表面活性剂对酸性蚀刻废液制备氧化铜形貌的影响研究

张添淳, 吴道新, 蒋峥瑾, 肖忠良

doi:10.16577/j.issn.1001-1560.2024.0209

材料保护 >

2024 , Vol. 57 >Issue 9: 125 - 136

DOI: https://doi.org/10.16577/j.issn.1001-1560.2024.0209

工艺篇

表面活性剂对酸性蚀刻废液制备氧化铜形貌的影响研究

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长沙理工大学化学化工学院

吴道新(1970-)，博士，教授，主要研究方向为电子精细化学品、功能材料，E-mail:daoxinwu＠126.com

收稿日期: 2023-12-26

修回日期: 2024-01-23

录用日期: 2024-01-26

网络出版日期: 2024-11-14

基金资助

湖南省战略性新型重大项目(2019GK4041)；长沙市科技计划项目(kql1907095)资助

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Influence of Surfactant on the Morphology of Copper Oxide Prepared from Acidic Etching Waste Solutions

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(College of Chemistry and Chemical Engineering， Changsha University of Science ＆ Technology， Changsha 410114， China)

WU Daoxin (1970-)， Ph.D.， Professor， Research Focus: Electronic Fine Chemicals， Functional Materials，E-mail: daoxinwu＠126.com

Received date: 2023-12-26

Revised date: 2024-01-23

Accepted date: 2024-01-26

Online published: 2024-11-14

Supported by

Hunan Province Strategic New Major Project (2019GK4041)； Changsha Science and Technology Plan Project (kq1907095)

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摘要

为探索十二烷基二甲基胺乙内酯(BS-12)、十二烷基硫酸钠(SDS)、十六烷基溴化吡啶(CPDB)、吐温80(Tween-80)4 种表面活性剂以及其加入顺序、煅烧温度对酸性蚀刻废液制备氧化铜(CuO)的形貌与粒径的影响，使用X 射线衍射仪(XRD)、红外光谱仪(FT-IR)、扫描电子显微镜(SEM)对所制备CuO 的性能进行了表征，通过粒径分析与热重(TG)测试研究了CuO 的粒径分布与热稳定性，使用MS 软件中的Forcite 模块在COMPASS 力场下进行分子动力学计算，研究了表面活性剂分子在CuO 表面吸附过程中的能量变化。结果表明:添加表面活性剂后，CuO 颗粒分布均匀、大小均一，较优的4 种表面活性剂为BS-12、SDS、CPDB、Tween-80。表面活性剂的加入顺序不影响CuO 产物的成分及形貌。先加入BS-12，比后加入BS-12 制备的CuO 样品的平均粒径小，分别为2.85、7.50 nm；在400 ℃下煅烧，添加BS-12、SDS、CPDB、Tween-80 制备的CuO 颗粒均为不规则片状结构，平均粒径增大，分别为25、27、40 和55 nm。 4 种表面活性剂通过模拟运动后都能自发吸附在CuO 表面，在此过程中温度和能量在短暂波动后迅速达到平稳状态，吸附模型体系相对稳定。 BS-12、SDS、CPDB、Tween-80 对CuO 表面的吸附能分别为-762.73、-556.10、-619.47、-739.81 kcal/mol，吸附能力大小为BS-12＞Tween-80＞CPDB＞SDS。在酸性蚀刻废液制备CuO 过程中加入表面活性剂，能有效提高CuO 颗粒的均匀性。

关键词： ; font-family:"; font-size:16px; font-style:normal; font-weight:400; ">蚀刻废液; 氧化铜; 表面活性剂; 分子动力学

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张添淳, 吴道新, 蒋峥瑾, 肖忠良 . 表面活性剂对酸性蚀刻废液制备氧化铜形貌的影响研究[J]. 材料保护, 2024 , 57(9) : 125 -136 . DOI: 10.16577/j.issn.1001-1560.2024.0209

Abstract

In order to study the effects of four surfactants， dodecyl dimethylamine ethylene lactone (BS-12)， sodium dodecyl sulfate (SDS)，cetyl pyridinium bromide (CPDB) and Tween-80， as well as their addition sequence and calcination temperature， on the morphology and particle size of copper oxide (CuO) prepared from acid etching waste solution.The microstructure of CuO was characterized using X-ray diffractometer (XRD) and infrared spectrometer (FT-IR).The micro-topography of copper oxide was examined with scanning electron microscope(SEM).The particle size distribution and thermal stability of CuO were investigated through particle size analysis and thermogravimetric (TG)testing.Molecular dynamics calculations were conducted using the Forcite module in MS software under the COMPASS force field to study the energy changes during the adsorption process of surfactant molecules on the CuO surface.Results showed that after the addition of surfactants，CuO particles exhibited uniform distribution and consistent size.The four optimal surfactants were identified as BS-12， SDS， CPDB and Tween-80.The order in which the surfactants were added did not affect the composition or morphology of the CuO product.The CuO samples prepared with BS-12 added first had a smaller average particle size compared to those with BS-12 added later， with sizes of 2.85 nm and 7.50 nm， respectively.When calcined at 400 ℃， CuO particles prepared with BS-12， SDS， CPDB and Tween-80 all exhibited irregular sheet-like structures with increased average particle sizes of 25，27，40 and 55 nm，respectively.After simulated motion，all four surfactants spontaneously adsorbed onto the CuO surface， with temperature and energy stabilizing rapidly after brief fluctuations， indicating the relative stability of the adsorption model systems.The adsorption energies of BS-12， SDS， CPDB and Tween-80 on the CuO surface were -762.73， -556.10，-619.47 and -739.81 kcal/mol， respectively， with the adsorption strength ranked as BS-12＞Tween-80＞CPDB＞SDS.The addition of surfactants in the preparation of CuO from acidic etching waste liquids effectively improved the uniformity of CuO particles.

Key words： etching waste; copper oxide; surfactant; molecular dynamics

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