一种苯并咪唑黄原酸酯的合成及其摩擦学性能

由于操作条件及环境保护的要求日益苛刻,环境友好型润滑油添加剂越来越受到人们的关注,润滑油添加剂向着低灰份、多功能、绿色环保方向发展。本文设计合成了三个环保型含氮硫化合物,采用质谱,红外光谱,元素分析对其结构进行了表征。考察了该类添加剂在菜籽油中的溶解性;采用热重分析对其热稳定性进行了评价;并在四球摩擦磨损试验机上考察了所合成的含氮硫化合物在菜籽油中的摩擦学性能。结果表明,该类添加剂在菜籽油中的溶解度都能达到2%,最低热分解温度为129℃,最高达532℃;在菜籽油中的极压值最高达1186N,是菜籽油的2倍,是ZDDP的1.3倍,抗磨性能最好的是B3,极压值最好的是B2。     

硫化菜籽油的催化合成及其摩擦学特性

以精制菜籽油为原料,天然丝光沸石为催化剂,研究了硫化菜籽油的催化合成,并借助FTIR测试技术分析了产物的化学结构. 通过四球摩擦磨损试验机考察了其摩擦学性能,同时对磨痕表面进行了XPS及显微分析,探讨了其润滑机理. 结果表明,随硫粉投料量的增大,菜籽油不饱和度逐渐降低,在丝光沸石催化下,硫化反应收率可达98%以上;含硫量从0增大到9.96%,硫化菜籽油的摩擦学性能明显提升,摩擦系数由0.085降为0.025,磨斑直径由0.56 mm降至0.42 mm,最大无卡咬负荷(PB值)由549 N升至745 N,烧结负荷(PD值)由1 960 N升至2 254 N;其润滑机理初步归结于硫化菜籽油在摩擦副表面上形成的吸附油膜,以及摩擦过程中由于摩擦化学反应形成的摩擦转移膜共同起减摩耐磨和极压作用.     

正丁基硫代磷酸酯的合成及其摩擦学性能研究

用MS、 FT-IR等方法对合成的三正丁基一硫代及四硫代磷酸酯进行了结构表征,并在四球摩擦磨损试验机上考察了其在液体石蜡中的摩擦学性能;用扫描电镜(SEM)和X射线光电子能谱(XPS)对钢球磨痕表面做了分析.结果表明: 对于钢-钢摩擦副,合成的两种硫代磷酸酯可以显著提高液体石蜡的极压抗磨性能,但不能改善其减摩性能.钢球磨损表面XPS和SEM分析结果表明,添加剂分子在金属表面发生物理或化学吸附,并导致金属表面的腐蚀和摩擦化学反应.     

C60-丙烯酸月桂酯共聚物的合成及其摩擦学行为

合成了一种新颖的油溶性C60-丙烯酸月桂酯共聚物,采用四球摩擦磨损试验机、扫描电子电镜研究了其作为液体石蜡润滑添加剂的摩擦学特性,结果表明,C60-丙烯酸月桂酯共聚物可提高石蜡基础液的抗磨性能,改善微观磨损状态.     

两种无灰型含磷/硫润滑添加剂在菜籽油中的摩擦学性能及膜分析

以合成的两种无灰型含磷/硫化合物为润滑添加剂, 以可生物降解的菜籽油作为基础油, 用四球机研究了体系的抗磨减摩性能, 以X射线光电子能谱(XPS)和X射线吸收精细结构光谱(XANES)对所形成的摩擦膜和热膜进行了表面分析, 并初步探讨了其润滑机理. 摩擦学研究结果表明, 两种含磷/硫化合物作为菜籽油的润滑添加剂时, 具有良好的抗磨减摩性能. XPS和XANES分析结果显示, 摩擦膜和热膜主要由吸附层和反应层组成; 在表面膜中, 磷主要以磷酸盐或焦磷酸盐等形式存在, 而硫主要以硫酸盐的形式存在. 研究结果还表明, 摩擦热在两种不同添加剂的摩擦膜形成过程中发挥着不同的作用.     

含氮杂环润滑油添加剂抗摩擦和膜化学性能

制备了N-二异辛基-2-苯并噻唑次磺酰胺(DIMB)和2-硫酮-苯并噻唑-3-甲基鄄巯基乙酸异辛酯(MBES)两种含氮杂环抗磨添加剂, 用SRV型高温摩擦磨损试验机评价它们在芋类基础油中的抗磨减摩性能, 对它们在不同条件下形成的摩擦膜进行X射线吸收精细结构光谱(XANES)分析, 用原子力显微镜(AFM)分析摩擦膜的表面形貌. 结果表明, 添加剂DIMB和MBES具有很好的抗磨性能, 但没有减摩性能. XANES分析结果表明, 添加剂MBES形成的摩擦膜完全由硫酸亚铁组成, 而添加剂DIMB形成的摩擦膜的次表面和本体主要由二硫化铁组成, 未测量到硫酸盐或硫化铁, 但摩擦膜表面部分被氧化成硫酸亚铁. AFM 测试结果表明, 与含1.5%(w)二烷基二硫代磷酸锌(ZDDP)抗磨添加剂的钢块磨损表面相比较, 分别含1.5%(w)DIMB 和1.5%(w)MBES添加剂的钢块磨损表面出现了深而宽的“犁沟”.     

含酯基苯并噻唑衍生物的摩擦膜及热膜化学结构

制备了两种苯并噻唑衍生物2-苯并噻唑基-巯基硫代乙酸正辛酯(MBTT)和2-苯并噻唑基-巯基乙酸正辛酯(MBTA), 并用元素分析和核磁共振谱表征其分子结构. 用X光吸收近边结构谱(X-ray absorption near edge structure, XANES)全面地分析了杂环化合物在矿物油和菜籽油中所形成的摩擦膜和热膜的化学态. 分析结果表明, 在矿物油中, 添加剂MBTT和MBTA摩擦反应生成的摩擦膜主要由FeS2组成, 而菜籽油中, 两种添加剂摩擦反应生成的摩擦膜由FeSO4组成; 在两种基础油中, 两种添加剂生成的热膜都是由FeSO4组成的.     

摩擦磨损试验机模拟活塞环-缸套摩擦行为的功能开发

参考活塞环-缸套的实际运行条件,结合SRV-4摩擦磨损试验机自身的性能特点和工作原理,通过开发设计,增加合理的硬件及软件测试条件,实现摩擦磨损试验机模拟活塞环-缸套摩擦行为的功能.系统测试结果表明：功能开发后的摩擦磨损试验机可在较短时间内获得活塞环-缸套摩擦副性能优劣的试验数据,满足快速、直观评价活塞环-缸套的摩擦磨损性能的需要,在活塞环-缸套摩擦副研究中具有重要的应用价值.     

一种高硫的噻二唑衍生物的摩擦学性能研究

合成了一种高硫含羟基和黄原酸的噻二唑衍生物(ESP),利用四球摩擦磨损试验机考察了其在Corda3970基础油中的摩擦磨损性能,表明所合成的添加剂能够有效的提高Corda 3970基础油的极压和抗磨性能,并且在一定的浓度范围内随着浓度的增加,其抗磨减摩性能增加。通过扫描电镜(SEM)分析了钢球表面形貌及元素分布,发现其主导作用的是边界膜中存在S、O、N活性元素,它们形成复合膜是添加剂具有摩擦学性能的主要原因。     

含氟不饱和聚酯的合成及其抗磨性能研究(英文)

将氟原子引入不饱和聚酯链中,合成了含氟不饱和聚酯,并探索了其合成条件;采用四球摩擦磨损试验机评价了含氟不饱和聚酯在液体石蜡中作为抗磨添加剂的摩擦学性能,并利用红外光谱仪、X射线光电子能谱仪和扫描电镜分析了摩擦表面膜的结构、形貌和化学状态.结果表明,氟原子的引入有利于降低聚酯的黏度,并改善聚酯在液体石蜡中的分散性;合成产物作为抗磨添加剂可以在钢球磨损表面形成聚合物膜,从而显著提高基础油的摩擦学性能.     

Naturally derived green bio-additives

During the last few years, special attention has been paid by the lubricant industry towards vegetable oil-based lubricants due to their biodegradability, renewability and excellent tribological properties. But to maintain the biodegradability of the final lubricants, the additive in the lubricants must also be biodegradable. Hence, in our present work, multifunctional lubricating oil additive based on castor oil has been investigated as a less toxic, feasible alternative to traditional petroleum based additives. Homopolymer of castor oil and its copolymer with α-pinene were synthesized by a thermal method using azobisisobutyronitrile as a radical initiator. Characterization of the prepared polymers was performed by spectral analysis and gel permeation chromatography (GPC). Additive performances of each of the prepared polymers as viscosity index improvers/viscosity modifiers and pour point depressants were carefully evaluated. Photo micrographic image was used to study the effectiveness of the additives as pour point depressants. Thermogravimetric analysis (TGA) was conducted to investigate the thermal response of the additives at high temperature. Finally, biodegradability of all the polymers was tested against fungal pathogen by the disc diffusion method and soil burial test. The study illuminated excellent additive performances of the polymers and thus their potential for acting as entirely naturally derived green bio-additives for lube oil.     

Rapeseed oil as main component in synthesis of bio-polyurethane-polyisocyanurate porous materials modified with carbon fibers

Porous polyurethane-polyisocyanurate (PUR-PIR) composites have been synthesized using two types of rapeseed oil-based bio-polyols. The bio-polyols from rapeseed oil were synthesized using two methods: (i) transesterification and (ii) epoxidation followed by oxirane ring opening. The PUR-PIR porous materials were prepared with two isocyanate indices, 150 and 250, and were modified with carbon fibres (CF) in an amount of 3 and 6 wt% of the total foam mass. The structure of the composites was examined using scanning electron microscopy. Thermal and mechanical properties of the composites were determined through a thermogravimetric analysis and measurements of the thermal conductivity, compressive strength, and Young modulus. The influence of CF on the composite flammability was analyzed using oxygen index and cone calorimeter tests. The investigations of the mechanical properties have shown that the compressive strength is the most beneficial in the case of the PUR-PIR foams modified with 6 wt % of CF. The studies have shown that the oxygen index of the composites increases with an increasing CF content and isocyanate index. An addition of CF reduces the heat rate release, especially for the materials with an isocyanate index of 250. An introduction of CF into the PUR-PIR foam structure is a way to improve the thermal stability and to decrease the flammability of final porous composites.     

Classification of rapeseed and soybean oils by use of unsupervised pattern-recognition methods and neural networks

Unsupervised pattern-recognition methods and Kohonen neural networks have been applied to the classification of rapeseed and soybean oil samples according to their type and quality by use of chemical and physical properties (density, refractive index, saponification value, and iodine and acid numbers) and thermal properties (thermal decomposition temperatures) as variables. A multilayer feed-forward (MLF) neural network (NN) has been used to select the most important variables for accurate classification of edible oils. To accomplish this task different neural networks architectures trained by back propagation of error method, using chemical, physical, and thermal properties as inputs, were employed. The network with the best performance and the smallest root mean squared (RMS) error was chosen. The results of MLF network sensitivity analysis enabled the identification of key properties, which were again used as variables in principal components analysis (PCA), cluster analysis (CA), and in Kohonen self-organizing feature maps (SOFM) to prove their reliability.     

碳质颗粒添加物对渣油热反应生焦的影响

在高压反应釜中研究了三种不同碳质颗粒添加物对克拉玛依常压渣油420℃氮气气氛下热反应生焦的影响。实验结果表明，反应初期碳质颗粒在一定程度上抑制渣油的热反应生焦。碳质颗粒抑制生焦的能力与其表面对极性组分的润湿吸附能力有直接关系，表面易被极性组分润湿的颗粒吸附沥青质的能力强，其抑制渣油生焦的能力也强。碳质颗粒对沥青质的吸附能力和抑制生焦的能力与其比表面积没有直接关系。生焦量随反应时间的变化表明，碳质颗粒在生焦的初期有抑制生焦的作用，后期有促进作用。对甲苯不溶物（TI）的扫描电子显微镜（SEM）和热重（TG）分析表明，和不含添加物的TI相比，含添加物的TI中，小球状甲苯不溶物的数量少、直径小。沥青质和生焦前驱相在碳质颗粒添加物表面的吸附和铺展作用是抑制渣油生焦的主要原因，该作用可以限制生焦前驱相的融并长大，在反应的初始阶段减少生焦量。     

Thermal and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) plasticized by biodegradable soybean oils

The effects of soybean oil (SO) and epoxidized soybean oil(ESO) as biodegradable plasticizers for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were studied using thermal and mechanical analyses. PHBV/SO and PHBV/ESO blends were prepared by evaporating solvent from blend solutions. The levels of additive in the blend varied from 5% to 30%. As a plasticizer for PHBV, ESO was more effective than SO in depression of the glass transition temperature as well as in increasing the elongation at break and the impact strength of the films with increasing levels of additive. Biodegradation of the plasticized PHBV films was carried out by accelerated compost method. The degradation rates of the blend films with SO or ESO were found to be faster than that of PHBV film. From the thermogravimetric analysis, it was found that the thermal reaction between the epoxide groups of ESO and PHBV fragments with carboxylic chain ends, occurred during the degradation of PHBV/ESO blends.     

Batch (one- and two-stage) production of biodiesel fuel from rapeseed oil

Biodiesel fuel is an alternative and renewable energy source, which may help to reduce air pollution, as well as our dependence on petroleum for energy. Several processes have already been developed for the production of biodiesel. Alkali-catalyzed transesterification with short-chain alcohols, for example, generates high yields of methyl esters in short reaction times. In this study, we have evaluated the efficacy of batch (one- and two-stage) transesterification of rapeseed oil in the production of rapeseed methyl ester. The conversion of rapeseed oil exhibited similar reaction patterns and yields in 30- and 1-L reaction systems. Approximately 98% of the rapeseed oil was converted at 400 rpm within 20 min, under the following conditions: 1% (w/w) KOH, 1∶10 methanol molar ratio, and at 60°C. In the 30-L, two-stage transesterification process, approx 98.5% of the rapeseed oil was converted at a 1∶4.5 molar ratio and 1% (w/w) KOH at 60°C for 30 min (first reaction condition), and at a 1∶1 molar ratio and 0.2% (w/w) KOH at 60°C for 30 min (second reaction condition).     

高压差示扫描量热法评价抗氧剂对润滑油基础油氧化稳定性的影响

结合环境友好润滑油产品的开发工作,利用高压差示扫描量热法(PDSC)研究了3种典型抗氧剂T501(2,6-二叔丁基对甲基苯酚)、T531(N-苯基-α-萘胺)和DNA(二壬基二苯胺)对菜籽油氧化稳定性的影响,并考察了浓度对抗氧剂作用效果的影响。结果证明,PDSC是一种快速简便评价基础油氧化稳定性的方法,适用于抗氧剂的筛选工作。另外,根据阿仑尼乌斯公式计算了不同油样氧化反应的表观活化能。     

硫化廿二酸中氧与硫在菜籽油中的协同减摩抗磨作用研究

采用低温硫化工艺和复分解反应制备了无臭硫化廿二酸,在四球摩擦磨损试验机上考察了其在菜籽油中的减摩抗磨行为及承载能力,并对钢球磨损表面进行了扫描电子显微（SEM）、电子探针（EPMA）以及X射线光电子能谱（XPS）分析。通过与廿二酸和硫化异丁烯的对比研究发现,在廿二酸中引入硫后,氧与硫产生了明显的协同减摩抗磨及承载作用。钢球磨损表面XPS分析结果表明,在摩擦过程中硫化廿二酸发生了摩擦化学变化,表面EPMA分析结果表明其表面保护膜富含氧和硫。     

抗氧剂对植物油氧化稳定性影响的高压差示扫描量热法评价

利用高压差示扫描量热法（ＰＤＳＣ）研究了二烷基二硫代氨基甲酸锌（ＶＡＺ）、２,２′－亚甲基双（４－甲基－６特丁基苯酚）（２２４６）、苯江三唑（ＢＴＺ）和二烷基对苯二胺（ＤＢＡ）４种抗氧添加剂对菜子油氧化稳定性的影响,得到了它们抗氧化作用的大小顺序。别外,根据队仑尼乌斯公式计算了不同油样氧化反应的活化能,证明了ＰＤＳＣ是一种快速简便评价基础油氧化稳定性的方法,适用于抗氧添加剂配方的设计工作。