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At least 811 records · Page 45

Synergistic Effects Between Phosphonium-Alkylphosphate Ionic Liquids and Zinc Dialkyldithiophosphate (ZDDP) as Lubricant Additives

Unique synergistic effects between phosphonium-alkylphosphate ionic liquids and zinc dialkyldithiophosphate (ZDDP) are discovered when used together as lubricant additives, resulting in significant friction and wear reduction along with distinct tribofilm composition and mechanical properties. The synergism is attributed to the 30-70× higher-than-nominal concentrations of hypothetical new compounds (via anion exchange between IL and ZDDP) on the fluid surface/interface.

36 MATERIALS SCIENCE↗

Synthesis of Biomass-Derived Ethers for Use as Fuels and Lubricants

Ethers synthesized from biomass-derived compounds have exceptional properties as fuels, lubricants, and specialty chemicals and can serve as replacements for petroleum-derived products. Recent efforts have identified heterogeneous catalysts for the selective synthesis of ethers from alcohols, aldehydes, ketones, furans, esters, olefins, carboxylic acids, and other molecules derived from biomass. This Review highlights the scope of etherification reactions and provides insights into the choice of catalysts and reaction conditions best suited for producing targeted ethers from the available starting materials. First, the properties of ethers for specific applications and the methods by which synthons for ether synthesis can be obtained from biomass are discussed. Then the progress that has been made on the synthesis of ethers via the following methods is summarized: direct etherification of alcohols; reductive etherification of alcohols with aldehydes or ketones; etherification of furanic compounds, esters, and carboxylic acids; and the addition of alcohols to olefins. Next, the mechanisms of these reactions and catalyst properties required to promote them are discussed, with the goal of understanding how reaction conditions can be tuned to optimize catalyst activity and selectivity towards desired ethers. Finally, the Review closes by examining the tradeoffs between catalyst selectivity, activity, stability, and reaction conditions required to achieve the most economically and environmentally favorable routes to biomass-derived ethers.

09 BIOMASS FUELS↗

Effect of Retained Austininte on White Etching Crack Behavior of Carburized AISI 8620 Steel Under Boundary Lubrication

The formation of white etching cracks (WECs) is a dominant failure mode in wind turbine gearbox bearings that can significantly shorten their operating life. Although the phenomenon of WECs has been communicated in the field for more than a decade, the driving mechanisms are still debated, and the impact of proposed mitigation techniques is not quantified. Leading hypotheses to inhibit the formation of WECs center on material solutions, including the use of steel with high levels of retained austenite (RA). The present work aims to explore the impact of RA on the formation of WECs within AISI 8620 steel under boundary lubrication. A three ring-on-roller benchtop test rig was used to replicate WECs in samples with different levels of RA. While varying levels of RA had a minimal effect on time until failure, a significant effect on crack morphology was observed. Additionally, potential underlying mechanisms of White Etching Area formation were elucidated. Under the current test conditions, the microstructural alterations adjacent to the cracks in the lower RA samples were more developed compared to those of the higher RA samples. Additionally, the WEC networks in the high RA samples contained significantly more crack branches than those of the low RA samples.

Bearing failure↗

Effect of Cu nanoparticles on the tribological performance of polydopamine + polytetrafluoroethylene coatings in oil-lubricated condition

For this study, the effect of Cu nanoparticles (NPs) on the tribological performance of the thick polydopamine (PDA) + polytetrafluoroethylene (PTFE) coatings in DTE-32 Mobil lubricated condition was investigated. PDA + PTFE + Cu NP coatings with 45 µm thickness were spray-coated with 0.12, 0.25, and 0.50 wt% of Cu NPs in an aqueous PDA + PTFE solution, respectively. The mechanical properties were studied by PeakForce quantitative nanomechanical (PFQNM) characterization and nanoindentation. The Young's modulus increased, and the coefficient of friction (COF) reduced with the addition of Cu NPs compared to PDA + PTFE coating. The PDA + PTFE + 0.25 wt% Cu and PDA + PTFE + 0.50 wt% Cu coatings increased the durability by 52% and 33%, respectively, compared to the coating without Cu NPs. The better tribological performance of the nanocomposite coatings is contributed by the better mechanical properties, better adherence, and enhanced cross-linking between the constituents of the nanocomposite coatings due to the presence of Cu NPs. The addition of 0.25 wt% Cu NPs in PDA + PTFE increased the thermal conductivity by 12%.

36 MATERIALS SCIENCE↗

Role of surface wetting on tribological behavior for laser nanotextured steel using ionic liquid lubricants

Here, this research evaluates the effect of surface wettability on the tribological performance through ball-on-flat tribology testing. The substrate material, M2 tool steel, is laser processed and then functionalized with fluorocarbon and nitrile chemistry to achieve distinct oleophobicity and oleophilicity, respectively, but with a similar nanoscale surface texture. The baseline lubricant is poly-alpha-olefin (PAO) oil, and ionic liquids (ILs) are used as additives for this study. The interaction between the nanoscale textured steel surface and ionic liquid-based oils is investigated. A set of reciprocating wear tests are performed to investigate the tribological behavior of the tribo-system consisting of the surface-engineered, flat M2 tool steel specimen and a standard, surface-polished steel ball. Results show that the oleophobic flat surface results in a lower friction, while the oleophilic surface modification leads to a better wear protection to the flat surface. Ammonium-based IL provides the highest friction reduction, while the phosphonium-based ILs provide an improved wear protection.

36 MATERIALS SCIENCE↗

Plasma-Functionalized Polytetrafluoroethylene Nanoparticles for Improved Wear in Lubricated Contact

Plasma-functionalized polytetrafluoroethylene (PTFE) nanoparticles were employed to evaluate their utility in improving the lubrication property of a group III mineral oil with a significantly low amount of zinc dialkyl dithiophosphate (ZDDP). The particles were coated with two consecutive films; the initial coating contained silica to enhance amorphous glassy tribofilm formation, followed by a methacrylate film to protect the silica coating and enhance dispersibility in the oil. The functionalized nanoparticles were evaluated for their tribological performance using a high-frequency reciprocating rig, in a cylinder-on-flat configuration. The oil formulations containing ZDDP (350 ppm phosphorus level) and the functionalized nanoparticles resulted in dramatic reductions in the friction coefficient and overall wear compared to the samples containing nonfunctionalized PTFE nanoparticles, ZDDP (350 ppm P), and samples devoid of nanoparticles but containing ZDDP with a 700 ppm P treat rate. XPS and XANES spectroscopy were employed to characterize the tribological films formed on the test samples. The samples with functionalized particles and ZDDP clearly exhibited tribofilms with Si- and F-doped polyphosphates of Zn coupled with the presence of ZnS at the metal-tribofilm interface. On the other hand, oils without the functionalized nanoparticles have oxides of Fe and to a lesser extent short-chain phosphates of Zn. The overall results suggest that the synergism between plasma-coated PTFE nanoparticles and ZDDP contributed to the development of protective tribofilms even at reduced amount of phosphorus in the oil. This new method of employing nanoparticles to deliver novel antifriction and antiwear chemistries at the tribological interfaces stands out as a promising approach to further reduce P levels in oils without compromising friction and wear performance.

plasma functionalization↗

Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformed a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated catalytic sequences for catalytic upgrading of bio-derived carboxylic acids to fuels, lubricants and chemical feedstocks

In the late 1850s, Charles Friedel's dry distillation of calcium acetate gave the world a novel route to the commercial production of acetone, a process that would later be referred to as decarboxylative dehydration (ketonization). While the subsequent development of the petrochemical industry made this route to acetone uncompetitive, today there is considerable interest in ketonization as means for converting biomass-derived fatty acids to produce longer-chained ketones, which could serve as precursors to fuels and lubricants. However, the lack of strategies beyond direct hydrogenation of the ketones into hydrocarbons has limited the practical application of ketonization for producing biofuels. In this paper, we describe here integrated catalytic sequences for converting a range of biomass-derived carboxylic acids, sourced through fermentation of sugars, hydrolysis of lipids, or biomass pyrolysis, to compounds that are fully compatible with the existing energy infrastructure and require minimal hydrogen input.

Shylesh, Sankaranarayanapillai↗

Supercritical CO 2 -induced atomistic lubrication for water flow in a rough hydrophilic nanochannel

We report a fluid flow in a nanochannel highly depends on the wettability of the channel surface to the fluid. The permeability of the nanochannel is usually very low, largely due to the adhesion of fluid at the solid interfaces. Using molecular dynamics (MD) simulations, we demonstrate that the flow of water in a nanochannel with rough hydrophilic surfaces can be significantly enhanced by the presence of a thin layer of supercritical carbon dioxide (scCO 2 ) at the water–solid interfaces. The thin scCO 2 layer acts like an atomistic lubricant that transforms a hydrophilic interface into a super-hydrophobic one and triggers a transition from a stick- to- a slip boundary condition for a nanoscale flow. Here, this work provides an atomistic insight into multicomponent interactions in nanochannels and illustrates that such interactions can be manipulated, if needed, to increase the throughput and energy efficiency of nanofluidic systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Thiol-promoted catalytic synthesis of high-performance furan-containing lubricant base oils from biomass derived 2-alkylfurans and ketones

About 97% of lubricant base oils are currently sourced from petroleum and the majority of the rest is produced from vegetable oils. We demonstrate a promising catalytic route to produce base oils from lignocellulosic biomass-derived 2-alkylfurans and ketones via carbon–carbon coupling in neat conditions. Among several homogeneous and heterogeneous acid catalysts tested, a perfluorinated sulfonic acid (Aquivion PW79S) exhibits the best catalytic performance and yields up to 90% renewable furan-containing base oils with the use of a thiol promotor. The effects of the acid strength of the catalysts, molecular size and structure of thiols and ketones, and fraction of thiols are studied. Electronic structure calculations elucidate the reaction pathway and indicate that the thiol reduces the barrier of the rate-determining dehydration step. The structure and properties of base oils can be tuned by using different synthons. Here, these base oils have excellent properties and can be competitive with or surpass the commercial synthetic alkylnaphthalene and furan-containing bio-ester base oils.

09 BIOMASS FUELS↗

Colloquium : Sliding and pinning in structurally lubric 2D material interfaces

A plethora of two-dimensional (2D) materials have been introduced in physics and engineering in the past two decades. Their robust, membranelike sheets permit (mostly require) deposition, giving rise to solid-solid dry interfaces whose mobility, pinning, and general tribological properties under shear stress are currently being understood and controlled, both experimentally and theoretically. Here, in this Colloquium simulated case studies of twisted graphene systems are used as a prototype workhorse tool to demonstrate and discuss the general picture of 2D material interface sliding. First highlighted is the crucial mechanical difference, often overlooked, between small and large incommensurabilities, which corresponds to, for example, small and large twist angles in graphene interfaces. In both cases, focusing on flat, structurally lubric or “superlubric” geometries, the generally separate scalings with the area of static friction in pinned states and of kinetic friction during sliding are elucidated and reviewed, tangled as they are with the effects of velocity, temperature, load, and defects. The roles of island boundaries and elasticity are also discussed, and compared when possible to results in the literature for systems other than graphene. It is proposed that the resulting picture of pinning and sliding should be applicable to interfaces in generic 2D materials that are of importance for the physics and technology of existing and future bilayer and multilayer systems.

2-dimensional systems↗