润滑油清净剂超重力合成过程的自动化控制技术研究

针对润滑油清净剂合成过程中碳酸化反应终点控制难的问题,同时结合高碱值石油磺酸钙润滑油清净剂的超重力合成工艺特点,建立了 pH 值-电导率的碳酸化反应终点控制系统,考察了高碱值石油磺酸钙润滑油清净剂的超重力合成工艺中包括中和反应和碳酸化反应的 pH 值和电导率.依据 pH 值和电导率对高碱值石油磺酸钙产品性质的影响,研究了中和过程和碳酸化过程中的 pH 值和电导率的变化规律,其中,中和反应结束时的 pH 值在 10 左右,碳酸化反应终点的 pH 控制范围为8,55±0,05,电导率的控制范围为 (0.25±0.01)μΩ-1～·cm-1.通过 pH 值-电导率控制技术实现了润滑油清净剂合成过程中碳酸化反应终点的自动化控制技术.     

高碱值磺酸钙对润滑脂性能的影响

高碱值磺酸盐是生产复合磺酸钙基润滑脂的重要原料,其质量是决定复合磺酸钙基润滑脂产品品质的关键因素之一.为选择合适的高碱值磺酸盐,考察不同高碱值磺酸盐从无定型碳酸钙转化为方解石型碳酸钙的转相时间、稠化能力,以及不同高碱值磺酸盐制备的润滑脂的滴点、锥入度、钢网分油和滚筒安定性能;筛选出的高碱值磺酸盐制备的复合磺酸钙基润滑脂...     

高碱性合成磺酸钙清净剂的研制

研究了以重烷基苯磺酸为原料制备高碱性合成磺酸钙清净剂的合成工艺，合成磺酸钙的中试研究考察了实验室合成工艺的可行性。在对影响中和反应和碳酸化反应的各类因素进行研究的基础上确定了工艺路线和条件，制备出总碱值大于295的产品，所得产品的理化指标、模拟评定结果都达到了国内外同类产品水平。为工业试验和工业生产提供了必要的依据。     

复合磺酸钙润滑脂的制备及机制研究

考察高碱值磺酸钙原料、转化工艺的加料顺序和高碱值磺酸钙与转化基础油加料比、增黏剂加入量及加入方式对复合磺酸钙润滑脂性能的影响,分析复合磺酸钙转化机制、稠化机制。结果表明,高碱值磺酸钙是制备润滑脂的关键原料,不同的高碱值磺酸钙原料对复合磺酸钙润滑脂性能影响最显著;改变转化过程中的加料顺序和高碱值磺酸钙与转化基础油加料比都会影响碳酸钙晶型转化,进而影响稠度、胶体安定性等性能;高温炼制前加入增黏剂可以较好地减小分油,提高黏附性。     

高碱值(性)硼化磺酸盐清净剂的研究应用

本文着重介绍了高碱值（性）硼化磺酸盐清净剂的性能，制备中的各种影响因素。并提出了将来的研究发展方向。     

高碱值硫化烷基酚钙抗磨机制分析

采用四球机、高频往复试验机(HFRR),考察了加入清净剂高碱值硫化烷基酚钙(T115B)前后油品抗磨性能的变化;并采用SEM和EDS分析了摩擦副表面的形貌和元素分布情况。结果表明,高碱值硫化烷基酚钙有助于增加油品的润滑性能,并且随着加入量的增加,抗磨性能逐渐增加;高碱值硫化烷基酚钙中的S元素与金属表面发生化学反应,生成了金属硫化物,从而提高了油品的抗磨性能。     

离子液体在润滑脂中的导电性和摩擦学性能研究

以聚亚烷基二醇(PAG)为基础油,LiBF_4和LiNTf_2锂盐为添加剂原位形成离子液体;制备以离子液体为基础油,以高碱值复合磺酸钙为稠化剂的导电润滑脂,考察其体积电阻率、接触电阻等导电性,在MFT-R4000高速往复摩擦磨损试验机上评定其摩擦学性能,并采用超高分辨率场发射扫描电子显微镜进行表面分析。结果表明:LiBF_4和LiNTf_2可显著提高高碱值复合磺酸钙基脂的导电性,且LiBF_4比LiNTf_2导电效果更好;在摩擦过程中LiBF_4能在摩擦副之间形成摩擦保护膜,因而其具有优异的减摩抗磨作用;含质量分数2%LiBF_4的高碱值复合磺酸钙基导电润滑脂,其导电性和摩擦学性能明显优于商用电力复合脂,可作为新型电力复合脂使用。     

蜡裂解α烯烃制备高碱性烷基苯磺酸钙的研究

采用石蜡裂解α烯烃为原料,合成了组分比较单一、结构合理的长链烷基苯,进而制备出总碱值大于305mgKOH.g-1高碱性烷基苯磺酸钙盐,所得产品的理化指标、模拟评定结果表明该产品性能优于目前国内产品,与国外同类产品的性能相当,为国内生产高碱性磺酸钙开辟了一条新的原料途径。     

改性复合磺酸钙基润滑脂的研究

高碱值复合磺酸钙基润滑脂综合性能优异,被称为全新理念的润滑脂,但容易产生硬化问题。对复合磺酸钙基润滑脂进行了改性处理,并且对其硬化机制作了初步分析。结果表明:改性后的复合磺酸钙基润滑脂综合了复合锂基脂、聚脲基脂和复合磺酸钙基脂的性能优势,不仅解决了硬化问题,且该润滑脂具有特殊的纤维结构,从而赋予其极高的滴点、良好的高温极压润滑性能和低的摩擦因数。     

发动机油的碱值保持能力与抗氧化性能关系

为探讨发动机油的碱值保持与抗氧化性能的关系,通过模拟试验和行车试验考察使用过程中发动机油的酸值、碱值的变化,分析发动机油抗氧化性能与碱值保持的关系,并从碱值分析技术缺陷入手初步探讨如何看待和分析发动机油碱值的变化。结果表明:油品氧化过程中碱值降低与酸值增加量之间无明确的对应关系,单纯使用碱值进行发动机油的性能监测和判断油品的抗氧化性能好坏并不科学;由于影响发动机油性能的因素较多,用行车试验来研究碱值的变化与抗氧化性能关系,很难得出理想的结果。     

Combination of ashless antiwear additives with metallic detergents: interactions with neutral and overbased calcium sulfonates

The interactions of neutral and overbased calcium sulfonate detergents with ashless thiophosphate oil additives under boundary lubrication were studied. The ashless additives used were neutral and acidic dialkyldithiophosphate (DTPs) and neutral triaryl monothiophosphate (MTP). This study uses three surface analytical tools to provide elemental and chemical information at the surface and in the bulk of the derived tribochemical films. The elemental composition of the tribofilms was studied using X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray analysis (EDX) (combined with scanning electron microscopy (SEM)). Corresponding P and S X-ray absorption near edge structure (XANES) spectroscopy was also used to provide further insight into the chemical composition of the films. SEM images of the derived tribofilms revealed that each film had distinct topographical features associated with it. XPS and EDX revealed that when oil is blended with calcium sulfonate, considerable amount of calcium is incorporated into all the tribochemical films. The phosphorus content of the tribofilm was reduced substantially when the overbased detergent was combined with MTP additive. XANES spectroscopy of the P L-edge provided direct evidence for the formation of calcium phosphate in tribofilms from the ashless additives in combination with the detergent.S K-edge revealed that sulfate is the main sulfur species formed in the bulk for all three tribofilms in the presence of the neutral detergent while a mixture of sulfite and sulfide species are formed when the overbased was used. S L-edge XANES showed that calcium sulfonate has undergone some oxidation at the surface. A more antagonistic effect was observed for MTP, with the formation of a very thin phosphate film.Tribological performance was also evaluated. Surprisingly, combination of the neutral detergent with any of the AW additives did not result in any significant change in wear to the substrate. For MTP plus neutral detergent, the thinner phosphate film produced, combined with very little change in wear protection confirms that, not only is the tribochemistry dominated by calcium sulfonate, but also confirms the anti-scuffing and AW properties that are associated with it as well. Even more surprising, was the significant decrease in wear when the overbased detergent is used. This illustrates not only that the tribochemistry was dominated by the detergent, but also the exceptional AW properties of calcium carbonate.     

Study of Hydroforming Lubricants with Overbased Sulfonates and Friction Modifiers

Due to the high cost of hydroforming equipment, attempts have been made to model this process using bench testing. While tensile and twist compression tests have yielded promising results, they do not simulate any single metal forming process. In this study we investigated the use of expansion zone, guiding zone, and twist-compression tests to simulate hydroforming processes and evaluated various overbased sulfonates and organic friction modifiers performance. The amorphous overbased magnesium sulfonate improved the performance of the hydroforming oil in the expansion zone and provided no harm in the guiding zone, while the crystalline overbased calcium sulfonate provided no harm in the expansion zone and improved performance in the guiding zone. It was found that the friction modifiers tested display an antagonism, where, as the expansion zone performance increased, the guiding zone performance decreased. Additionally, we found in twist-compression testing that the initial coefficient of friction displayed a small correlation with the guiding zone test (from r = 0.26–0.47), while the failure time displayed a small correlation with the expansion zone test (r = 0.36–0.40).     

Study of surface films of overbased sulfonates and sulfurized olefins by X-Ray Absorption Near Edge Structure (XANES) spectroscopy

The X-Ray Absorption Near Edge Structure (XANES) spectroscopy technique has been successfully applied to complex matrices such as tribological films, coal, DLC films and, where other instrumental analytical techniques are less sensitive for molecular analysis. Four-ball tests were performed for lubricating oils containing the synergistic combination of overbased sulfonate (calcium and magnesium) and sulfurized olefin. The surface films were analyzed by XANES using C K-edge, Ca L-edge and S L- and K-edge. Using this technique we were able to differentiate the carbonate from organic carbon in C K-edge spectra, as well as, determining the difference between FeS, FeS_2, RSO₃⁻ and SO₄²⁻ in the sulfur spectra. It was found while the sulfurized olefin reacts very strongly with the substrate to form FeS, the overbased calcium sulfonate and overbased magnesium sulfonate do not react strongly with the substrate without sulfurized olefin present. There is evidence to suggest that the overbased sulfonate promotes decomposition of the sulfurized olefin on the surface to form both CaSO₄ and FeS, which improves the EP performance of the lubricant.     

高碱值磺酸盐对汽车自动传动液摩擦耐久性及抗磨的影响

采用传动油摩擦特性试验机和四球试验机考察高碱值磺酸盐对油品摩擦耐久性和抗磨性的影响。高碱值磺酸盐可改善油品的摩擦耐久性。试验片经XPS分析 ,发现试验片表面有明显的SO4 2 - 峰 ,除钢表面外 ,Ca也存在于钢的亚表层     

Study of surface films of crystalline and amorphous overbased sulfonates and sulfurized olefins by X-ray absorption near edge structure (XANES) spectroscopy

In the past large synergistic effects have been reported for combinations of overbased sulfonate and sulfurized olefin in four-ball EP testing. In this study, we examined the effect of crystallinity on the formation of the tribofilms using X-ray absorption near edge structure (XANES) spectroscopy. Using this technique, we were able to differentiate the carbonate from organic carbon in C K-edge spectra, as well as, determining the difference between FeS, FeS_2, RSO₃⁻, and SO₄²⁻ in the sulfur spectra. While the overbased calcium sulfonates do not react strongly with the substrate there is evidence to suggest that the overbased sulfonate promotes decomposition of the sulfurized olefin on the surface to form both CaSO₄ and FeS, which improves the EP performance of the lubricant. A putative intermediate is H₂S from the decomposition of the sulfurized olefin which can react with O₂ and the Fe-rich surface to form FeSO₄ and FeS, respectively. A new ‘FeS’ species has been detected in the tribofilms that is believed to be a non-stoichiometric Fe-enriched FeS. Depending on the presence or absence of the overbased calcium sulfonate either FeSO₄ or FeS formation is favored and changing the concentration of the crystalline, C300C, or amorphous, C400A, overbased calcium sulfonate from 5% to 10% does not appear to have any effects on FeS formation, although the C300C produces more Fe-enriched FeS than the C400A in the bulk.     

Tribological performance and mechanism of action of overbased detergents

The antifriction properties of calcium phenate-, sulphonate- and alkylsalicylate-type detergent additives were investigated. The influence of the detergent type and its basicity on engine oil antifriction properties was determined. The tribological performance of different detergents was characterised by laboratory methods. Auger spectroscopy was used for surface layer composition and thickness determination. The experimental data allowed the mechanism of action and the tribological performance characteristics of overbased detergents to be more precisely identified.