Molecular Mechanism and Molecular Design of Lubricating Oil Antioxidants

To overcome the limitations of traditional experimental“trial and error”methods in lubricant additive design,a new molecular design method based on molecular structure parameters is established here.The molecular mechanism of the antioxidant reaction of hindered phenol,diphenylamine,and alkyl sulfide are studied via molecular simulations.Calculation results show that the strong electron-donating ability and high hydrogen-donating activity of the antioxidant molecule and the low hydrogen-abstracting activity of free radicals formed after dehydrogenation are the internal molecular causes of the shielding of phenol and diphenylamine from scavenging peroxy free radicals,and the strong electron-donating ability is the internal molecular cause of the high activity of thioether in decomposing alkyl hydrogen peroxide.Based on this antioxidant molecular mechanism,a molecular design rule of antioxidant is proposed,namely“high EHOMO,large Q(S),low bond dissociation energy BDE(O—H)and BDE(N—H)”.Two new antioxidants,PAS-I and PAS-II,are designed and prepared by chemical bonding of hindered phenol,diphenylamine,and sulfur atoms.Experimental results show that these antioxidants both have excellent antioxidant effects in lubricating oil,and that PAS-II is the superior antioxidant,consistent with theoretical predictions.

Identification of Lubricating Oil Additives Using XGBoost and Ant Colony Optimization Algorithms

To address the problem of identifying multiple types of additives in lubricating oil,a method based on midinfrared spectral band selection using the eXtreme Gradient Boosting(XGBoost)algorithm combined with the ant colony optimization(ACO)algorithm is proposed.The XGBoost algorithm was used to train and test three additives,T534(alkyl diphenylamine),T308(isooctyl acid thiophospholipid octadecylamine),and T306(trimethylphenol phosphate),separately,in order to screen for the optimal combination of spectral bands for each additive.The ACO algorithm was used to optimize the parameters of the XGBoost algorithm to improve the identification accuracy.During this process,the support vector machine(SVM)and hybrid bat algorithms(HBA)were included as a comparison,generating four models:ACO-XGBoost,ACO-SVM,HBA-XGboost,and HBA-SVM.The results showed that all four models could identify the three additives efficiently,with the ACO-XGBoost model achieving 100%recognition of all three additives.In addition,the generalizability of the ACO-XGBoost model was further demonstrated by predicting a lubricating oil containing the three additives prepared in our laboratory and a collected sample of commercial oil currently in use。

OBJECT-ORIENTED IMPLEMENTATION OF EXPERT SYSTEMS FOR ENGINE LUBRICATING OIL INSPECTION

The inspection of engine lubricating oil can give an indication of the internal condition of an engine. By means of the Object-Oriented Programming (OOP), an expert system is developed in this paper to computerize the inspection. The traditional components of an expert system, such us knowledge base, inference engine and user interface are reconstructed and integrated, based on the Microsoft Foundation Class (MFC) library. To testify the expert system, an inspection example is given at the end of this paper.

Predictive methods for density and refractive index of naphthenic lubricating oils during solvent extraction process

Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.

Mechanism,Kinetics,and Thermodynamic Characteristics for the Demetallization of Used Lubricating Oil via Pyrolysis

This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate(T-115B)as a model compound.The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures.The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis,which revealed two distinct pyrolysis phases.Thus,the pyrolysis mechanism can be described by a twostep model.The activation energy and thermodynamic parameters(ΔH,ΔG,andΔS)were determined by applying the Kissinger-Akahira-Sunose,Flynn-Wall-Ozawa,Friedman,and Starink methods;the average activation energies for T-115B pyrolysis obtained using these methods were 115.80,119.84,124.96,and 116.14 kJ/mol,respectively.Further,both stages of the pyrolysis reaction followed Fn mechanisms with n=1.39 in the first stage and n=0.86 in the second stage.This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.

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.

Tribological effects of oxide based nanoparticles in lubricating oils

In order to enhance the tribological properties of lubricating oil, suitable surfactants such as Tween-20, Tween-60, Span-20 and Sodium sodecylbenzenesulfonate were selected and lubricating oils containing CeO2 and TiO2 nanoparticles were prepared. The morphology and size of CeO2 and TiO2 nanoparticles were examined with a transmission electron microscope （TEM）. The tribological properties of the oils were tested using an MRS-1J four-ball tribotester. The research results show that when the proportion by weight of CeO2 nanoparticles to TiO2 nanoparticles is 1：3, and the total weight fraction is 0.6%, the lubricating oil has optimal anti-wear and friction reducing properties. The addition of CeO2 nanoparticles reduces the required amount of TiO2 nanoparticles.

Rapidly determining kinematic viscosity of aviation lubricating oil 50-1-4Φ by mid-infrared spectrometry

This paper analyzed 11 lubricating oil 50-1-4Ф samples of different base oil content （standard oil） and 28 used oil samples by Fourier transform mid-infrared spectrometer （FTIR）. First, the absorption peak of 1 465 cm 1 was selected as the characteristic peak for determining their kinematic viscosities. And then correlation of the kinematic viscosity and the absorbance at characteristic peaks of corresponding infrared spectrum of standard oil and used oil samples was analyzed, re- spectively, and two regression equations were proposed. Finally, the regression equation of standard oil was corrected through other 20 new oil samples. The results show that determining kinematic viscosity of new lubricating oil 50-1-4Ф and the used one by FTIR is feasible and reliable.

Rapidly determining fuel pollution level of aviation lubricating oil 50-1-4Φby mid-infrared spectrometry

A series of aviation lubrication oil 50-1-4φ samples were prepared with different RP-3 content, and then these sam- ples were analyzed by Fourier transform mid-infrared spectrometer （FTIR）. The infrared region of 805--755 cm-1 was selected as quantitative area for determining fuel pollution level of aviation lubrication oil. Finally, correlation of the testing peak area and the fuel pollution level of corresponding samples were analyzed, and the regression equation was proposed. The results show that determining jet fuel pollution level of aviation lubricating oil by FTIR is feasible and reliable.

Study on application of CeO_2 and CaCO_3 nanoparticles in lubricating oils

The ceria （CeO2） nanoparticles and calcium carbonate （CaCO3） nanoparticles were chosen as additives of anti-wear and extreme pressure for lubricating oils, and the morphology and sizes of nanoparticles were examined using Transmission Electron Microscope （TEM）. The tribological performance of lubricating oils containing combined nanoparticles were determined by four-ball friction and wear tester, and the chemical composition of steel ball with worn surface were analyzed by X-ray Photoelectron Spectrurn（XPS）. The results showed that the lubricating oils containing combined nanoparticles had good anti-wear and friction reducing effects, and the tribological properties were optimal when WCeO2＋CaCO3=0.6%, WCeO2：WCaCO3=1：1. The extreme pressure value increased by 40.25%, the wear spot diameter reduced by 33.5%, and friction coefficient reduced by 32% compared with 40CD oil. The coordinated action of big and small particles made anti-wear and friction reducing effective. Tribological chemical reactions resulting from the friction surface formed metal calcium, metal cerium and oxides film, and they could fill up the concave surface and protect the worn surface.

Tribological Performances of Fatty Acyl Amino Acids Used as Green Additives in Lubricating Oil

The friction and wear characteristics of lauroyl glutamine, lauroyl glycine and lauroyl alanine, used as green additives in HVI 350 mineral lubricating oil, were evaluated on a four-ball tribotester. The morphologies and chemical species of the worn surfaces were analyzed by scanning electron microscope （SEM） and X-ray photoelectron spectroscope （XPS）, respectively. The test results indicated that the three fatty acyl amino acids could effectively improve the anti-wear and friction-reducing abilities of the HVI 350 mineral oil. The improvement in anti-wear and friction-reducing abilities of the mineral oil by the related amino acids was mainly ascribed to the formation of a composite boundary lubrication film due to the adsorption of amino acids on the friction surfaces.

Nanosized copper powders prepared by gel-casting method and their application in lubricating oil

Nanosized copper powders were prepared by a gel-casting method using copper nitrate, acrylamide（AM） and N, N′-methylenebisacrylamide（MBAM） as the main raw materials. The as-prepared copper powders were characterized by X-ray diffractometry and scanning electron microscopy, and then added into a 48# industrial white oil. Dispersion and wear properties of the compounded lubricating oil were tested. The results show that the copper powders prepared are of high purity, fine dispersibility with mean particle size of about 60 nm and with a narrow particle size distribution. The nanosized copper powders can be well dispersed in the lubricating oil. The addition of the copper powders obviously improves the anti-wear properties of the lubricating oil owing to their good self-repairing performance. Compared with 48# industrial white lubricating oil, the friction coefficient of GCr15 steel with the compounded oil containing 0.6% copper powders reduces by 0.07 and nearly no wear chippings are found in the scratches of the friction counter parts.

A Generalized Correlation for Characterization of Lubricating Base-oils from Their Viscosities

Lubricating mineral base oils are normally extracted from lube-oil cuts with furfural solvent.Aromatic content in the raffinate phase from extraction process is an essential parameter that affects the quality of the lubricating base-oils.For determination of aromatic content by the usual ASTM D3238 method,density,refractive index and molecular weight of the raffinate are required.In this work,a new generalized correlation is developed for de-termination the aromatic content by using only the measured viscosity of lubricating oil.With a mole fraction of aromatic compounds,the kinematic viscosity may be obtained at any temperature between 60-100°C along with their molecular weight and refractive index.

Prediction of Density and Refractive Index of Lubricating Oils during Secondary Solvent Extraction Process by Furfural

To meet the requirements for high aromatic content and low polycyclic aromatic(PCA)concentration,eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furfural.Among the different properties of rubber processing oils,density and refractive index are some of the most important properties related to their final quality.Two types of methods,including a pseudo-component approach by using mixing rules and several correlations,were used for calculation of density and refractive index at 20℃ of paraffinic furfural-extract oils and their secondary raffinates.Results indicated that similar accuracy was obtained for predicting the density and the refractive index of furfural+furfural-extract paraffinic oil systems.However,the quadratic correlation presents its advantage over the pseudo-component approach when the composition of oils is not available.Moreover,the quadratic correlation was also used for naphthenic lubricating oils during two-stage solvent extraction processes.The predictions showed much larger discrepancies with respect to experimental values than those of paraffinic lubricating oils,which indicated that the quadratic correlation was more suitable for paraffinic oils with a CN value of below 37%.

CONSTITUTIVE EQUATION OF A NEW AVIATION LUBRICATING OIL

The traction of a new aviation lubricating oil was measured on a self-made test rig. The calculating formulae of the rheological parameters of the oil such as Erying stress, limiting shear stress and shear elastic modulus were obtained under the condition of the high shear strain rate in elastohydrodynamic lubrication（EHL）. The constitutive equation of this oil was determined and verified by test. The results of experiments show that the behavior of the new aviation lubricating oil behaves as visco-elastic fluid and the theoretical value agrees fairly well with the measured data, which implies that the constitutive equation of this oil is correct and feasible.

Biodegradation of Lubricating Oil in Wastewater with Zoogloea sp.

The purpose of this study was to identify microbial strains that have a strong ability to biodegrade lubricating oil. No. 20 lubricating oil was used as the sole carbon source in an isolation medium to screen bacteria from sludge that had been contaminated with crude oil. Through both morphological and biochemical methods, the bacterial strain that had the highest biodegrading capacity was identified as Zoogloea sp. On the basis of these preliminary results, a biological contact oxidation method was employed to further assess the ability of the Zoogloea sp. strain to treat wastewater contaminated by No. 20 lubricating oil using three oxidation cabins and two hydraulic retaining times （HRT）. Results showed that the concentration of No. 20 lubricating oil with a 12 h hydraulic retaining time and 16.5 L h^-1 inflow rate was reduced by 99.3% in 15 d, and with a 6 h hydraulic retaining time and 33 L h%^-1 inflow rate it decreased by 98.6070 in 12 d. The results from this study indicated that Zoogloea sp. had a strong potential to be utilized in biodegradation of lubricating oil.

Effects of used lubricating oil on two mangroves Aegiceras corniculatum and Avicennia marina

An outdoor experiment was set up to investigate the effects of used lubricating oil （5 L/m^2） on Aegiceras corniculatum Blanco. and Avicennia marina （Forsk） Vierh., two salt-excreting mangroves. A. marina was more sensitive to used lubricating oil than A. corniculatum and canopy-oiling resulted in more direct physical damage and stronger lethal effects than base-oiling. When treated with canopy-oiling, half of A. corniculatum plants survived for the whole treatment time （90 d）; but, for A. marina, high mortality （83%） resulted from canopy-oiling within 3 weeks and no plants survived for 80 d. Base-oiling had no lethal effects on A. corniculatum plants even at the termination of this experiment, but 83% of A. marina plants died 80 d after treatment. Forty days after canopyoiling, 93% ofA. corniculatum leaves fell and no live leaves remained on A. marina plants. By the end of the experiment, base-oiling treatment resulted in about 45% ofA. corniculatum leaves falling, while all A. mar/na leaves and buds were burned to die. Lubricating oil resulted in physiological damage to A. corniculatum leaves, including decreases in chlorophyll and carotenoid contents, nitrate reductase, peroxidase and superoxide dismutase activities, and increases in malonaldehyde contents. For both species, oil pollution significantly reduced leaf, root, and total biomass, but did not significantly affect stem biomass. Oil pollution resulted in damage to the xylem vessels of fine roots but not to those of mediate roots.

Selection of Sinopec Lubricating Oil Producing Bases by Using the AHP Model

The factors affecting the developmcnt of Sinopec lubricating oil were analyzed in this paper, and an analytic hierarchy process （AHP） model for selecting lubricating-oil producing bases was developed. By using this model, nine lubricating oil producing companies under Sinopec were comprehensively evaluated. The evaluation result showed that the Maoming Lubricating Oil Company （Guangdong province）, Jingmen Lubricating Oil Company （Hubei province） and Changcheng Lube Oil Company （Beijing） are top three choices, and should be developed preferentially for the development of Sinopec producing bases of lubricating oil in the future. The conclusions provide the theoretical basis for selecting lubricating oil producing bases for decision makers.

Diester Derivatives from Chemically Modified Waste Cooking Oil as Substitute for Petroleum Based Lubricating Oils

In order to provide a new way for waste cooking oil(WCO) resource utilization, several diester derivatives were obtained from WCO through a three-step chemical modifications, viz.: transesterification, epoxidation and oxirane ring opening with carboxylic acids. The effects of the chain length of side chain groups on the viscosity, acid value, low temperature fluidity, thermo-oxidative stability, tribological properties and surface tension of diester derivatives were investigated. The results showed that increasing the chain length of side chain groups had a positive influence on the viscosity, viscosity index, acid value, pour point, friction coefficient and wear scar diameter along with a negative influence on the oxidation onset temperature, volatile loss, insoluble deposit, maximum non-seizure load and surface tension. These diester derivatives exhibited improved physicochemical and tribological properties that make themselves promising environmentally friendly biolubricant basestocks.

Friction Characteristics of Space Lubricating Oil No.4129 in Rolling and Sliding Contact

The friction coefficients between the surfaces of a ball and a disc lubricated by a space lubricating oil No.4129 were measured at various operating conditions on a ball-disc friction test rig. Friction characteristic curves were obtained under sliding and rolling movements at point contact. A new model for calculation of the friction coefficient was presented. The results show that the bigger the load is, the larger the friction coefficient becomes. The rolling speed ranging from 1 m/s to10 m/s has an important effect on the friction coefficient. The friction coefficient increases with the increase in sliding speed and the decrease in rolling speed. The linear variation region of the friction coefficient versus the sliding speed at high rolling speed is wider than that at low rolling speed. The model for calculation of the friction coefficient is accurate for engineering use.