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。

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.

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.

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.

Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties

Naphthenic base oil is an important lubricating base oil and very scarce in the global petroleum resources.Herein,a series of alkylated tetralin fluids similar to naphthenic base oils were produced by the alkylation of tetralin and a-olefins(n-hexene,n-octene,n-decene)with ionic liquid Et_3NHCl/AlCl_(3)as the catalyst,where the applied raw materials are totally derived from the coal chemical industry.The product composition could be controlled by adjusting the feeding ratio of tetralin and olefin.The synthetic fluids were evaluated as lubricating base oils to reveal the structure-property correlations.Their principal physicochemical and tribological properties depend on the chain-length of a-olefins and the number of alkyl groups onto the aromatic rings.Bis-(octyl-or decyl-)alkyl tetralin exhibited good properties in terms of viscosity,thermo-oxidation stability and pour point,as well as friction-reducing and anti-wear performance,showing great potential for producing naphthenic base synthetic oils from coal-based chemicals.

Versatile MXene Gels Assisted by Brief and Low‑Strength Centrifugation

Due to the mutual repulsion between their hydrophilic surface terminations and the high surface energy facilitating their ran-dom restacking,2D MXene nanosheets usually cannot self-assemble into 3D macroscopic gels with various applications in the absence of proper linking agents.In this work,a rapid spontaneous gelation of Ti3C2Tx MXene with a very low dispersion concentration of 0.5 mg mL^(-1) into multifunctional architectures under moderate centrifugation is illustrated.The as-prepared MXene gels exhibit reconfigurable internal structures and tunable rheological,tribological,electrochemical,infrared-emissive and photothermal-conversion properties based on the pH-induced changes in the surface chemistry of Ti_(3)C_(2)T_(x) nanosheets.By adopting a gel with optimized pH value,high lubrication,exceptional specific capacitances(~635 and~408 F g^(-1) at 5 and 100 mV s^(-1),respectively),long-term capacitance retention(~96.7%after 10,000 cycles)and high-precision screen-or extrusion-printing into different high-resolution anticounterfeiting patterns can be achieved,thus displaying extensive potential applications in the fields of semi-solid lubrication,control-lable devices,supercapacitors,information encryption and infrared camouflaging.

Synthetic polymers:A review of applications in drilling fluids

With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.

Design and optimization of fluid lubricated bearings operated with extreme working performances——a comprehensive review

Fluid lubricated bearings have been widely adopted as support components for high-end equipment in metrology,semiconductor devices,aviation,strategic defense,ultraprecision manufacturing,medical treatment,and power generation.In all these applications,the equipment must deliver extreme working performances such as ultraprecise movement,ultrahigh rotation speed,ultraheavy bearing loads,ultrahigh environmental temperatures,strong radiation resistance,and high vacuum operation,which have challenged the design and optimization of reliable fluid lubricated bearings.Breakthrough of any related bottlenecks will promote the development course of high-end equipment.To promote the advancement of high-end equipment,this paper reviews the design and optimization of fluid lubricated bearings operated at typical extreme working performances,targeting the realization of extreme working performances,current challenges and solutions,underlying deficiencies,and promising developmental directions.This paper can guide the selection of suitable fluid lubricated bearings and optimize their structures to meet their required working performances.

Silicone oil as a corneal lubricant to reduce corneal edema and improve visualization during

AIM:To evaluate the efficacy and safety of silicone oil(SO)as a corneal lubricant to improve visualization during vitrectomy.METHODS:Patients who underwent vitreoretinal surgery were divided into two groups.Group 1 was operated on with initial SO(Oxane 5700)as a corneal lubricant.Group 2 was operated on with initial lactated ringer’s solution(LRS)and then replaced with SO as required.Fundus clarity was scored during the surgery.Fluorescein staining was performed to determine the damage to corneal epithelium.RESULTS:Totally 114 eyes of 114 patients were included.Single SO use maintained a clear cornea and provided excellent visualization of surgical image.In group 1,the fundus clarity was grade 3 in 41/45 eyes and grade 2 in 4/45 eyes.In group 2,corneal edema frequently occurred after initial LRS use.The fundus clarity was grade 3 in 19/69 eyes,2 in 37/69 eyes and 1 in 13/69 eyes(P<0.05).SO was applied in 29 eyes of initial LRS use with subsequent corneal edema,which eliminated the corneal edema in 26 eyes.Corneal fluorescein staining score in group 1 was 0 in 28 eyes,1 in 11 eyes and 2 in 6 eyes,and 40,20 and 9,respectively,in group 2(all P>0.05).CONCLUSION:The use of SO as a corneal lubricant is effective and safe for preserving and improving corneal clarity and providing clear surgical field during vitrectomy.

FlowBreakdown of Hybrid Nanofluid on a Rigid Surface with Power Law Fluid as Lubricated Layers

Thiswork investigates an oblique stagnation point flowof hybrid nanofluid over a rigid surface with power lawfluidas lubricated layers. Copper (Cu) and Silver (Ag) solid particles are used as hybrid particles acting in water H2O asa base fluid. The mathematical formulation of flow configuration is presented in terms of differential systemthat isnonlinear in nature. The thermal aspects of the flow field are also investigated by assuming the surface is a heatedsurface with a constant temperature T. Numerical solutions to the governing mathematical model are calculatedby the RK45 algorithm. The results based on the numerical solution against various flow and thermal controllingparameters are presented in terms of line graphs. The specific results depict that the heat flux increases over thelubricated-indexed parameter.

空气润滑系统通风设计与CFD数值模拟

为增强通风系统设计的针对性和可靠性,提出一种满足空气润滑系统(AirLubrication System,ALS)压缩机正常运行的通风设计方案,并采用ANSYSFLUENT软件对温度场和压力场的分布情况进行分析,对通风设计的可靠性和合理性进行验证。研究成果可为空气润滑系统的通风设计提供一定参考。

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.

Consistency-dependent optical properties of lubricating grease studied by terahertz spectroscopy

The optical properties of four kinds of lubricating greases （urea, lithium, extreme pressure lithium, molybdenum disulfide lithium greases） with different NLGL （National Lubricant Grease Institute of America） numbers were investigated using terahertz time-domain spectroscopy. Greases with different NLGL grades have unique spectral features in the terahertz range. Comparison of the experimental data with predictions based on Lorentz Lorenz theory exhibited that the refractive indices of each kind of lubricating grease were dependent on the their consistency. In addition, molybdenum disullfide （MoS2） aa a libricant additive shows strong absorption from 0.2 to 1.4 THz, leading to higher absorption of MoS2-1ithium grease than that of lithium grease.

3D Two-way Coupled TEHD Analysis on the Lubricating Characteristics of Thrust Bearings in Pump-turbine Units by Combining CFD and FEA

The thermal elastic hydro dynamic （TEHD） lubrication analysis for the thrust bearing is usually conducted by combining Reynolds equation with finite element analysis （FEA）. But it is still a problem to conduct the computation by combining computational fluid dynamics （CFD） and FEA which can simulate the TEHD more accurately. In this paper, by using both direct and separate coupled solutions together, steady TEHD lubrication considering the viscosity-temperature effect for a bidirectional thrust bearing in a pump-turbine unit is simulated combining a 3D CFD model for the oil film with a 3D FEA model for the pad and mirror plate. Cyclic symmetry condition is used in the oil film flow as more reasonable boundary conditions which avoids the oil temperature assumption at the leading and trailing edge. Deformations of the pad and mirror plate are predicted and discussed as well as the distributions of oil film thickness, pressure, temperature. The predicted temperature shows good agreement with measurements, while the pressure shows a reasonable distribution comparing with previous studies. Further analysis of the three-coupled-field reveals the reason of the high pressure and high temperature generated in the film. Finally, the influence of rotational speed of the mirror plate on the lubrication characteristics is illustrated which shows the thrust load should be balanced against the oil film temperature and pressure in optimized designs. This research proposes a thrust bearing computation method by combining CFD and FEA which can do the TEHD analysis more accurately.

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%.

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.

Preparation and Rheological Properties of Vacuum Lubricating Grease

A kind of vacuum lubricating grease was prepared by using perfluoropolyether as base oil,perfluorinated polymer as thickener,and self-made additives.The colloidal stability of the grease was greatly improved by introducing a colloidal structure modifier.The rheological properties of the self-made grease(SMG),such as viscosity versus time,thixotropy,etc.,were studied by a rheometer at different temperatures and were compared with those of foreign brand grease(FBG).The results show that the performance of SMG reached the level of similar FBG,and some properties such as mechanical stability,colloidal stability,extreme pressure and antiwear properties were better.It can be used for long life lubrication of moving parts in a vacuum environment.

Synergistic Effect between Nano-ceramic Lubricating Additives and Electroless Deposited Ni-W-P Coating

The major solving ways for the material wear are surface modification and lubrication. Currently, the researches at home and abroad are all limited to the single study of either nano-lubricating oil additive or electroless deposited coating. The surface coating has high hardness and high wear resistance, however, the friction reduction performance of the coating with high hardness is not good, the thickness of the coating is limited, and the coating can not regenerate after wearing. The nano-lubricating additives have good tribological performance and self-repair function, but under heavy load, the self-repair rate to the worn surface with the nano-additives is smaller than the wearing rate of the friction pair. To solve the above problems, the Ni-W-P alloy coating and deposition process with excellent anti-wear, and suitable for industrial application were developed, the optimum bath composition and process can be obtained by studying the influence of the bath composition, temperature and PH value to the deposition rate and the plating solution stability. The tribological properties as well as anti-wear and friction reduction mechanism of wear self-repair nano-ceramic lubricating additives are also studied. The ring-block abrasion testing machine and energy dispersive spectrometer are used to explore the internal relation between the coating and the nano-lubricating oil additives, and the tribology mechanism, to seek the synergetic effect between the two. The test results show that the wear resistance of Ni-W-P alloy coating （with heat treatment and in oil with nano-ceramic additives） has increased hundreds times than 45 steel as the metal substrate in basic oil, the friction reduction performance is improved. This research breaks through the bottleneck of previous separate research of the above-mentioned two methods, and explores the combination use of the two methods in industrial field.

Discussion on the Mechanism of Boric Acid and Phosphoric Acid to Improve the Hardening of Complex Calcium Lubricating Grease

In order to solve the hardening problem of complex calcium lubricating grease, the water absorption test of several calcium salts was carried out, and it was found that calcium 12-hydroxystearate did not absorb water, and calcium acetate, calcium phosphate and calcium borate had different degrees of water absorption. Calcium acetate has the highest water absorption rate, while calcium phosphate and calcium borate show comparable water absorption rates. Upon using the molecular simulation technology, it is found that in the complex calcium grease system, calcium phosphate and calcium borate tend to combine with water, which inhibits the water absorption of calcium acetate and alleviate the hardening problem.