Molecular Simulation of Chain Initiation Mechanism in Oxidation of Lubricant Base Stock

Chain initiation reactions in the oxidation process of lubricant base stock molecules were studied by molecular simulations.Two ways to initiate lubricant oxidation were investigated.They included the dissociation of chemical bonds in base stock molecules and the reaction between base stock molecules and oxygen(O_(2)),respectively.Reaction activation energy of above methods was calculated.The results show that C‒C bonds are more likely to break than C‒H bonds to generate free radicals by the pyrolysis of chemical bonds.The C‒C bonds with tertiary carbon atoms are preferential positions to crack.However,their bond dissociation energy is above 360 kJ/mol,which is difficult to occur under lubricant working conditions.The chain initiation is more likely to occur by the way that O_(2) attacks the two atoms in C‒H bonds at the same time,and is then embedded into the C‒H bond to produce hydrocarbon peroxides.And then,the O‒O bond is cracked to form hydroxyl radicals and alkoxy radicals.The C‒H bonds with tertiary carbon atoms are preferential reaction sites,the reaction activation energy of which is about 190.11 kJ/mol.

Preparation and Characterization of Multiester Derivative from Plant Oil as Base Stock for Biolubricants

As an alternative to petroleum-based lubricants, which are harmful to the environment in excessive amounts, a biodegradable multiester derivative(OFANE) was obtained from plant oil through a chemical modification process with four steps as follows: hydrolysis, esterification, epoxidation, and ring-opening reaction. The physical and chemical properties of OFANE, such as viscosity, acid value, pour point, evaporation loss, and oxidation induction time were measured. Results showed that OFANE had good low-temperature fluidity, thermal-oxidative stability, and tribological properties. The tribological properties of OFANE with dimeric acid additive were evaluated. The final biodegradation experiment indicated that OFANE had excellent biodegradability. The prepared OFANE showed great potential as substitute for petroleum-based lubricating base oils.

Tribological Properties of Few-layer Graphene Oxide Sheets as Oil-Based Lubricant Additives

The performance of a lubricant largely depends on the additives it involves. However, currently used additives cause severe pollution if they are burned and exhausted. Therefore, it is necessary to develop a new generation of green additives. Graphene oxide（GO） consists of only C, H and O and thus is considered to be environmentally friendly. So the tribological properties of the few-layer GO sheet as an additive in hydrocarbon base oil are investigated systematically. It is found that, with the addition of GO sheets, both the coefficient of friction（COF） and wear are decreased and the working temperature range of the lubricant is expanded in the positive direction. Moreover, GO sheets has better performance under higher sliding speed and the optimized concentration of GO sheets is determined to be 0.5wt%. After rubbing, GO is detected on the wear scars through Raman spectroscopy. And it is believed that, during the rubbing, GO sheets adhere to the sliding surfaces, behaving like protective films and preventing the sliding surfaces from contacting with each other directly. This paper proves that the GO sheet is an effective lubricant additive, illuminates the lubrication mechanism, and provides some critical parameters for the practical application of GO sheets in lubrication.

Simulation of Solvent Extraction for Naphthenic Lubricating Base Oils

Solvent extraction is the process of separating aromatics from vacuum distillates for the production oflubricating base oils. In this study, the authors use dimethyl sulfoxide (DMSO) instead of furfural as solvent, in light of itshigher selectivity, to obtain extracts with a high aromatic content for naphthenic lubricating base oils. We systematicallyinvestigated effects of the solvent-to-oil (S/O) ratio and extraction temperature on the yield of the extract, efficiency ofaromatic removal, and composition of the extracts and raffinates. The results showed that the aromatic content of extractsfor naphthenic oils could reach a high value of about 80%. The solvent maintained a high selectivity for aromatics fornaphthenic oils even under a high S/O ratio and a high extraction temperature. Moreover, the efficiency of aromatic removalfor naphthenic lubricating base oils could be enhanced by increasing either the S/O ratio or the extraction temperature,although these measures had limited effects in practice. Following this, we used the non-random two-liquid (NRTL) modelbased on the pseudo-component approach to simulate the liquid-liquid equilibrium of the system of DMSO + naphtheniclubricating base oils, and determined the parameters of binary interaction through regression based on the data on phaseequilibrium. The modeling results showed that the predicted yield, content of the solvent, and composition of the raffinatesand extracts were in good agreement with those obtained in the experiments. This validates the reliability of the model usedto represent the DMSO + naphthenic lubricating base oil system. Both the experimental data and the method of simulationreported here can help optimize the extraction of naphthenic lubricating base oils, and provide a better understanding of thecorresponding process.

Coal Tar Derived Metallocene Catalyst for Polymerization of 1-Decene into Low-viscosity Poly-α-Olefin Lubricating Base Oil

The production of poly-α-olefins(PAOs)has attracted attention due to their excellent viscosity-temperature dependence,wear characteristics,oxidative properties,and high thermal stability.In this study,indene extracted during coal tar refining was used as a raw material to synthesize a bis(indenyl)zirconium dichloride metallocene catalyst.A PAO with low viscosity and a high viscosity index was produced via the oligomerization of 1-decene in the presence of both the prepared metallocene and a methylaluminoxane(MAO)co-catalyst.Notably,the effects of different synthesis reaction parameters,such as Al:Zr ratio,amount of catalyst,and reaction temperature,on the conversion ratio and product selectivity were investigated in detail.The produced PAO was thoroughly characterized using Fourier-transform infrared,^(13)C,and^(1)H nuclear magnetic resonance spectroscopies;gas chromatography;and viscosity measurements.At 70℃,the metallocene catalyst created more stable active sites.In addition,the alkylation effect of MAO was noticeable.Interestingly,the obtained catalysis results demonstrated that a high conversion ratio of~93%was achieved at a low reaction temperature of 70℃,with a catalyst dosage of 0.0848 mmol and Al:Zr ratio of 8.48mmol:0.0848mmol.Moreover,under these optimal conditions,the kinematic viscosity of PAO was 4.25 mm2/s at 100℃,and the viscosity index was 139,indicating good viscosity-temperature properties.

蓖麻油硼酸酯水基润滑剂的制备及性能

利用蓖麻油、有机醇胺和硼酸合成出一种环境友好型水基润滑剂,利用四球试验机考察了其摩擦学性能,并初步探讨了润滑剂的润滑机理。试验结果表明:用NaOH溶液和有机醇胺将蓖麻油充分皂化后与硼酸反应,生成一种水基润滑剂,可以大大提高其润滑性能。

Alkylation of naphthalene with n-butene catalyzed by liquid coordination complexes and its lubricating properties

With the development of coal chemical industry,large amounts of naphthalene and n-butene are produced,and converting them into high value-added products through alkylation has gained particular importance and interest.In this work,liquid coordination complexes(LCCs)were used as acid catalysts for the first time in the naphthalene alkylation reaction under mild conditions to obtain multibutylnaphthalenes with high yield.Various reaction conditions were thoroughly investigated.The LCC consisting of urea and AlCl_(3) showed excellent catalytic performance under optimal reaction conditions,giving 100%conversion of naphthalene and 99.66%selectivity towards multi-butylnaphthalenes.Combining the catalyst properties and catalytic results,a plausible reaction mechanism was proposed.The lubricating properties of the synthesized products were investigated for their potential application as lubricating base oils.The synthesized multi-butylnaphthalenes showed comparable physicochemical properties and tribological performances as the commercial cycloalkyl base oil.

Superlubricity of a Mixed Aqueous Solution

A super-low friction coefficient of 0.0028 is measured under a pressure of 300MPa when the friction pair(the silicon nitride ball sliding on the silicate glass)is lubricated by the mixed aqueous solution of glycerol and boric acid.The morphorlogies of the hydroxylated glass plate are observed by an atomic force microscope(AFM)in deionized water,glycerol,boric acid and their mixed aqueous solution.Bonding peaks of the retained liquids adhered on the surface of the sliding track are detected by an infrared spectrum apparatus and a Raman spectrum apparatus.The mechanism of the superlubricity of the glycerol and boric acid mixed aqueous solution is discussed.It is deduced that the formation of the lubricant film has enough strength to support higher loads,the hydration effect offering the super lower shear resistance.

Controllable synthesis of different morphologies of CuO nanostructures for tribological evaluation as water-based lubricant additives

In this study,water soluble CuO nanostructures having nanobelt,nanorod,or spindle morphologies were synthesized using aqueous solutions of Cu(NO_(3))_(2)·3H_(2)O and NaOH by adjusting the type of surface modifier and reaction temperature.The effect of morphologies of these various CuO nanostructures as water‐based lubricant additives on tribological properties was evaluated on a UMT‐2 micro‐friction tester,and the mechanisms underlying these properties are discussed.The three different morphologies of CuO nanostructures exhibited excellent friction‐reducing and anti‐wear properties.Tribological mechanisms differed in the initial stage of frictional interactions,but in the stable stage,a tribochemical reaction film and adsorbed lubricious film on the rubbing surfaces played important roles in hindering direct contact between friction pairs,leading to improved tribological properties.