迷迭香提取物在二氯乙酸介质中对冷轧钢的缓蚀作用及吸附机理研究

doi:10.11902/1005.4537.2025.206

中国腐蚀与防护学报

2026, Vol. 46

Issue (3): 807-820 CSTR: 32134.14.1005.4537.2025.206 DOI: 10.11902/1005.4537.2025.206

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迷迭香提取物在二氯乙酸介质中对冷轧钢的缓蚀作用及吸附机理研究

白子俊¹, 朱平¹^,², 高芸¹, 李向红¹, 邵丹丹¹, 徐娟¹(

)

^1.西南林业大学材料与化学工程学院昆明 650224
^2.云南省特种设备安全检测研究院昆明 650228

Corrosion Inhibition Effect and Adsorption Mechanism of Rosemary Extract for Cold-rolled Steel in a Dichloroacetic Acid Medium

BAI Zijun¹, ZHU Ping¹^,², GAO Yun¹, LI Xianghong¹, SHAO Dandan¹, XU Juan¹(

)

^1.College of Materials and Chemical Engineering, Southwest Forestry University, Kunming 650224, China
^2.Yunnan Provincial Special Equipment Safety Testing and Research Institute, Kunming 650228, China

引用本文:

白子俊, 朱平, 高芸, 李向红, 邵丹丹, 徐娟. 迷迭香提取物在二氯乙酸介质中对冷轧钢的缓蚀作用及吸附机理研究[J]. 中国腐蚀与防护学报, 2026, 46(3): 807-820.
Zijun BAI, Ping ZHU, Yun GAO, Xianghong LI, Dandan SHAO, Juan XU. Corrosion Inhibition Effect and Adsorption Mechanism of Rosemary Extract for Cold-rolled Steel in a Dichloroacetic Acid Medium[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(3): 807-820.

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摘要:

采用失重法、动电位极化曲线法、表面技术等综合表征手段，系统探究了迷迭香提取物(RWE)对冷轧钢在0.10 mol·L^-1二氯乙酸(DCA)溶液中的缓蚀作用机制。研究表明：20 ℃时，50 mg·L^-1 RWE缓蚀率可达94.86%，缓蚀性能呈现显著的质量浓度正效应和温度负效应。且RWE在冷轧钢表面遵循以物理吸附为主导的混合吸附机制，其低温(20~40 ℃)吸附过程符合Langmuir等温模型，而高温(50 ℃)条件下更符合Temkin等温模型。缓蚀系统中的腐蚀速率变化模式既符合Arrhenius方程，也符合过渡态理论，其表观活化能E_a、指前因子A、活化焓ΔH及活化熵ΔS均呈现上升趋势。根据动态电位极化曲线的分析结果，RWE被证实是一种混合型的缓蚀剂，它能有效阻滞金属阳极的溶解过程，并同时抑制阴极发生的析氢反应。结合XPS表面分析证实，RWE分子可通过在金属表面构建有机吸附膜层，有效抑制腐蚀反应。用液相色谱-高分辨质谱联用(LC-MS)分析计算表明，RWE含有的迷迭香酸、茉莉酸磺酸酯等活性物质，这些组分中含有苯环、O/N杂环和-OH等活性官能团，其能够通过物理或者化学吸附作用于冷轧钢表面。RWE在DCA溶液中具有较好的缓蚀性能和吸附性能，是传统缓蚀剂的优良替代品，具有良好的经济和环境价值。

关键词 ：迷迭香提取物, 二氯乙酸, 缓蚀性能, 吸附机理, 冷轧钢

Abstract：

The inhibition mechanism of rosemary extract (RWE) on cold-rolled steel in 0.10 mol·L^-1 dichloroacetic acid (DCA) solution was studied via gravimetry, potentiodynamic polarization, and surface analysis etc. The results showed that with a dosage of 50 mg·L^-1 RWE an inhibition efficiency of 94.86% at 20 ℃ may be reached. The inhibition performance exhibited a significant positive dependence on the concentration and a negative dependence on temperature. The adsorption of RWE on the steel surface followed a mixed mechanism dominated by physical adsorption. At lower temperatures (20-40 ℃), the process adhered to the Langmuir isotherm model, while at higher temperature (50 ℃), it better conformed to the Temkin isotherm model. The corrosion rate in the inhibited system satisfied both the Arrhenius equation and transition state theory. The apparent activation energy (E_a), pre-exponential factor (A), activation enthalpy (ΔH), and activation entropy (ΔS) all showed increasing trends. Based on potentiodynamic polarization curves, RWE was identified as a mixed-type inhibitor, effectively retarding both anodic metal dissolution and the cathodic hydrogen evolution reaction. XPS analysis confirmed the formation of an organic adsorption layer on the metal surface by RWE molecules, which effectively suppressed corrosion. LC-MS analysis revealed that active components such as rosmarinic acid and sulfonated jasmonates are present in RWE. These constituents contain active functional groups including benzene rings, O/N-heterocycles, and -OH, which facilitate interaction with the steel surface via physical and/or chemical adsorption. RWE demonstrates excellent corrosion inhibition and adsorption properties in DCA solution, serving as a promising environmentally friendly alternative to traditional inhibitors with significant economic and environmental value.

Key words： rosemary extract dichloroacetic acid corrosion inhibition performance adsorption mechanism cold-rolled steel

收稿日期: 2025-06-30 32134.14.1005.4537.2025.206

ZTFLH:

TG174

基金资助:国家自然科学基金(32360362);国家自然科学基金(52161016);云南省专家工作站项目(202305AF150009);云南省农业基础研究联合专项重点项目(202301BD070001-158);西南林业大学博士研究启动基金(110224051)

通讯作者: 徐娟，E-mail：58045846@qq.com，研究方向为生物质资源高值化利用

Corresponding author: XU Juan, E-mail: 58045846@qq.com

作者简介: 白子俊，男，2001年生，硕士生

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图1 RWE提取流程示意图

图2 20~50 ℃下冷轧钢在0.10 mol·L-1 DCA介质中的v、ηw与c的关系

图3 在含有不同质量浓度RWE下0.10 mol/L DCA溶液中的吸附等温线

表1 线性拟合参数

图4 腐蚀动力学拟合直线及腐蚀动力学参数与RWE质量浓度变化关系曲线图

图5 20 ℃时冷轧钢在0.10 mol·L-1 DCA溶液中不同RWE质量浓度下的极化曲线以及fa、fc和Rp与RWE质量浓度的关系及两种不同方法下缓蚀率的对比

表2 动电位极化曲线拟合数据

图6 不同条件下测试溶液的FTIR光谱、UV-vis吸收曲线和电导率

图7 RWE的总离子色谱图及主要化学组成

图8 冷轧钢表面的金相形貌和接触角及AFM

表3 冷轧钢表面粗糙度参数

图9 20 ℃下冷轧钢在含50 mg/L RWE 的1.0 mol/L DCA溶液浸泡6 h后的XPS

图10 主要成分的LUMO、HOMO、$f{{\left( {\vec{r}} \right)}^{-}}$的Fukui函数分布和$f{{\left( {\vec{r}} \right)}^{+}}$的Fukui函数分布

表4 主要成分的量子化学相关参数

图11 5种成分在Fe(110)表面平衡吸附构型的侧视图

表5 5种活性物质的吸附能及结合能数值

图12 RWE对冷轧钢的腐蚀抑制机制

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