<strong>CrMoTi</strong>中熵合金的性能及其原位合金化增材制造

doi:10.11900/0412.1961.2021.00030

金属学报

2022, Vol. 58

Issue (8): 1055-1064 DOI: 10.11900/0412.1961.2021.00030

研究论文

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CrMoTi中熵合金的性能及其原位合金化增材制造

刘广¹^,², 陈鹏¹^,³, 姚锡禹¹, 陈朴¹, 刘星辰¹, 刘朝阳⁴, 严明¹(

)

^1.南方科技大学材料科学与工程系深圳 518055
^2.哈尔滨工业大学材料科学与工程学院哈尔滨 150001
^3.School of Metallurgy and Materials, University of Birmingham, Birmingham B15 2TT, United Kingdom
^4.南方科技大学机械与能源工程系深圳 518055

Properties of CrMoTi Medimum-Entropy Alloy and Its In Situ Alloying Additive Manufacturing

LIU Guang¹^,², CHEN Peng¹^,³, YAO Xiyu¹, CHEN Pu¹, LIU Xingchen¹, LIU Chaoyang⁴, YAN Ming¹(

)

^1.Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China
^2.School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
^3.School of Metallurgy and Materials, University of Birmingham, Birmingham B15 2TT, United Kingdom
^4.Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen 518055, China

引用本文:

刘广, 陈鹏, 姚锡禹, 陈朴, 刘星辰, 刘朝阳, 严明. CrMoTi中熵合金的性能及其原位合金化增材制造[J]. 金属学报, 2022, 58(8): 1055-1064.
Guang LIU, Peng CHEN, Xiyu YAO, Pu CHEN, Xingchen LIU, Chaoyang LIU, Ming YAN. Properties of CrMoTi Medimum-Entropy Alloy and Its In Situ Alloying Additive Manufacturing[J]. Acta Metall Sin, 2022, 58(8): 1055-1064.

全文: PDF(2446 KB) HTML

摘要:

以新型模具材料为应用背景,首先从多主元合金设计的角度,预测了CrMoTi中熵合金成分,并在实验中验证了其单相bcc结构。对CrMoTi中熵合金的硬度和热学性能进行了测试。结果表明,电弧熔炼样品在室温下硬度为520.6 HV_0.3,在600℃时硬度为356.0 HV_0.3；在室温下比热容为371 J/(kg·K),热导率为14.0 W/(m·K)。随后以金属元素粉为原材料,对比研究了直接激光沉积(DLD)和选区激光熔化(SLM) 2种增材制造技术在原位合金化成型CrMoTi中熵合金的加工适性。其中DLD样品在打印态密度最高达7.46 g/cm³,硬度达到634.6 HV_0.3。SLM的原位合金化加工适性相对较差,样品密度最高为7.27 g/cm³,硬度为605.9 HV_0.3,且在其内部残留有未熔Mo粉。相比较而言,在作为模具的性能方面,CrMoTi合金表现出略优于H13钢的硬度和高温热导率。在原位合金化方面,CrMoTi合金的原料包含了熔沸点差异较大的金属元素,且形成相为硬脆bcc结构相,对增材制造技术而言有较大的加工难度,而DLD技术相对SLM表现出更好的原位合金化加工适性。

关键词 ：中熵合金, 增材制造, 原位合金化, 直接激光沉积, 选区激光熔化, 热学性能

Abstract：

This study verifies the body-centered cubic (bcc) formability of CrMoTi medium-entropy alloy (MEA) as a potential mold material via theoretical calculations based on the concepts of multiprincipal element alloys and practical experiments employing arc melting and additive manufacturing (AM) techniques. The hardness and thermal properties of arc-melted CrMoTi MEA were tested at room and elevated temperatures. At room temperature, the alloy possesses a hardness of 520.6 HV_0.3, thermal capacity of 371 J/(kg·K), and heat conductivity of 14.0 W/(m·K). Its hardness drops to 356.0 HV_0.3 at 600^oC, and its thermal capacity and heat conductivity increase to 446 J/(kg·K) and 28.4 W/(m·K), respectively, at 709^oC, exhibiting the characteristic of semimetals. AM techniques are efficient for fabricating highly customized molds and have been widely used. Moreover, in situ alloying can further improve the compositional flexibility in the AM process. The in situ alloying printability of two AM techniques, i.e., direct laser deposition (DLD) and selective laser melting (SLM), was investigated using a blend of elemental powders. The best densification within the AM approaches (7.46 g/cm³) is achieved using DLD, and the microhardness of DLDed samples reaches 634.6 HV_0.3. Conversely, the printability of SLM is relatively restricted. The optimal density and microhardness of the SLMed sample are 7.27 g/cm³ and 605.9 HV_0.3, respectively, which are lower than those of the DLDed samples. In the DLDed samples, the large melt pool can homogenize most elements but with a Cr burning loss. Mo melts insufficiently during the SLM process and remains a partially melted powder in as-built samples. Moreover, cracking is already inevitable in SLMed samples, indicating that homogenization can hardly be improved by applying excessive energy input. As a brittle bcc alloy, its matrix tends to fail under the thermal stress of the heat accumulation in the AM process. Furthermore, the phase transformation in a small melt pool also intrinsically harms printability for in situ alloying studies through AM. Results from this study reveal that DLD possesses advantages over SLM for the in situ alloying of brittle materials like CrMoTi MEA. Combining elements with adequate overlapping of the liquid zone could be essential for superior printability of AM in situ alloying, especially with a high ratio of introduced elements.

Key words： medium-entropy alloy additive manufacturing in situ alloying direct laser deposition selective laser melting thermal property

收稿日期: 2021-01-18

ZTFLH:

TG144.3

基金资助:广东省重点领域研发计划项目(2019B010943001);深圳市科创委学科布局项目(JCYJ20180504165824643);深圳市科创委学科布局项目(JCYJ-20170817111811303)

作者简介: 刘广,男,1996年生,硕士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00030 或 https://www.ams.org.cn/CN/Y2022/V58/I8/1055

表1 Cr、Mo和Ti元素的物理性质[13]

表2 增材制造原料粉体的C、N、O、H含量和粒径分布

图1 直接激光沉积(DLD)使用的混合元素粉末的SEM-EDS像

图2 DLD混合粉末的XRD谱

图3 通过电弧熔炼、DLD和选区激光熔化(SLM)成型的CrMoTi中熵合金XRD谱

图4 电弧熔炼制备CrMoTi中熵合金的EBSD像

图5 不同温度下电弧熔炼CrMoTi中熵合金的Vickers硬度

图6 不同温度下CrMoTi中熵合金的比热容(cp )与热导率(κ)

图7 增材制造原位合金化CrMoTi中熵合金成型效果

图8 SLM加工CrMoTi中熵合金试样截面形貌的SEM像

图9 DLD原位合金化CrMoTi中熵合金的密度-激光功率(ρ-P)曲线

图10 SLM原位合金化CrMoTi中熵合金的密度-体能量密度(ρ-VED)曲线

图11 增材制造原位合金化DLD1350W和SLM167J样品的SEM像和EDS分析

表3 CrMoTi中熵合金的名义成分和电弧熔炼及增材制造成型CrMoTi中熵合金的主元素含量 (atomic fraction / %)

表4 电弧熔炼CrMoTi中熵合金的硬度和热学性能

图12 增材制造块体的CT分析结果

图13 DLD加工CrMoTi中熵合金中的枝晶结构与元素分布图

图14 DLD加工CrMoTi中熵合金的EBSD像

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