Thickening Castor Oil with a Lignin-Enriched Fraction from Sugarcane Bagasse Waste via Epoxidation: A Rheological and Hydrodynamic Approach

Thickening vegetable oils to different extents is of great interest in the design and development of new bio-based lubricant formulations, as achieving a wide range of rheological properties is crucial to the successful replacement of petroleumbased traditional counterparts. With this aim, the influence of epoxidation degree, modified by altering the reaction conditions, on the viscous flow properties of epoxidized castor oil was investigated together with the incorporation of a lignin-enriched fraction from sugarcane bagasse waste to more extensively modify the rheological properties, thereby valorizing this waste fraction. Oil thickening was achieved by promoting the cross-linking between the epoxidized oil and the lignin-enriched fraction that enables the compatibilization of both components. Castor oil epoxidation was assessed by means of standard volumetric titration methods and infrared spectroscopy. In addition, a fully rheological characterization of both epoxidized and lignin-thickened castor oils was carried out. A hydrodynamic approach was also followed, aiming to provide an estimation of the Mark−Houwink−Sakurada parameters and relate the intrinsic viscosity with the average molecular weight of the resulting epoxidized castor oil/lignocellulose macromolecular compounds. The chemical interaction between castor oil and the lignocellulosic material increased as the extent of epoxidation was increased, yielding a variety of rheological responses from Newtonian liquids of increasing viscosities (from around 1 to 500 Pa·s) to viscoelastic liquids.This work is part of a research project (RTI2018-096080-B- C21) sponsored by the MICINN-FEDER I+D+i Spanish Programme. The financial support is gratefully acknowledged. The authors are also grateful to Dr. Ignacio Ballesteros (CIEMATMadrid, Spain) for kindly providing the ligninenriched waste fraction used in this study.Funding for open access charge: Universidad de Huelva / CBU

On the Steady-State Flow and Yielding Behaviour of Lubricating Greases

Practical steady-state flow curves were obtained from different rheological tests and protocols for five lubricating greases, containing thickeners of a rather different nature, i.e., aluminum complex, lithium, lithium complex, and calcium complex soaps and polyurea. The experimental results demonstrated the difficulty to reach “real” steady-state flow conditions for these colloidal suspensions as a consequence of the strong time dependence and marked yielding behavior in a wide range of shear rates, resulting in flow instabilities such as shear banding and fracture. In order to better understand these phenomena, transient flow experiments, at constant shear rates, and creep tests, at constant shear stresses, were also carried out using controlled-strain and controlled-stress rheometers, respectively. The main objective of this work was to study the steady-state flow behaviour of lubricating greases, analyzing how the microstructural characteristics may affect the yielding flow behaviou

AFM and SEM assessment of lubricating grease microstructures : influence of sample preparation protocol, frictional working conditions and composition

The microstructure of lubricating greases greatly conditions their in-service performance. In that sense, optimal testing protocols are required in order to accomplish their correct morphological characterization. This study explores and compares the suitability of atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques for imaging six different commercial metallic soap-based greases and two novel biopolymer-based formulations. Pros and cons of both techniques and the effect of sample preparation protocol were analysed. The results revealed a wide variety of morphological characteristics depending on composition. Thus, the four anhydrous calcium-based greases demonstrated two clearly distinct microstructures (fibrous and granular) determined by the type of base oil employed. With regard to the lithium complex greases, the typically reported microstructure characterized by well-defined entangled and fibrous network was observed in both AFM and SEM techniques. As for the two biopolymer-based greases, fibre networks were also encountered. Besides this, selected greases were subjected to different tribological tests, and the effect of high-shear frictional working treatments on their microstructure was also analysed. As a result of the friction and internal wear, the AFM results evidenced microstructural changes which depended on grease composition. Overall, the combined use of AFM and SEM techniques was demonstrated to be a powerful approach to microstructurally characterize lubricating greases.This work is part of two research projects (CTQ2014-56038-C3-1R and TEP-1499) sponsored by MINECO-FEDER and Junta de Andalucia programmes, respectively. The authors gratefully acknowledge the financial support. Authors also acknowledge Castrol (Germany) and Verkol S.A. (Spain) for kindly providing commercial samples

Rheology of lignin-based chemical oleogels prepared using diisocyanate crosslinkers : effect of the diisocyanate and curing kinetics

In this work, alkali lignin together with different diisocyanates (hexamethylene diisocyanate (HDI), isophorone diisocyanate (IDI), toluene diisocyanate (TDI) and 4,4′-methylenebis (phenyl isocyanate) (MDI)) have been tested as gelling agents in a castor oil medium. A two-step process comprising first lignin functionalization with a diisocyanate and then the formation of a bio-based polyurethane with gel-like characteristics by combining the functionalized lignin with castor was followed. FTIR and thermogravimetry analysis were carried out on both the gelling agents and resulting oleogels. Moreover, oleogel rheological properties were evaluated by means of small-amplitude oscillatory shear (SAOS) tests and viscous flow measurements. The influences of time-temperature processing conditions during oleogel formation, lignin/diisocyanate ratio and functionalized lignin concentration on the rheological properties of oleogels were analyzed using HDI as crosslinker. 30% (w/w) thickener concentration and room temperature processing were selected to prepare oleogels with the rest of diisocyanates considered. Under the same conditions, HDI-functionalized lignin-based oleogels showed the strongest gel-like behavior whereas TDI-, IDI- and especially MDI-functionalized lignin-based oleogels displayed weak gel-like, or even a liquid-like, behaviors as a consequence of the respective chemical structures, which guide to higher steric hindrance, diminishing the formation of urethane linkages and/or Van der Waals forces. In general, oleogels exhibited an internal curing process due to the progressive formation of urethane linkages, which is closely related to the evolving rheological properties. The kinetics of this curing process was studied and an empirical model has been proposed to predict the evolution of the rheological properties with time.This work is a part of two research projects (CTQ2014-56038-C3-1R and TEP-1499) sponsored by the MINECO-FEDER and Junta de Andalucía programmes, respectively

Electrospun lignin-PVP nanofibers and their ability for structuring oil

This work explores the electrospinnability of low-sulfonate Kraft lignin (LSL)/polyvinylpyrrolidone (PVP) solutions in N,N-dimethylformamide (DMF) and the ability of the different micro- and nano-architectures generated to structure castor oil. LSL/PVP solutionswere prepared at different concentrations (8–15wt%) and LSL:PVP ratios (90:10–0:100) and physico-chemically and rheologically characterized. The morphology of electrospun nanostructures mainly depends on the rheological properties of the solution. Electrosprayed nanoparticles or micro-sized particles connected by thin filamentswere obtained fromsolutionswith lowLSL/PVP concentrations and/or high LSL:PVP ratios,whereas beaded or bead-free nanofibers were produced by increasing concentration and/or decreasing LSL:PVP ratio, due to enhanced extensional viscoelastic properties and non-Newtonian characteristics. Electrospun LSL/PVP nanofibers are able to form oleogels by simply dispersing them into castor oil at concentrations between 10 and 30 wt%. The rheological properties of the oleogels may be tailored bymodifying the LSL:PVP ratio and nanofibers content. The potential application of these oleogels as bio-based lubricants was also explored in a tribological cell. Satisfactory friction and wear results are achieved when using oleogels structured by nanofibers mats with enhanced gel-like properties as lubricants. Overall, electrospinning of lignin/ PVP solutions can be proposed as a simple and effective method to produce nanofibers for oil structuringThis work is part of a research project (RTI2018-096080-B-C21) sponsored by the MICINN-FEDER I+D+i Spanish ProgrammeFunding for open access charge: Universidad de Huelva / CBU

Influence of surfactants on the electrospinnability of lignin‑PVP solutions and subsequent oil structuring properties of nanofiber mats

This work focuses on the improvement of the electrospinnability of low-sulfonate lignin (LSL)/polyvinylpyrrolidone (PVP) solutions by the addition of surfactants (SDS, CTAB and Tween-20) as well as on the ability of resulting nanofibers to structure castor oil. Solutions with two LSL/PVP weight ratios (70:30 and 90:10) in DMF were prepared by adding variable surfactant concentrations (0–1 wt.%), and physicochemically characterized. Electrical conductivity, surface tension and rheological measurements were performed. Variations of these physicochemical properties were explained on the basis of surfactant-polymer interactions. The addition of surfactants to LSL/PVP solutions improves electrospinnability, producing more compact and uniform fiber mats in 70:30 LSL/PVP systems, generally reducing the average diameter of the nanofibers and the number of beads. In contrast, nanofiber mats were not obtained with 90:10 LSL/PVP solutions, but different nanostructures composed of particle clusters. Dispersions of nanofiber mats obtained by electrospinning from 70:30 LSL/PVP solutions in castor oil were able to generate physically stable strong oleogels. In general, linear viscoelastic functions of oleogels increased with surfactant concentration. In addition, these oleogels exhibited excellent lubrication performance in a tribological contact, with extremely low values of the friction coefficient and wear diameters, which may lead to potential applications as lubricants.Research project (RTI2018-096080-B-C21) funded by MCIN/ AEI/10. 13039/ 501100011033 and by “ERDF A way of making Europe.” Funding for open access charge Universidad de Huelva/CBU

Impact of the Morphology of Electrospun Lignin/Ethylcellulose Nanostructures on Their Capacity to Thicken Castor Oil

This study reports on a novel strategy for manufacturing thickened gel-like castor oil formulations by dispersing electrospun lignin/ethylcellulose nanostructures. These thickened formulations were rheologically and tribologically evaluated with the aim of being proposed as alternative ecofriendly lubricating greases. Low-sulfonate kraft lignin (LSL) and ethylcellulose (EC) were dissolved in a DMAc:THF mixture at different concentrations (8, 10, and 15 wt.%) and LSL:EC ratios (50:50, 70:30, and 90:10) and subjected to electrospinning. The resulting electrospun nanostructures were morphologically characterized. EC acting as the cospinning polymer improved both LSL spinnability and the oil structuring ability. Solutions with a high lignin content achieved microsized particles connected by fibrils, whereas solutions with a high EC content (50:50 ratio) and LSL/EC total concentration (10 and 15 wt.%) yielded beaded or bead-free nanofibers, due to enhanced extensional viscoelastic properties and nonNewtonian characteristics. The gel-like properties of electrospun nanostructure dispersions in castor oil were strengthened with the nanostructure concentration and the EC:LSL ratio, as a result of the formation of a more interconnected fiber network. The oleodispersions studied exhibited a satisfactory frictional response in a tribological contact, with friction coefficient values that were comparable to those achieved with traditional lithium-lubricating greases: This work was supported by MCIN/AEI/10.13039/501100011033, by “ERDF—A way of making Europe” (grant number: RTI2018-096080-BC21) and by Junta de Andalucía/EPIT2020-UHU (grant numbers: PY20_00751 and UHU202029) by the FEDER European Programm

Influence of Base Oil Polarity on the Transient Shear Flow of Biodegradable Lubricating Greases

The scope of this study is to elucidate the physical mechanisms influencing the transient flow behavior of lubricating greases based on biogenic oleochemicals from a polarity point of view. This includes the mutually interacting influence of base oil polarity and thickening agents on the rheologically-measured mechanical structural degradation in transient shear flow. Due to the high temperature dependence of Keesom forces in the background of polar-active bond mechanisms, the analysis of the transient flow response as a function of temperature allows to attribute the observed influences to differences in base oil polarity. In general, clay-thickened greases show a greater tendency to be rheologically influenced by base oil polarities than soap-thickened lubricating greases

Different Kraft lignin sources for electrospun nanostructures production: Influence of chemical structure and composition

This work focuses on the structural features and physicochemical properties of different Kraft lignins and how they can influence the electrospinning process to obtain nanostructures. Structural features of Kraft lignins were characterized by nuclear magnetic resonance, size exclusion chromatography, fourier-transform infrared spectroscopy, and thermal analysis, whereas chemical composition was analyzed by standard method. The addition of cellulose acetate (CA) improves the electrospinning process of Kraft lignins (KL). Thus, solutions of KL/CA at 30 wt% with a KL:CA weight ratio of 70:30 were prepared and then physicochemical and rheologically characterized. The morphology of electrospun nanostructures depends on the intrinsic properties of the solutions and the chemical structure and composition of Kraft lignins. Then, surface tension, electrical conductivity and viscosity of eucalypt/CA and poplar/CA solutions were suitable to obtain electrospun nanostructures based on uniform cross-linked nanofibers with a few beaded fibers. It could be related with the higher purity and higher linear structure, phenolic content and S/G ratios of lignin samples. However, the higher values of electrical conductivity and viscosity of OTP/CA solutions resulted in electrospun nanostructure with micro-sized particles connected by thin fibers, due to a lower purity, S/G ratio and phenolic content and higher branched structure in OTP lignin.This work is part of two coordinated research projects (RTI2018-096080-B-C21 and RTI2018-096080-B-C22) funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. The authors also wish to thank the Comunidad de Madrid and MCIU/AEI/FEDER, EU for funding this study via Projects SUSTEC-CM S2018/EMT-4348. The authors also acknowledge the pre-doctoral grants from José Fernando Rubio Valle (Ref. PRE2019-090632). The contribution of COST Action LignoCOST (CA17128), supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorization is gratefully acknowledged

Oil structuring properties of electrospun Kraft lignin/ cellulose acetate nanofibers for lubricating applications: influence of lignin source and lignin/cellulose acetate ratio

In the present work, electrospun Kraft lignin/cellulose acetate nanostructures were produced, assessed and proposed as structuring or thickening agents of castor oil for lubricating applications. Solutions of Kraft lignins (KL) derived from different sources (eucalyptus, poplar and olive tree pruning) and cellulose acetate (CA) were prepared and used as feed for electrospinning. The rheological properties (shear and extensional viscosity), electrical conductivity and surface tension of KL/CA solutions influence the morphology of the electrospun nanofibers, which in turn is affected by the chemical structure and composition of the Kraft lignins. Electrospun KL/CA nanostructures consisting of filament-interconnected nanoparticles, beaded nanofibers or uniform nanofiber mats were able to form gel-like homogeneous fine dispersions by simply mechanically dispersing them into castor oil. The swelling of KL/ CA nanofibers in the percolation network was demonstrated. The rheological, tribological and microstructural properties of these oleogels are essentially governed by the morphological characteristics of the electrospun nanostructures, i.e. fiber diameter, number of beads and porosity. Rheological properties of the resulting oleogels may be tailored by modifying the lignin source and KL:CA weight ratio. According to their rheological and tribological properties, KL/ CA electrospun nanostructures-based oleogels can be proposed as a sustainable alternative to conventional lubricating greases.This work is part of a research project (RTI2018-096080-B-C21) funded by MCIN/AEI/10. 13039/501100011033 and by “ERDF A way of making Europe”. J.F. Rubio-Valle has also received a Ph.D. Research Grant PRE2019-090632 from Ministerio de Ciencia e Innovación (Spain). The financial support is gratefully acknowledged. Universidad de Huelva/CBUA thanks to the CRUE-CSIC agreement with Springer Nature