Formation mechanism and kinetics of Ni3CuN complex nitride in solution combustion synthesis

IF 5.8 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2025-04-24 DOI:10.1016/j.combustflame.2025.114195

Marieta K. Zakaryan , Narine H. Amirkhanyan , Suren L. Kharatyan , Ani Aprahamian , Khachatur Manukyan

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引用次数: 0

Abstract

This study investigates the formation mechanism of Ni₃CuN complex nitride during combustion of aqueous solutions of nickel and copper nitrates and hexamethylenetetramine. The impact on the combustion process and final product formation was analyzed by varying the hexamethylenetetramine concentration. Time-temperature measurements during solution combustion synthesis (SCS) reactions coupled with X-ray diffraction (XRD), transmission electron microscopy, electron diffraction, and high-resolution element analysis of reacted materials revealed a complex reaction mechanism. Thermogravimetric analysis (TGA) provided detailed insights into the combustion dynamics, identifying several distinct stages: partial dehydration of metal nitrates, decomposition of intermediate nitrates forming oxides, metal and alloy formation, and final nitridation to produce Ni₃CuN. The TGA results highlighted the significant influence of heating rate on reaction dynamics, with lower rates (0.083–0.25 K/s) leading to gradual weight loss and higher rates (0.33–0.5 K/s) resulting in abrupt reactions. The effective activation energy calculations from TGA data, supported by XRD and electron microscopy findings, identified nickel nitrate decomposition as the rate-limiting step, with an effective activation energy of 179 ± 27 kJ/mol for lower heating rates and 217 ± 36 kJ/mol for higher rates. These integrated analyses enhance the understanding of the SCS mechanism for synthesizing Ni₃CuN and demonstrate the potential for producing complex nitrides with tailored properties for applications in catalysis, magnetic devices, and other advanced materials technologies.

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溶液燃烧合成Ni3CuN络合氮化物的形成机理及动力学

研究了硝酸镍铜和六亚甲基四胺溶液燃烧过程中Ni3CuN络合氮化物的形成机理。分析了不同浓度的六亚甲基四胺对燃烧过程和最终产物生成的影响。溶液燃烧合成（SCS）反应的时间-温度测量，结合x射线衍射（XRD）、透射电镜、电子衍射和高分辨率元素分析，揭示了复杂的反应机理。热重分析（TGA）提供了燃烧动力学的详细信息，确定了几个不同的阶段：金属硝酸盐部分脱水，中间硝酸盐分解形成氧化物，金属和合金形成，最终氮化生成Ni3CuN。TGA结果表明，升温速率对反应动力学有显著影响，较低的升温速率（0.083-0.25 K/s）导致失重，较高的升温速率（0.33-0.5 K/s）导致反应突然。根据TGA数据计算的有效活化能，结合XRD和电镜结果，确定硝酸镍的分解为限速步骤，低加热速率下的有效活化能为179±27 kJ/mol，高加热速率下的有效活化能为217±36 kJ/mol。这些综合分析增强了对合成Ni3CuN的SCS机制的理解，并展示了生产具有特定性能的复杂氮化物的潜力，可用于催化，磁性器件和其他先进材料技术。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Combustion and Flame 工程技术-工程：化工

CiteScore

9.50

自引率

20.50%

发文量

631

审稿时长

3.8 months

期刊介绍： The mission of the journal is to publish high quality work from experimental, theoretical, and computational investigations on the fundamentals of combustion phenomena and closely allied matters. While submissions in all pertinent areas are welcomed, past and recent focus of the journal has been on: Development and validation of reaction kinetics, reduction of reaction mechanisms and modeling of combustion systems, including: Conventional, alternative and surrogate fuels; Pollutants; Particulate and aerosol formation and abatement; Heterogeneous processes. Experimental, theoretical, and computational studies of laminar and turbulent combustion phenomena, including: Premixed and non-premixed flames; Ignition and extinction phenomena; Flame propagation; Flame structure; Instabilities and swirl; Flame spread; Multi-phase reactants. Advances in diagnostic and computational methods in combustion, including: Measurement and simulation of scalar and vector properties; Novel techniques; State-of-the art applications. Fundamental investigations of combustion technologies and systems, including: Internal combustion engines; Gas turbines; Small- and large-scale stationary combustion and power generation; Catalytic combustion; Combustion synthesis; Combustion under extreme conditions; New concepts.