieving the stress induced during the milling of Nd-Fe-B sintered magnets. The effect of MA processing parameters and particle size on the magnetic properties were investigated. Based on the results, magnetic field annealing is more effective in improving the magnetic properties of larger size particles, compared to finer particles. Our computational study on the role of particle surface defects in bi-modal particle distribution agrees with results obtained experimentally. In conclusion, magnetic field annealed powder has been successfully used to develop 4.6 g.cm -3 density bonded magnets with 75 vol% of magnetic powder and polyamide 12 (nylon 12) polymer binder resulting in 11.3 MGOe energy product.

36 MATERIALS SCIENCE↗

Reconfigurable Magnetic Liquid Building Blocks for Constructing Artificial Spinal Column Tissues

All-liquid molding can be used to transform a liquid into free-form solid constructs, while maintaining internal fluidity. Traditional biological scaffolds, such as cured pre-gels, are normally processed in solid state, sacrificing flowability and permeability. However, it is essential to maintain the fluidity of the scaffold to truly mimic the complexity and heterogeneity of natural human tissues. Here, this work molds an aqueous biomaterial ink into liquid building blocks with rigid shapes while preserving internal fluidity. The molded ink blocks for bone-like vertebrae and cartilaginous-intervertebral-disc shapes, are magnetically manipulated to assemble into hierarchical structures as a scaffold for subsequent spinal column tissue growth. It is also possible to join separate ink blocks by interfacial coalescence, different from bridging solid blocks by interfacial fixation. Generally, aqueous biomaterial inks are molded into shapes with high fidelity by the interfacial jamming of alginate surfactants. The molded liquid blocks can be reconfigured using induced magnetic dipoles, that dictated the magnetic assembly behavior of liquid blocks. The implanted spinal column tissue exhibits a biocompatibility based on in vitro seeding and in vivo cultivating results, showing potential physiological function such as bending of the spinal column.

60 APPLIED LIFE SCIENCES↗

Hard and semi-hard Fe-based magnetic materials

Iron (Fe) is the most important ferromagnetic element, not only for its high magnetic moment and high Curie temperature but for its abundance as well. Fe-based magnetic materials are therefore widely applied in technologies and industries, with most of the applications for soft magnetic materials, because of the low magnetocrystalline anisotropy (MCA) of Fe. However, it is possible to realize magnetic hardening in Fe-based materials as we have learned from the early carbon steel permanent magnets although their coercivity was modest. Recent efforts to search for rare-earth-free hard magnetic materials have shown more promising evidences for achieving high MCA in Fe-based materials. In this paper, we review the history and the recent developments of Fe-based hard and semi-hard magnetic materials with a focus on mechanisms of high MCA in Fe-based phases and the related crystal and electronic structures. Here, we have tabulated and discussed the structures and the magnetic properties of the Fe-based binary or ternary systems containing p-block and d-block elements, with many of them showing considerable MCA. Furthermore, it is important to know and to understand that the MCA in Fe-based magnetic materials can be tailored/enhanced through chemical and/or structural modifications that will lead to “artificially engineered” hard and semi-hard magnetic materials for advanced permanent magnets in the future.

36 MATERIALS SCIENCE↗

Toughening Sm–Co sintered magnets via microstructure modification with additives

We report the mechanical properties of the brittle Smsingle bondCo permanent magnets are of great practical significance. However, studies on the magnets have mostly focused on their magnetic properties. This paper reports the modified microstructure and refined unimodal grain size, enhanced flexural strength, and magnetic properties of Sm 2 (Co,Fe,Cu,Zr) 17 sintered magnets doped with La 2 O 3 , MgO, and CaF 2 fine particulates. The correlations between microstructure, phase composition, and mechanical and magnetic properties were studied. Doping of a small amount (e.g., 0.5–3 wt%) of La 2 O 3 , MgO, or CaF 2 fine particulates could significantly refine the unimodal grain sizes of the Smsingle bondCo magnets via the Zener pinning effect. Moreover, doping significantly improved the flexural strengths σ of the magnets. For example, the σ values of the magnets with 0.5 wt% MgO, 1 wt% La 2 O 3 , and 1 wt% CaF 2 were approximately 65%, 63%, and 42% higher than that of the reference magnet, respectively. Micromechanical simulations revealed that the fine particles of La 2 O 3 could deflect crack growth, while the CaF 2 particles could attract or arrest cracks during the fracture process. The mechanical strengthening effect was mainly due to grain size refinement. The Smsingle bondCo magnets with 0.5–1.5 wt% CaF2 and 0.5 wt% La 2 O 3 exhibited excellent magnetic properties while doping 1–3 wt% La2O3 and 0.5–3 wt% MgO deteriorated magnetic performance. The rational design of CaF 2 - or La 2 O 3 -doped microstructure can be an economical and effective method for producing toughened Sm–Co sintered magnets with high magnetic performance.

36 MATERIALS SCIENCE↗

Engineering microstructure to improve coercivity of bulk MnBi magnet

MnBi is a candidate material for high-temperature magnets because of its increasing coercivity with increasing temperatures up to 255 °C. However, most efforts in fabricating bulk MnBi magnets have run into the problem of preserving the coercivity (H cj) of its feedstock powders. About 70% of powder’s H cj would be lost during the densification process. Our micromagnetic modeling shows that the coercivity mechanism of the MnBi bulk magnet is controlled by nucleation of the reversal magnetization domains, and the large H cj loss that occurred during the powder consolidation process can be attributed to the inter-grain magnetic coupling. To attain a high H cj , the grains in the MnBi bulk magnet must be separated with a non-magnetic grain boundary phase (GBP). To validate this GBP hypothesis, we engineered MnBi bulk magnets with two different types of GBP. The first type of GBP was created in-situ by precipitating excessive Bi from the grains; the second type was created ex-situ by coating silicates on the feedstock powders before the consolidation. While both GBP work, the ex-situ approach resulted in a better H cj due to a more uniform GBP distribution. We report the H cj loss was reduced from 70% to 15%, and the (BH)max of a warm sintered bulk magnet reached 8.9 MGOe.

36 MATERIALS SCIENCE↗

Mechanically robust high magnetic-performance Sm-Co sintered magnets through microstructure engineering

Samarium-cobalt (Sm-Co) sintered magnets have high magnetic energy densities, great resistance to demagnetization and corrosion, and excellent thermal stability in a wide temperature range (–50–550 °C). However, the utilization of these magnets is restricted by their brittleness. Based on micromechanical and the Zener pinning model, Sm-Co sintered magnets with improved mechanical properties have been designed and fabricated via microstructure engineering. A small amount of fine Sm 2 O 3 particulates (0–3 wt%) has been incorporated into Sm 2 (CoFeCuZr) 17 sintered magnets to refine the grain size by up to approximately 50% (from 45 to 22 µm) and narrow the grain size distribution. Doping with 3 wt% Sm 2 O 3 increased the flexural strength by 62% while maintaining magnetic performance. Both grain-refined unimodal microstructure and heterogeneous laminated coarse/fine grain microstructure were formed by strategically designed assemblies of Sm 2 O 3 -added Sm-Co powder feedstock mixtures. The technology is compatible with existing magnet manufacturing processes. Numerical micromechanics simulation indicates that the fracture is dominated by intragranular mode. The mechanical strength is mainly enhanced by the additive-induced grain refinement, while the small amount of Sm 2 O 3 addition has a small direct positive contribution. Finally, these magnets will be more cost-effective, efficient, and robust for various functional applications.

36 MATERIALS SCIENCE↗

Thermal stability of anisotropic bonded magnets prepared by additive manufacturing

Abstract In this research, anisotropic NdFeB + SmFeN hybrid and NdFeB bonded magnets are additively printed in a polyphenylene sulfide (PPS) polymer binder. Printed NdFeB + SmFeN PPS bonded magnets displayed excellent magnetic properties ( B r [remanence] = 6.9 kG [0.69 T], H cj [coercivity] = 8.3 kOe [660 kA/m], and BH max [energy product] = 9.9 MGOe [79 kJ/m 3 ]) with superior corrosion resistance and thermal stability. The anisotropic NdFeB bonded magnet shows a high coercivity of 14.6 kOe (1162 kA/m) with a BH max of 8.7 MGOe (69 kJ/m 3 ). The coercivity and remanence temperature coefficients for NdFeB + SmFeN hybrid bonded magnets are −0.10%/K and −0.46%/K, and for NdFeB bonded magnets are −0.14%/K and −0.53%/K in the range of 300–400 K, indicating that the hybrid bonded magnets are thermally stable. The average flux aging loss for hybrid magnets was also determined to be very stable over 2000 h at 448 K (175°C) in air with 2.04% compared to that of NdFeB magnets with 3.62%.

thermal stability↗

Mechanically strengthened heterogeneous Sm-Co sintered magnets

Samarium-cobalt sintered magnets offer excellent magnetic properties, thermal stability, and corrosion resistance. They are used in a variety of defense and civilian applications, especially when elevated operation temperatures (e.g., 200 ºC to 550 ºC) are required. However, the utilization of these materials is restricted by their brittleness. Improving their mechanical resilience would make them more cost-effective, efficient, and robust in decarbonization and other function-related applications while reducing the pressure on critical material supply chains. In this paper, we engineer a series of novel heterogeneous microstructures, such as laminated coarse grain (CG)/fine grain (FG) and core/shell CG/FG microstructures, to produce unprecedented combinations of superior mechanical and magnetic properties without altering the chemical compositions of the magnets or common heat treatment procedures. Further, a 60% flexural strength enhancement is obtained using heterogeneous Sm 2 (CoFeCuZr) 17 sintered magnets with little impact on their magnetic properties. The mechanically robust heterogeneous Sm-Co sintered magnets have a minor (e.g., less than 4.6%) reduction in the energy product (BH) max due to a slightly reduced squareness of the demagnetization curve, with no decrease in either the remanence (B r ) or the intrinsic coercivity (H ci ). The flexural strengths of these heterogeneous Sm-Co magnets depend on the volume ratios and mean grain sizes of the FG/CG regions, as well as their microstructural architectures. The fine-grained regions act as mechanical strengthening sites, which can be strategically used when designing the magnet for different applications. This technology is highly compatible with existing magnet manufacturing processes and thus can be adopted readily by the magnet industry.

36 MATERIALS SCIENCE↗

Challenges in Postprocessing of Hybrid Manufacturing of Magnet Polymer Composites to Enhance the Energy Product of NdFeB Bonded Magnets

Bonded permanent magnets need to process magnetic filler particles and binder together which is a form of hybrid or composite manufacturing that needs to simultaneously process multimaterials. Polymer bonding of the permanent magnets decreases the energy product of the bonded magnets which varies with square of loading fraction of magnetic materials. However, due to high viscosity of bonding polymer prohibits loading higher than 80 volume % of magnetic materials in most efficient loading process such as compression molding. To further increase the loading of magnetic fraction in the bonded permanent magnets, it is expected to be beneficial to introduce a fraction of nonreacting thermally sacrificial polymer along with permanent bonding polymer in the least permissible of about 20 volume % of the polymer. This process of first adding the sacrificial polymer for higher processability for composites and later removing it via post processing such as heat treatment provides a simple example of inclusion of both the additive and the subtractive stages of hybrid manufacturing. These hybrid composite magnets can be heat treated to remove the sacrificial polymer to further increase the density and energy product which might require to implement hot isostatic pressing for compaction. Although the identification of such ideal polymer requires an extensive polymer chemistry research, we have compression molded several permanent bonding polymers such as nylon, polycarbonate (PC) and polyphenyl sulfide (PPS) and potential sacrificial polymer such as polyoxymethylene (POM), polystyrene (PS), and Acrylonitrile Butadiene Styrene (ABS) and heat treated to remove the sacrificial polymers. It is discovered that oxygen free low temperature pyrolizable polymers could be the potential candidates for increasing the magnet particles loading for achieving high energy products.

36 MATERIALS SCIENCE↗

The Buckling Spectra of Nanoparticle Surfactant Assemblies

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. In this study, we show that the bending modulus, B , of thin assemblies of nanoparticle surfactants (NPSs) at the oil–water interface can be varied continuously from sub- k B T to 10 6 k B T , by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

77 NANOSCIENCE AND NANOTECHNOLOGY↗