油溶性纳米TiO_2防锈机理及应用研究
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摘要
随着纳米技术、表面分析技术的飞速发展，许多学者期望把纳米粒子作为研制新型润滑油添加剂的突破口，从而实现润滑油性能质的飞跃。由于纳米粒子的小尺寸效应、表面效应，使纳米TiO2表面存在大量的羟基，具有较大的比表面积和较高的表面能，因而极易团聚，在润滑油中难以均匀分散，并且稳定性极差。为了有效控制纳米TiO2粒子的粒径，提高在润滑油的分散稳定性，必须对纳米粒子表面进行有机修饰。
本文以油酸和十二烷基三甲氧基硅烷（DTMS）为表面修饰剂，研究或改进纳米TiO2粒子的制备和表面修饰工艺，制备在润滑油中具有良好分散稳定性的油溶性纳米TiO2粒子；系统研究纳米TiO2粒子对润滑油腐蚀与防护性能的影响，及其在润滑油中的腐蚀与防护作用机理；在此基础上对纳米粒子作为润滑油添加剂的可行性进行分析，并应用于新型军械油料产品的设计和开发。
采用微乳液原位合成法，制备了油酸修饰的油溶性纳米TiO2粒子，所得油酸修饰纳米TiO2粒子粒径分布均匀，平均粒径44nm，并且修饰剂油酸和纳米粒子之间不是简单的物理吸附，而是形成稳定的双齿螯合共价键结构。由于表面修饰剂层的存在，阻止了纳米粒子在基础油中的团聚和沉淀。油酸修饰纳米TiO2粒子有助于增加基础油对金属的防锈性能，油酸:钛酸丁酯为3:4，添加量为5%(质量百分比)时，基础油的防锈效果最好，盐水浸渍试验时间为9h；湿热试验时间为463h，缓蚀效率达到88.21%。
采用液相沉淀法制备了十二烷基三甲氧基硅烷（DTMS）修饰的油溶性纳米TiO2粒子，修饰温度40℃、修饰时间12h、修饰剂与Ti为2:1(摩尔比)时，所得粒子具有最佳亲油化度和分散稳定性。在基础油中粒径基本呈正态分布，平均粒径60nm左右。纳米TiO2粒子表面的DTMS修饰膜，有效控制了粒径的过度增长，避免粒子间的团聚，增强了纳米TiO2在基础油中的分散稳定性。基础油中加入5%(质量百分比)纳米TiO2粒子，可有效提高油膜对金属表面的防锈性能。
采用电化学阻抗技术，研究了添加纳米TiO2的基础油对金属表面防锈机理，金属腐蚀过程可分为四个阶段：点蚀诱导期、点蚀发展期、腐蚀中期和全面腐蚀期。油溶性纳米TiO2粒子防锈作用主要体现在延长金属表面的点蚀诱导期和点蚀发展期。
根据纳米粒子在润滑油品中防锈机理，以及军械油品的特殊要求，对纳米TiO2粒子进行了应用研究，采用油溶性纳米TiO2作为防锈添加剂，成功研制了液气悬挂装置工作液。性能评价表明：该纳米粒子与其它油品添加剂相容性好，对油品高低温性能无负面影响，可显著提高防锈性能和润滑性能。
With the rapid development of nano and surface modification technology, manyscholars expected a breakthrough in the application of nanoparticles as new lubricantadditives,and significant achievement in the qualitative leap of lubricant performance.Because of small size effect and surface effect, there are a large number of hydroxylgroups on nano-TiO2surface,so the nanoparticles were vulnerable to agglomeration.Itwas difficult for nanoparticles to dispersing in oil. In order to effectively controllingsize of nano-TiO2particles,and improveing the dispersion stability in the lubricatingoil, organic surface modification was employed.
In this paper, the process of preparation and surface modification of nano-TiO2particles using oleic acid and DTMS as modifier was studied. Oil-soluble TiO2nanoparticles which had excellent suspension stability and dispersion stability inlubricating oil were prepared. Influence of TiO2on anticorrosive properties oflubricating oil and anticorrosive mechanism was researched. The feasibility of TiO2asanticorrosive additives was explored, and the obtained TiO2was successfully appliedin new ordnance oil.
TiO2nanoparticles modified by oleic acid were prepared by the in-situ synthesismethod. The particles were relatively uniform with average particle size of44nm. Theinteraction between carboxyl and nanoparticles was not physical adsorption, but viathe formation of bidentate chelate. The modified layer on the surface of TiO2nanoparticles prohibited effectively the agglomeration of particles while improved theanticorrosion properties of lubricating oil. The highest anticorrosive properties of TiO2nanoparticles in lubricating oil were found under the conditions of modifyingagent:TiO2=3:4(mol) by adding5%(mass)TiO2.
TiO2nanoparticles modified by DTMS were prepared by the liquid phasedeposition method. The highest lipophilic degree and suspension stability of TiO2nanoparticles in lubricating oil were showed with the modifying agent:TiO2=2:1(mol)and modified time of12h at40℃. The particle size distribution in lubricating oil wasalmost gaussian distribution with the average particle diameter of60nm.According tothe results of FT-IR and TEM, the modified layer on the surface of TiO2nanoparticlescontrolled effectively the excessive growth of particles, prevent the agglomeration ofparticles, and enhanced the suspension stability and dispersion stability ofnanoparticles in lubricating oil. According to the results of electrochemical experiment and humidity cabinet test, the anticorrosive properties of oil film wasimproved evidently by adding5%(mass)TiO2to lubricating oil.
Anticorrosive Mechanism of oil-soluble TiO2nanoparticles in0.5%neutral NaClsolutions were studied by electrochemical impedance spectroscopy.The wholecorrosion processes could be separated into several periods:(l) induction period ofpitting corrosion;(2) development period of pitting corrosion;(3) general corrosionregion;(4) accelerated corrosion region. The anticorrosive ability of oil-soluble TiO2was mainly reflected in increasing induction period of pitting corrosion anddevelopment period of pitting corrosion.
On the basis of the above research and special demand of the ordnance oil, theapplication research of oil-soluble TiO2nanoparticles modified by DTMS werecarried out. Thereafter the working fluid for oil-gas suspension was preparedsuccessfully using TiO2as anticorrosive additives. The studies indicated that TiO2nanoparticles had compatibility to other oil additives. No negative effect was found onhigh and low temperature performance of the working fluid. Because of the TiO2nanoparticles, the anticorrosive properties and lubricating performance of the workingfluid were significantly increased.
本文以油酸和十二烷基三甲氧基硅烷（DTMS）为表面修饰剂，研究或改进纳米TiO2粒子的制备和表面修饰工艺，制备在润滑油中具有良好分散稳定性的油溶性纳米TiO2粒子；系统研究纳米TiO2粒子对润滑油腐蚀与防护性能的影响，及其在润滑油中的腐蚀与防护作用机理；在此基础上对纳米粒子作为润滑油添加剂的可行性进行分析，并应用于新型军械油料产品的设计和开发。
采用微乳液原位合成法，制备了油酸修饰的油溶性纳米TiO2粒子，所得油酸修饰纳米TiO2粒子粒径分布均匀，平均粒径44nm，并且修饰剂油酸和纳米粒子之间不是简单的物理吸附，而是形成稳定的双齿螯合共价键结构。由于表面修饰剂层的存在，阻止了纳米粒子在基础油中的团聚和沉淀。油酸修饰纳米TiO2粒子有助于增加基础油对金属的防锈性能，油酸:钛酸丁酯为3:4，添加量为5%(质量百分比)时，基础油的防锈效果最好，盐水浸渍试验时间为9h；湿热试验时间为463h，缓蚀效率达到88.21%。
采用液相沉淀法制备了十二烷基三甲氧基硅烷（DTMS）修饰的油溶性纳米TiO2粒子，修饰温度40℃、修饰时间12h、修饰剂与Ti为2:1(摩尔比)时，所得粒子具有最佳亲油化度和分散稳定性。在基础油中粒径基本呈正态分布，平均粒径60nm左右。纳米TiO2粒子表面的DTMS修饰膜，有效控制了粒径的过度增长，避免粒子间的团聚，增强了纳米TiO2在基础油中的分散稳定性。基础油中加入5%(质量百分比)纳米TiO2粒子，可有效提高油膜对金属表面的防锈性能。
采用电化学阻抗技术，研究了添加纳米TiO2的基础油对金属表面防锈机理，金属腐蚀过程可分为四个阶段：点蚀诱导期、点蚀发展期、腐蚀中期和全面腐蚀期。油溶性纳米TiO2粒子防锈作用主要体现在延长金属表面的点蚀诱导期和点蚀发展期。
根据纳米粒子在润滑油品中防锈机理，以及军械油品的特殊要求，对纳米TiO2粒子进行了应用研究，采用油溶性纳米TiO2作为防锈添加剂，成功研制了液气悬挂装置工作液。性能评价表明：该纳米粒子与其它油品添加剂相容性好，对油品高低温性能无负面影响，可显著提高防锈性能和润滑性能。
With the rapid development of nano and surface modification technology, manyscholars expected a breakthrough in the application of nanoparticles as new lubricantadditives,and significant achievement in the qualitative leap of lubricant performance.Because of small size effect and surface effect, there are a large number of hydroxylgroups on nano-TiO2surface,so the nanoparticles were vulnerable to agglomeration.Itwas difficult for nanoparticles to dispersing in oil. In order to effectively controllingsize of nano-TiO2particles,and improveing the dispersion stability in the lubricatingoil, organic surface modification was employed.
In this paper, the process of preparation and surface modification of nano-TiO2particles using oleic acid and DTMS as modifier was studied. Oil-soluble TiO2nanoparticles which had excellent suspension stability and dispersion stability inlubricating oil were prepared. Influence of TiO2on anticorrosive properties oflubricating oil and anticorrosive mechanism was researched. The feasibility of TiO2asanticorrosive additives was explored, and the obtained TiO2was successfully appliedin new ordnance oil.
TiO2nanoparticles modified by oleic acid were prepared by the in-situ synthesismethod. The particles were relatively uniform with average particle size of44nm. Theinteraction between carboxyl and nanoparticles was not physical adsorption, but viathe formation of bidentate chelate. The modified layer on the surface of TiO2nanoparticles prohibited effectively the agglomeration of particles while improved theanticorrosion properties of lubricating oil. The highest anticorrosive properties of TiO2nanoparticles in lubricating oil were found under the conditions of modifyingagent:TiO2=3:4(mol) by adding5%(mass)TiO2.
TiO2nanoparticles modified by DTMS were prepared by the liquid phasedeposition method. The highest lipophilic degree and suspension stability of TiO2nanoparticles in lubricating oil were showed with the modifying agent:TiO2=2:1(mol)and modified time of12h at40℃. The particle size distribution in lubricating oil wasalmost gaussian distribution with the average particle diameter of60nm.According tothe results of FT-IR and TEM, the modified layer on the surface of TiO2nanoparticlescontrolled effectively the excessive growth of particles, prevent the agglomeration ofparticles, and enhanced the suspension stability and dispersion stability ofnanoparticles in lubricating oil. According to the results of electrochemical experiment and humidity cabinet test, the anticorrosive properties of oil film wasimproved evidently by adding5%(mass)TiO2to lubricating oil.
Anticorrosive Mechanism of oil-soluble TiO2nanoparticles in0.5%neutral NaClsolutions were studied by electrochemical impedance spectroscopy.The wholecorrosion processes could be separated into several periods:(l) induction period ofpitting corrosion;(2) development period of pitting corrosion;(3) general corrosionregion;(4) accelerated corrosion region. The anticorrosive ability of oil-soluble TiO2was mainly reflected in increasing induction period of pitting corrosion anddevelopment period of pitting corrosion.
On the basis of the above research and special demand of the ordnance oil, theapplication research of oil-soluble TiO2nanoparticles modified by DTMS werecarried out. Thereafter the working fluid for oil-gas suspension was preparedsuccessfully using TiO2as anticorrosive additives. The studies indicated that TiO2nanoparticles had compatibility to other oil additives. No negative effect was found onhigh and low temperature performance of the working fluid. Because of the TiO2nanoparticles, the anticorrosive properties and lubricating performance of the workingfluid were significantly increased.
引文
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