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At least 55 records · Page 3

Methods to Observe Tribological Failures in Self-Mated Steel Contacts

Scuffing, a type of wear found in highly stressed or poorly lubricated contacts, is characterized by a rapid increase in friction and severe plastic deformation of the near-surface material. Scuffing has proven difficult to study because it initiates unpredictably, progresses rapidly, and typically develops within an inaccessible contact interface. Although there have been successful in-situ studies of scuffing in real-time, the transparent counter body needed for these studies changes the interactions between the surfaces and the lubricant, which affects the scuffing process in unknown ways. This paper describes the development of X-ray-compatible tribometry to study the scuffing of self-mated steels in-situ and in real-time. The method uses a crossed cylinders configuration with a thin (500 μm thick) stationary component and a small (≈200 μm) contact width to maximize X-ray interactions with atoms within the stress field generated by the contact. The resulting instrument and method are used to benchmark the scuffing response of self-mated 52,100 steel under tribologically challenging ‘oil-off’ lubrication conditions. The results demonstrate reliable scuffing in this configuration despite the relatively small contact areas and loads used. Following scuffing, gross plastic deformation was observed on both surfaces along with significant subsurface grain refinement and flow only on the stationary surface, which experienced constant contact. Interestingly, high friction initiated at specific locations of the migratory surface, which experienced intermittent contact, and then propagated across the track over time, suggesting that local conditions of the migratory surface dominated friction leading into the failure event.

36 MATERIALS SCIENCE↗

Hydrogenolysis Versus Hydrocracking for Polyolefin Upcycling

Global plastic production has reached 413.8 million metric tons in 2024 and is forecasted to surpass 1.2 billion metric tons by 2050. Polyolefins, mainly polyethylene (PE) and polypropylene (PP), dominate single-use packaging and account for approximately 55% of global plastic waste. The chemical inertness that makes these materials desirable for commercial applications also renders them persistent in the environment. Current recycling technologies have proven to be insufficient to divert plastic waste from landfills or environmental loss due to technical limitations and poor economic incentives. Conventional mechanical recycling is a form of downcycling, in which the polymer remelting process results in products with inferior material properties and reduced market value. Pyrolysis, a thermochemical route used for the chemical recycling of plastic wastes into refinery feedstock, requires severe conditions, typically 400–600 °C in an oxygen-free environment. The high temperature drives up energy costs and produces a wide range of poorly defined products, including undesirable light gases and heavy tars that pose challenges for downstream processing. As an alternative, catalytic chemical recycling offers a promising route for converting waste polyolefins back into value-added hydrocarbons—such as fuels, lubricant base oils, and other chemical feedstocks—at temperatures typically below 300 °C. This opinion article focuses on two dominant pathways in heterogeneous catalysis that are used to cleave the C–C bonds of polyolefins: hydrogenolysis and hydrocracking. Both catalytic pathways have the potential to selectively convert polyolefin waste into valuable fuels and chemical feedstocks under mild conditions. Notably, while hydrocracking primarily yields branched hydrocarbon products, hydrogenolysis predominantly produces linear hydrocarbons. Here, we compare the mechanisms and catalyst designs for hydrocracking and hydrogenolysis, analyze critical technical challenges from catalyst stability to process engineering, and provide an outlook on how these complementary pathways can be used to repurpose plastic waste into valuable products.

Zhang, Ruoxi [Iowa State Univ., Ames, IA (United S↗

The effect of electrical current on premature failures and microstructural degradation in bearing steel

Premature failures associated with microstructural degradation, i.e. white etching cracks (WECS), are becoming commonplace as applications are requiring tribological components to operate under extreme conditions. Although the specific drivers of WECs are still debated, the failures are often found in applications where cyclic loading is combined with added energy from stressors such as slip, impacts, or stray current. The aim of the current work is to elucidate effect that variable current has on premature failure. Numerous commercially available lubricants were tested, and both lubricant base oil type and additive package were found to have an effect on WEC failure time.

Bearing failure↗

Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

Hydrogenolysis of plastic waste using Ru-based catalysts is promising for deconstructing polyolefins into lower molecular weight products. Yet, the effect of catalyst atomic structure and size on activity and product selectivity is poorly understood. Herein, we expose the effect of metal particle size and atomic structure on isotactic-polypropylene (i-PP) hydrogenolysis over Ru supported on carbon. Despite similar molecular weight distributions of solid and liquid products, their physical properties are distinct due to different chain regio-irregular CH3 sequences of steric pentads containing racemo configurations. We propose that i-PP hydrogenolysis entails an interplay of C–C bond scission and stereoisomerization. The active site’s local electronic environment and structure dictate the former, whereas polymer–catalyst surface interactions creating suitable polymer conformations control the latter. C–C scission and stereoisomerization are structure-sensitive. Small, disordered nanoclusters are effective in C–C bond scission, whereas larger metal nanoparticles promote stereoisomerization. Finally, we hypothesize that a heterogeneous distribution of metal active sites is essential for deconstruction and product (lubricant base oil) quality control.

36 MATERIALS SCIENCE↗

Chemical Recycling of Plastic Waste to Higher Value Lubricants

The aim of this project was to develop scalable methods to convert plastic waste to petrochemical-equivalent feedstocks and demonstrate their utility in lubricant base oil and wax applications. These objectives were partially accomplished, by scaling up the synthesis of platinum-on-strontium titanate catalysts to twenty gram batches, scaling up the conversion of plastic waste to twenty-five grams of plastic, producing high-melt waxes and characterizing their properties, and demonstrating the purification of high-melt waxes. High-melt waxes are one petrochemical-equivalent feedstock that can be made from plastic waste, consisting of a hard wax with a melt point above 65 C. They are used as ingredients in hot melt adhesives, coatings, and cosmetics. Producing a petrochemical-equivalent feedstock from plastic waste provides an advantage in lower carbon footprint and manufacturing cost, as the waste feedstock costs less than crude oil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Silicone modified lubricant

A silicone modified lubricant includes a Group I, II, III, IV or V base oil in combination with a minor amount of a silicone oil. Further, the lubricant includes a dispersant such as a dispersant olefin copolymer which maintains the silicone oil dispersed in the base oil. The silicone oil reduces the surface tension of the lubricant thereby reducing power loss. Preferably the lubricant formation has a surface tension less than 28 mN/m, making it particularly suitable for dip lubrication systems.

Kolekar, Anant S.↗

Investigations on the Thermal Stability and Kinetics of Biolubricants Synthesized from Different Types of Vegetable Oils

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soybean oil (HOSOY), regular soybean oil (RSOY), and waste cooking oil (WCO) were subjected to chemical modification, where isopropyl groups were attached to the fatty acid chains of the oils to produce branched oils, i.e., b-HOSOY, b-RSOY, and b-WCO. The detailed kinetic study of each regular and modified sample was investigated using thermogravimetric analysis. The kinetic parameters, such as the activation energies, reaction rate, and pre-exponential factor, were generated via Friedman methods. The differential thermal gravimetric (DTG) analysis showed low volatilization at the onset temperature in each modified oil as compared with the unmodified samples under an oxidative environment. Furthermore, the comparative kinetic studies demonstrated the enhanced thermoxidative stability of the modified products relative to their unaltered counterparts. Among the tested oils, the b-RSOY showed an average activation energy of 325 kJ/mol, followed by the b-WCO: 300 kJ/mol and the b-HOSOY: 251 kJ/mol, indicating the most stable modified product under an oxidative environment. For all the samples, the pre-exponential factors were in good agreement with the activation energies, which validates that finding the pre-exponential components is crucial to the kinetic analysis.

Sarker, Majher I. (ORCID:0000000299509274)↗

Competitive Adsorption of Ionic Liquids Versus Friction Modifier and Anti-Wear Additive at Solid/Lubricant Interface—Speciation with Vibrational Sum Frequency Generation Spectroscopy

A modern lubricant contains various additives with different functionalities and the interactions or reactions between these additives could induce synergistic or antagonistic effects in tribological performance. In this study, sum frequency generation (SFG) spectroscopy was used to investigate competitive adsorption of lubricant additives at a solid/base oil interface. A silica substrate was used as a model solid surface. The lubricant additives studied here included two oil-soluble ionic liquids (ILs, [N888H][DEHP] and [P8888][DEHP]), an antiwear additive (secondary ZDDP), an organic friction modifier (OFM), and a dispersant (PIBSI). Our results showed that for mixtures of ZDDP and IL in a base oil (PAO4), the silica surface is dominated by the IL molecules. In the cases of base oils containing OFM and IL, the silica/lubricant interface is dominated by OFM over [N888H][DEHP], while it is preferentially occupied by [P8888][DEHP] over OFM. The presence of PIBSI in the mixture of PAO4 and IL leads to the formation of a mixed surface layer at the silica surface with PIBSI as a major component. The SFG results in this investigation provide fundamental insights that are helpful to design the formulation of new lubricant additives of desired properties.

25 ENERGY STORAGE↗

Deconvoluting Structures of Component Plant Biopolymers Using Deuterium Labeled Brassica oleracea Stems

Several Brassica species are cultivated globally for the production of seed oils as food, lubricants, and increasingly biofuels. The stem and leaf residues of these herbaceous dicotyledonous crops constitute another feedstock for biofuels and other products. Plant cell walls are complex, multipolymeric structures that consist primarily of polysaccharides and lignin. Cellulose chains coalesce to form crystalline microfibrils while the amorphous biopolymers, hemicellulose, and lignin form a network structure and fill the interstitial space. Neutron scattering has been used for the structural study of the assembly and deconstruction of the plant cell walls. However, similar neutron sensitivity of the different amorphous biopolymers has made structural association to individual component biopolymers nontrivial and ambiguous. To improve the association of structural features to specific biopolymer components, partial deuteration of the plant cell wall can be employed to increase the difference in the neutron scattering length density between amorphous carbohydrate and lignin plant polymers. Vegetative stems from partially deuterated Brassica oleracea acephala (kale) plants were obtained commercially, and the plant cell wall structures were studied by contrast-variation small-angle neutron scattering (CV-SANS) and Fourier-transform infrared spectroscopy (FTIR). FTIR results indicated that deuterium substitution for hydrogen in the carbohydrates was higher than that in lignin. By combining CV-SANS and FTIR results, the neutron scattering length density (nSLD) of the polysaccharides and lignin was determined to match nSLD of 65%:35% and 48%:52% D 2 O/H 2 O solvent mixtures, respectively. These nSLD values were higher than the nSLD values of polysaccharides and lignin for H 2 O grown biopolymers. The nSLD increase correlates to replacing about 42.5% of hydrogens present as both C–H and O–H groups in cellulose with deuterium atoms, while only 21% for lignin. In conclusion, this study lays the foundation to use partially deuterated plants to deconvolute structural features of the different component biopolymers, especially cellulose, hemicellulose, and lignin, of the plant cell wall without introducing unintended structural modifications due to the pretreatment extraction processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthetic Lubricants Derived from Plastic Waste and their Tribological Performance

The energy efficiency, mechanical durability, and environmental compatibility of all moving machine components rely heavily on advanced lubricants for smooth and safe operation. Herein an alternative family of high-quality liquid (HQL) lubricants was derived by the catalytic conversion of pre- and post-consumer polyolefin waste. The plastic-derived lubricants performed comparably to synthetic base oils such as polyalphaolefins (PAOs), both with a wear scar volume (WSV) of 7.5×10 -5 mm -3 . HQLs also performed superior to petroleum-based lubricants such as Group III mineral oil with a WSV of 1.7×10 -4 mm -3 , showcasing a 44% reduction in wear. Furthermore, a synergistic reduction in friction and wear was observed when combining the upcycled plastic lubricant with synthetic oils. Additionally, life cycle and techno-economic analyses also showed this process to be energetically efficient and economically feasible. This novel technology offers a cost-effective opportunity to reduce the harmful environmental impact of plastic waste on our planet and to save energy through reduction of friction and wear-related degradations in transportation applications akin to synthetic oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Combustion Gas Temperatures on Piston Deposits for Diesel and Ammonia Dual-Fuel Combustion

As new fuels are adopted for marine engines, it is necessary to understand their impact on lubricant performance. In order to evaluate the performance of existing lubricants and inform the development of new ones, a deposit control test protocol has been developed using the ExxonMobil Enterprise two-stroke marine diesel research engine. Repeated tests at the target speed/load operating condition but different thermal conditions show that the temperature of the combustion gases is a key driver in the formation of deposits on piston surfaces, impacting both the quantity of deposits and whether they are hard or gummy. These impacts are examined for diesel combustion as well as ammonia dual-fuel combustion. Among alternative marine fuels, ammonia has perhaps the most unanswered questions regarding interactions with cylinder lubricants. The influence of ammonia dual-fuel combustion on the thermal conditions experienced by the lubricant are discussed. Scrape down oil samples were collected after operation with ammonia for analysis and comparison with fresh oil. Chemical analysis using a GC/MS instrument did not show significant permanent chemical changes in the lubricant due to ammonia exposure.

Kaul, Brian [ORNL] (ORCID:0000000184813620)↗

Lubricant impacts on piston deposit formation in the Enterprise marine diesel research engine

The impact of lubricant formulation on piston deposits was studied using the Enterprise, a reduced-scale, single-cylinder, two-stroke crosshead marine diesel research engine. The Enterprise engine was specially designed for marine diesel lubricant research, with a custom reduced-scale cylinder lubricant injection system and extensive instrumentation of thermal boundary conditions on both the liner and piston. Lubricant conditions typical of full-scale marine diesel engines are obtained by matching mean piston speed, liner temperature profile, and combustion metrics to realistic values.Piston deposit thicknesses were measured after a set period of operation, with a focus on lubricant-based deposits on the lands and ring grooves, using both optical and contact-based measurement techniques. Engine operation for each lubricant was conducted according to a standardized protocol, with precise control of engine speed and load, cylinder lubricant injection rate, coolant temperatures, and system oil temperature; the liner and piston temperatures are continuously monitored during operation. After operation with each lubricant was completed, the engine was disassembled, and the piston and ring deposits were characterized. The piston was then thoroughly cleaned, and the lubricant system flushed, between each lubricant formulation being evaluated. The impacts on piston deposits of the lubricants being evaluated can thus be accurately quantified and are described herein.

Kaul, Brian↗

Minimizing Toxicity and Optimizing Lubricity of Ionic Liquids for Eco-Friendly Lubrication

As much as 60 million liters of lubricating fluids end up in the environment annually, and thus, the environmental impact of lubricants is increasingly recognized in addition to meeting the rheological and tribological requirements. Although US Environmental Protection Agency-approved environmentally acceptable base fluids are available, there is a lack of additives that are both nontoxic and effective in wear protection. Here, this study reports the successful development of a new class of ionic liquids (ILs) with demonstrated significantly lower aquatic toxicity and superior friction reduction and wear protection capabilities compared with a commercial lubricant additive and some ILs reported in the literature. Specifically, ammonium phosphate and phosphonium phosphate ILs with four-carbon alkyls have been identified with balanced oil solubility, thermal stability, toxicity, and lubricity, which provide fundamental insights for future development of eco-friendly ILs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced condensation heat transfer using porous silica inverse opal coatings on copper tubes

Abstract Phase-change condensation is commonplace in nature and industry. Since the 1930s, it is well understood that vapor condenses in filmwise mode on clean metallic surfaces whereas it condenses by forming discrete droplets on surfaces coated with a promoter material. In both filmwise and dropwise modes, the condensate is removed when gravity overcomes pinning forces. In this work, we show rapid condensate transport through cracks that formed due to material shrinkage when a copper tube is coated with silica inverse opal structures. Importantly, the high hydraulic conductivity of the cracks promote axial condensate transport that is beneficial for condensation heat transfer. In our experiments, the cracks improved the heat transfer coefficient from ≈ 12 kW/m 2 K for laminar filmwise condensation on smooth clean copper tubes to ≈ 80 kW/m 2 K for inverse opal coated copper tubes; nearly a sevenfold increase from filmwise condensation and identical enhancement with state-of-the-art dropwise condensation. Furthermore, our results show that impregnating the porous structure with oil further improves the heat transfer coefficient by an additional 30% to ≈ 103 kW/m 2 K. Importantly, compared to the fast-degrading dropwise condensation, the inverse opal coated copper tubes maintained high heat transfer rates when the experiments were repeated > 20 times; each experiment lasting 3–4 h. In addition to the new coating approach, the insights gained from this work present a strategy to minimize oil depletion during condensation from lubricated surfaces.

Adera, Solomon↗

Wear penalty for steel rubbing against hard coatings in reactive lubricants due to tribochemical interactions

Hard coatings and surface adsorptive/reactive lubricants are two common strategies for improving wear protection, but what if they are used together? In this study, steel-steel and steel-coating sliding was investigated in boundary lubrication of polar and non-polar oils containing a ZDDP or an ionic liquid. Two hard coatings, diamond-like-carbon (DLC) and chromium nitride (CrN), were used. Furthermore, for a steel-steel contact, wear was effectively reduced by using a more surface reactive lubricant, as expected. However, the steel ball wear was increased against a hard coating and further worsened with a more polar oil and/or a more surface reactive additive. The wear mechanism is proposed as a combined effect of physicochemical interactions with the lubricant, mechanical polishing by the counterface, and material adhesion.

36 MATERIALS SCIENCE↗

Comparison of Eco-Friendly Ionic Liquids and Commercial Bio-Derived Lubricant Additives in Terms of Tribological Performance and Aquatic Toxicity

Approximately half of the lubricants sold globally find their way into the environment. The need for Environmentally Acceptable Lubricants (EALs) is gaining increased recognition. A lubricant is composed of a base oil and multiple functional additives. The literature has been focused on EAL base oils, with much less attention given to eco-friendly additives. This study presents the tribological performance and aquatic toxicity of four short-chain phosphonium-phosphate and ammonium-phosphate ionic liquids (ILs) as candidate anti-wear and friction-reducing additives for EALs. The results are benchmarked against those of four commercial bio-derived additives. The four ILs, at a mere 0.5 wt% concentration in a synthetic ester, demonstrated a 30–40% friction reduction and >99% wear reduction, superior to the commercial baselines. More impressively, all four ILs showed significantly lower toxicity than the bio-derived products. In an EPA-standard chronic aquatic toxicity test, the sensitive model organism, Ceriodaphnia dubia, had 90–100% survival when exposed to the ILs but 0% survival in exposure to the bio-derived products at the same concentration. This study offers scientific insights for the future development of eco-friendly ILs as lubricant additives.

36 MATERIALS SCIENCE↗