By virtue of the unique advantages of compensating and controlling thermal expansion, negative thermal expansion (NTE) materials have attracted great attention and have gained rapid development in the last two decades. The history of NTE can be traced back to the discovery of magnetic Invar alloy in 1897. Due to the complexity and variability of magnetism, studies on the magnetic NTE materials, including the discovery of new materials, the controllable thermal expansion, and the origin of magnetic NTE, have never stopped for more than one century. In this review, we will summarize the progress in the magnetic NTE materials from the prototype Invar alloys to the recently discovered materials such as Mn-based antiperovskites, Laves phases, La(Fe,Si)₁₃, Mn₃Ge, R₂Fe₁₇, R(Fe,V)₁₂, and R₂Fe₁₄B (R = rare earth elements). Based on the variable magnetic transition types, the magnetic NTE materials are reviewed in detail from magnetic and crystal structures, NTE properties, and mechanisms. The main mechanisms of the NTE of magnetic materials are summarized for the first time, including order-to-disorder transition, the change of local moment, metamagnetic transition, short-range magnetic ordering, structural phase transition, and the coexistence of magnetic phases. The NTE properties of magnetic materials can be controlled by adjusting magnetic exchange interaction via the methods of chemical substitution, nanocrystallization, external field, and interstitial atoms. More importantly, by enhancing the negative contribution of the magnetic transition to thermal expansion, the new magnetic NTE materials can be found from the normal positive thermal expansion materials. This review will be helpful for the design of novel magnetic NTE materials, the control of thermal expansion properties, and the understandings of magnetic NTE mechanisms.

近二十年来，负热膨胀（NTE）材料凭借其独特的补偿和控制热膨胀的优势而受到广泛关注并得到快速发展。NTE的历史可以追溯到1897年磁性因瓦合金的发现。由于磁性的复杂性和可变性，对磁性NTE材料的研究，包括新材料的发现、可控的热膨胀、磁性NTE，一个多世纪以来从未停止过。在这篇综述中，我们将总结磁性 NTE 材料的进展，从原型因瓦合金到最近发现的材料，如锰基反钙钛矿、Laves 相、La(Fe,Si) ₁₃、Mn ₃ Ge、R ₂Fe ₁₇、R(Fe,V) ₁₂和 R ₂ Fe ₁₄B（R = 稀土元素）。基于可变磁跃迁类型，从磁性和晶体结构、NTE特性和机制等方面详细回顾了磁性NTE材料。首次总结了磁性材料NTE的主要机制，包括有序到无序转变、局部矩的变化、变磁转变、短程磁有序、结构相变和磁相共存。磁性材料的NTE特性可以通过化学取代、纳米化、外场和填隙原子等方法调节磁交换相互作用来控制。更重要的是，通过增强磁跃迁对热膨胀的负贡献，新型磁性NTE材料可以从普通的正热膨胀材料中找到。这篇综述将有助于新型磁性 NTE 材料的设计、热膨胀特性的控制以及对磁性 NTE 机制的理解。