雷然,李向红,石成杰,谭照源,张富.荞麦提取物对钢在HCl介质中的缓蚀机理[J].表面技术,2023,52(1):162-177.
LEI Ran,LI Xiang-hong,SHI Cheng-jie,TAN Zhao-yuan,ZHANG Fu.NP Inhibition Mechanism of Fagopyrum Esculentum Moench. Extract on Steel in HCl Media[J].Surface Technology,2023,52(1):162-177
荞麦提取物对钢在HCl介质中的缓蚀机理
NP Inhibition Mechanism of Fagopyrum Esculentum Moench. Extract on Steel in HCl Media
  
DOI:10.16490/j.cnki.issn.1001-3660.2023.01.017
中文关键词:  荞麦提取物  冷轧钢  盐酸  缓蚀  吸附  有效成分
英文关键词:Fagopyrum esculentum Moench. extract  cold rolled steel  hydrochloric acid  corrosion inhibition  adsorption  active ingredient
基金项目:国家自然科学基金(52161016,51761036);云南省基础研究计划杰出青年项目(202001AV070008);云南省万人计划“青年拔尖人才”专项(51900109);西南林业大学西南地区林业生物质资源高效利用国家林业和草原局重点实验室开放基金项目(2020-KF10)
作者单位
雷然 西南林业大学 化学工程学院,昆明 650224;西南林业大学 西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明 650224 
李向红 西南林业大学 化学工程学院,昆明 650224;西南林业大学 西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明 650224 
石成杰 西南林业大学 化学工程学院,昆明 650224;西南林业大学 西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明 650224 
谭照源 西南林业大学 化学工程学院,昆明 650224;西南林业大学 西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明 650224 
张富 西南林业大学 化学工程学院,昆明 650224;西南林业大学 西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明 650224 
AuthorInstitution
LEI Ran College of Chemical Engineering,Kunming 650224, China;Key Laboratory of National Forestry and Grassland Administration on Efficient Utilization of Forest Biomass Resources in Southwest China, Southwest Forestry University, Kunming 650224, China 
LI Xiang-hong College of Chemical Engineering,Kunming 650224, China;Key Laboratory of National Forestry and Grassland Administration on Efficient Utilization of Forest Biomass Resources in Southwest China, Southwest Forestry University, Kunming 650224, China 
SHI Cheng-jie College of Chemical Engineering,Kunming 650224, China;Key Laboratory of National Forestry and Grassland Administration on Efficient Utilization of Forest Biomass Resources in Southwest China, Southwest Forestry University, Kunming 650224, China 
TAN Zhao-yuan College of Chemical Engineering,Kunming 650224, China;Key Laboratory of National Forestry and Grassland Administration on Efficient Utilization of Forest Biomass Resources in Southwest China, Southwest Forestry University, Kunming 650224, China 
ZHANG Fu College of Chemical Engineering,Kunming 650224, China;Key Laboratory of National Forestry and Grassland Administration on Efficient Utilization of Forest Biomass Resources in Southwest China, Southwest Forestry University, Kunming 650224, China 
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中文摘要:
      目的 提取制备一种环境友好型缓蚀剂,并研究缓蚀剂对冷轧钢在1.0 mol/L盐酸溶液中的缓蚀性能。方法 利用超声波提取法从荞麦中提取得到荞麦提取物。采用失重法和电化学法研究荞麦(Fagopyrum esculentum Moench.)提取物(FEME) 对冷轧钢在HCl介质中的缓蚀性能,测试缓蚀溶液的紫外光谱(UV)、电导率及表面张力,并通过扫描电子显微镜(SEM)、原子力显微镜(AFM)、X–射线光电子能谱(XPS)、红外光谱(FTIR)表征钢表面的微观形貌、化学组成,用接触角测量仪测定钢表面的亲水/疏水性,分析FEME中的主要成分,进而深入探究了其缓蚀有效成分及作用机理。结果 FEME在1.0 mol/L HCl中具有良好的缓蚀性能,100 mg/L FEME的缓蚀率达90.1%(30 ℃);FEME在钢表面的吸附服从Langmuir吸附等温式,标准吸附Gibbs自由能(∆GΘ)为–32~–27 kJ/mol,电化学缓蚀机理为“几何覆盖效应”。添加FEME后,有效降低了钢/酸界面的双电层电容值,提升了电荷转移电阻。缓蚀钢表面的SEM和AFM微观形貌表明,其腐蚀程度明显下降,接触角变大,疏水性增强,FTIR和XPS证实了FEME能有效吸附在钢表面形成缓蚀膜层,且缓蚀膜层主要是通过FEME在钢表面的物理吸附和化学吸附而形成,FEME成分中含有大量的—OH,—OH的存在会使这些成分质子化,从而与带负电荷的钢表面通过静电引力而发生吸附,而且分子中含有大量的O、N等杂原子和不饱和基团结构,有大量的孤对电子可以与Fe的空d轨道配位,从而产生缓蚀剂在钢表面的化学吸附。与浸泡前相比,在钢腐蚀浸泡后,缓蚀溶液的表面张力增加,是由于浸泡后部分缓蚀剂分子在钢表面发生了吸附,致使溶液体相中的缓蚀剂分子浓度下降而引起。钢在腐蚀浸泡后,因H+的消耗,电导率明显降低,但浸泡钢表面后的缓蚀溶液随着FEME浓度的增加,电导率增加,说明缓蚀剂在钢表面吸附后,与钢表面发生腐蚀反应的H+消耗减少。20 ℃时,质量浓度为100 mg/L的芦丁的缓蚀率为57.8%,FEME的缓蚀性能优于其主成分芦丁,其机理为黄酮类化合物与其他成分的协同缓蚀作用。结论 FEME是一种高效、环保的混合抑制型缓蚀剂。
英文摘要:
      The work aims to extract and prepare an environmentally friendly corrosion inhibitor, and study the corrosion inhibition performance of the inhibitor on cold rolled steel in 1.0 mol/L hydrochloric acid solution. Fagopyrum esculentum Moench. extract was obtained from Fagopyrum esculentum Moench. through ultrasonic extraction. The inhibition performance of Fagopyrum esculentum Moench. extract (FEME) on cold rolled steel in HCl media was investigated with weight loss and electrochemical techniques. The ultraviolet spectroscopy (UV), conductivity and surface tension of inhibited solution were measured. The micrographs, chemical compositions and hydrophilic/hydrophobic property of steel surfaces were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and the hydrophilic/hydrophobic properties of steel surfaces were determined through contact angle measurements. The main components of FEME were fully analyzed, and then the effective components and mechanism of corrosion inhibition were explored in depth. The results showed that FEME exhibited efficient inhibition performance in 1.0 mol/L HCl. The inhibition efficiency of 100 mg/L FEME reached 90.1% at 30 ℃ in 1.0 mol/L HCl. The adsorption of FEME on CRS surface obeyed Langmuir adsorption isotherm, the standard Gibbs adsorption free energy (∆Go) was from –32 to –27 kJ/mol. FEME was a mixed-type inhibitor with “geometric blocking effect”. With the addition of FEME, the double capacitance at the steel/acid interface was dropped, while the charge transfer resistance increased significantly. SEM and AFM microstructures on the inhibited steel surface indicated that the corrosion degree was dropped apparently. Larger contact angles indicated the increase of hydrophobicity for the inhibited surface. FTIR and XPS confirmed that FEME could efficiently adsorb on steel surface to form the inhibitive film. The corrosion inhibitor film layer was mainly formed through the physical adsorption and chemical adsorption of FEME on the steel surface. FEME components contained a large number of —OH. The presence of —OH would cause these components to protonate, thus with the negatively charged steel surface through electrostatic gravity and adsorption, and the composition of the molecule contained a large number of O, N and other heteroatoms and unsaturated group structure, there were a large number of lone pairs of electrons can be ligated with the unoccupied d orbitals of Fe, thus producing the chemical adsorption of corrosion inhibitor on the steel surface. Compared with the inhibitor without immersion, the surface tension was increased. This was caused by the adsorption of some corrosion inhibitor molecules on the steel surface after immersion, resulting in a decrease in the concentration of corrosion inhibitor molecules in the bulk phase of the solution. For steel after corrosion immersion, the conductivity decreased significantly due to the consumption of H+. But after soaking of the steel surface in the corrosion inhibitor, the conductivity increased with the increase of FEME concentration, indicating that after the corrosion inhibitor was adsorbed on the steel surface, the corrosion reaction with the steel surface to reduce the consumption of H+ corrosion reaction. The corrosion inhibition rate of rutin at 100 mg/L reached a maximum of 57.8% at 20 ℃. The inhibition of FEME was better than that of its main component of rutin. The inhibitive mechanism of FEME was mainly attributed to the synergistic adsorption of flavonoids with other components. FEME is a highly efficient and environmentally friendly hybrid corrosion inhibitor.
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