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磁制冷技术具有绿色环保和节能高效等优点, 被认为是有望取代气体压缩制冷技术的新一代制冷技术. 但目前磁制冷材料往往相变温区过窄(≤10 K), 需多个成分的材料叠加才能满足实际的制冷温跨. 本研究选择典型的La(Fe, Si)13基磁制冷材料, 创新采用梯度激光粉末床熔融技术, 3D打印出水平成分梯度的La0.70Ce0.30Fe11.65–xMnxSi1.35 (Mn含量从0—0.64连续变化)合金. 系统表征其显微结构、磁学性能及磁热效应可知, 该技术可实现成分沿粉末床平面的可控梯度分布与高通量制备, 从而实现了该梯度合金居里温度从134—174 K宽温区的连续变化. 随Mn含量增加, 合金相变从弱一级相变逐渐变为二级相变, 磁熵变曲线峰型从“尖而高”变为“宽而平”, 半高宽温区扩大至83.3 K, 使得梯度合金始终保持较高的制冷能力RC (~130 J/kg, 3 T). 本研究通过梯度增材制造突破传统材料制备与性能瓶颈, 为磁制冷材料高通量制备与性能优化提供全新技术路径.Magnetic refrigeration technology, featuring environmental friendliness, energy efficiency and high performance, is recognized as a next-generation refrigeration technology with the potential to replace gas compression refrigeration technology. However, current magnetic refrigeration materials typically exhibit an excessively narrow phase transition temperature range (≤10 K), thus necessitating the stacking of materials with multiple compositions to meet the practical refrigeration temperature span. In this study, the typical La(Fe, Si)13-based magnetic refrigeration material is selected, and an innovative gradient laser powder bed fusion technology is adopted to obtain 3D-print La0.70Ce0.30Fe11.65–xMnxSi1.35 alloys with horizontal compositional gradients (where the Mn content varies continuously from 0 to 0.64). Systematic characterization of their microstructures, magnetic properties, and magnetocaloric effects indicates that this technology enables a controllable gradient distribution of compositions along the powder bed plane and high-throughput preparation, thereby achieving a continuous variation of the Curie temperature of the gradient alloy over a wide temperature range from 134 K to 174 K. With the increase of Mn content, the phase transition of the alloy gradually changes from a weak first-order phase transition to a second-order phase transition, and the peak shape of the magnetic entropy change curve shifts from “sharp and high” to “broad and flat”. The full width at half maximum of the temperature range is extended to 83.3 K, allowing the gradient alloy to maintain high refrigeration capacity (RC ~130 J/kg, 3 T) at all time. This study breaks through the bottlenecks of traditional material preparation and performance via gradient additive manufacturing, providing a novel technical pathway for achieving high-throughput preparation and performance optimization of magnetic refrigeration materials.
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图 1 La(Fe, Si)13原始粉末的形状和尺寸分布 (a), (b) Mn0和Mn0.64粉末的SEM图像; (c), (d) Mn0和Mn0.64粉末的粒径分布结果
Fig. 1. Morphology and size distribution of as-prepared La(Fe, Si)13 powders: (a), (b) SEM images of Mn0 and Mn0.64 powders; (c), (d) particle size distribution results of Mn0 and Mn0.64 powders.
图 2 打印态CGAs的制备 (a) 制备流程图; (b) 不同形状梯度样品的宏观图像; (c) 沿梯度方向切片所得的62个样品, 编号为S1—S62
Fig. 2. Preparation of as-printed CGAs: (a) Preparation flow chart; (b) macrographs of gradient samples with different shapes; (c) 62 samples obtained by slicing along the gradient direction, numbered as S1—S62.
图 3 退火态CGAs的结构和成分演变 (a) XRD图谱; (b) 通过Rietveld精修得到的对应晶格参数; (c) EDS点扫描得到的1:13相Fe和Mn含量
Fig. 3. Microstructural and compositional evolution of as-annealed CGAs: (a) XRD patterns; (b) corresponding lattice parameters via Rietveld refinement; (c) Fe and Mn contents of the 1:13 phase by EDS point scanning.
图 4 退火态CGAs的磁相变 (a) 10 mT外磁场下的M-T曲线; (b) dM/dT曲线; (c) 居里温度
Fig. 4. Magnetic phase transition temperatire of as-annealed CGAs: (a) M-T curves under magnetic field of 10 mT; (b) dM/dT curves; (c) Curie temperature results.
图 5 退火态CGAs在0—3 T磁场下测得的磁化等温线
Fig. 5. Magnetization isotherms of as-annealed CGAs measured under a magnetic field of 0–3 T.
图 6 3 T磁场下退火态CGAs的磁熵变随温度的变化曲线
Fig. 6. Temperature dependence of |ΔSM| for CGAs under a magnetic field change of 3 T.
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