C. Valencia

Development of new green lubricating grease formulations based on cellulosic derivatives and castor oil

Environmentally friendly lubricating greases may be produced by solely replacing the mineral base oil for vegetable oil. However, the substitution of traditional metallic soaps by biodegradable and renewable thickeners is, up to now, much less considered. This work is focused on the development of new oleogels, using castor oil and cellulose derivatives, which could be potentially used as biodegradable lubricating greases. Thermal and thermo-rheological behaviours of these materials were characterised by means of TGA analysis and SAOS measurements, in order to evaluate the evolution of oleogel microstructure with temperature. Moreover, both roll-stability and leakage tendency standard tests, usually performed in the grease industry, were used to evaluate the mechanical resistance of each sample. The evolution of biogrease linear viscoelasticity functions with frequency is quite similar to that found for traditional lithium lubricating greases. However, the influence of temperature on biogreases linear viscoelasticity functions is less important than that found for traditional greases. In general, the biogrease samples studied show both slightly lower mechanical stability and higher leakage tendency than traditional lubricating greases. The use of a blend of ethyl and methyl cellulose as thickener provides a mechanical stability comparable to that found for commercial greases.

Modeling of the non-linear rheological behavior of a lubricating grease at low-shear rates

This paper deals with modeling the non-linear rheological behavior of lubricating greases at very low shear rates. With this aim, dynamic linear viscoelastic, non-linear stress relaxation, transient and steady-state shear flow, and transient first normal stress difference measurements have been carried out on a diurea-derivative lubricating grease. A factorable non-linear viscoelasticity model, the Wagner integral model, derived from the K-BKZ constitutive equation, was used in order to predict the non-linear rheological response of the above-mentioned lubricating grease under shear. The time-dependent part of the model was described by its linear relaxation spectrum, whilst two different damping functions (Wagner and Soskey-Winters damping functions) were analysed as the strain-dependent factor. The continuous linear relaxation spectrum was estimated, using regularization techniques, from the dynamic linear viscoelasticity functions. The damping function was calculated from non-linear stress relaxation tests. The constitutive model, with Soskey-Winters damping function, predicted the steady-state flow curve, the transient shear stress and the transient first normal stress differences of the lubricating grease studied fairly well.

Non-linear viscoelasticity modeling of tomato paste products

Abstract This paper deals with the characterization and modeling of the non-linear rheological properties of tomato paste samples manufactured under different conditions (sieve pore size and breaking temperature). With this aim, flow measurements, dynamic linear viscoelastic and linear and non-linear stress relaxation tests have been carried out on the above-mentioned tomato paste samples. Different geometries with smooth and serrated surfaces have been used to optimize the viscous flow measurements and avoid wall-depletion phenomena. The viscous flow properties of tomato paste samples depend on water insoluble solids (WIS) content and particle size, which may be highly influenced by processing conditions. In general, viscosity follows a power-law relationship with tomato paste water insoluble content and particle diameter. A factorable non-linear viscoelasticity model, the Wagner integral equation, predicts the non-linear rheological response of these products under shear fairly well. The time-dependent part of this model is described by a continuous linear relaxation spectrum, calculated from regularization techniques. The use of the Soskey–Winter damping function provides the best predictions of the viscous flow curves.

Rheology and thermal degradation of isocyanate-functionalized methyl cellulose-based oleogels.

The -NCO-functionalization of methyl cellulose with HMDI and its application to chemically gel the castor oil is explored in this work by analyzing the influence of functionalization degree on the rheological and thermogravimetric behavior of resulting chemical oleogels. With this aim, different methyl cellulose chemical modifications were achieved by limiting the proportion of HMDI and, subsequently, oleogels were obtained by dispersing these polymers in castor oil and promoting the reaction between those biopolymers and the hydroxyl groups located in the ricinoleic fatty acid chain. -NCO-functionalized methyl cellulose-based oleogels were characterized from themogravimetric and rheological points of view. Suitable thermal resistance and rheological characteristics were found in order to propose these oleogels as promising bio-based alternatives to traditional lubricating greases based on non-renewable resources. In general, -NCO-functionalized methyl cellulose thermally decomposed in three main steps whereas resulting oleogels thermal decomposition takes place in one main single stage which comprises the thermal degradation of both the polymer and the castor oil. Temperature range for thermal degradation is broadened when using highly -NCO-functionalized methyl cellulose. A cross-linked viscoelastic gel was obtained with methyl cellulose functionalized in a relatively low degree (around 6% -NCO molar content). The rheological properties of highly functionalized methyl cellulose-based oleogels evolve during several months of aging, but mainly during the first week, due to the progress of the reaction between -NCO functional groups and castor oil -OH groups. SAOS functions analyzed and oleogel relative elasticity increase with the functionalization degree. Oleogel linear viscoelastic response is also extremely dependent on NCO-functionalized methyl cellulose concentration.

Isocyanate-Functionalized Chitin and Chitosan as Gelling Agents of Castor Oil

The main objective of this work was the incorporation of reactive isocyanate groups into chitin and chitosan in order to effectively use the products as reactive thickening agents in castor oil. The resulting gel-like dispersions could be potentially used as biodegradable lubricating greases. Three different NCO–functionalized polymers were obtained: two of them by promoting the reaction of chitosan with 1,6-hexamethylene diisocyanate (HMDI), and the other by using chitin instead of chitosan. These polymers were characterized through 1H-NMR, FTIR and thermogravimetric analysis (TGA). Thermal and rheological behaviours of the oleogels prepared by dispersing these polymers in castor oil were studied by means of TGA and small-amplitude oscillatory shear (SAOS) measurements. The evolution and values of the linear viscoelasticity functions with frequency for –NCO–functionalized chitosan- and chitin-based oleogels are quite similar to those found for standard lubricating greases. In relation to long-term stability of these oleogels, no phase separation was observed and the values of viscoelastic functions increase significantly during the first seven days of ageing, and then remain almost constant. TGA analysis showed that the degradation temperature of the resulting oleogels is higher than that found for traditional lubricating greases.

Chemical modification of methyl cellulose with HMDI to modulate the thickening properties in castor oil

This work deals with the selective incorporation of reactive isocyanate groups into methyl cellulose in order to be used as reactive thickening agent in castor oil. Resulting gel-like dispersions may have potential applications as green lubricating greases formulated from renewable resources. Two different isocyanate-functionalized methyl cellulose-based polymers were obtained by reaction of methyl cellulose with 1,6-hexamethylene diisocyanate. The functionalization degree, from fully functionalized to a certain number of free hydroxyl groups (58:36:6 ratio between –OMe, –NCO and free –OH groups), was controlled by modifying the reagents molar ratio. These polymers were characterized through nuclear magnetic resonance of protons (1H-NMR), Fourier transform infrared spectroscopy and thermogravimetric analysis (TGA). Thermal and rheological responses of oleogels prepared by dispersing these polymers in castor oil were studied by means of TGA analysis and small-amplitude oscillatory shear measurements. The evolution of linear viscoelasticity functions with frequency of the oleogel containing isocyanate-functionalized methyl cellulose with lower –NCO content is quite similar to that found for traditional lithium lubricating greases. In relation to long-term stability of these oleogels, the values of viscoelastic functions significantly increase during the first 7 days of ageing and then remain almost constant.

Evaluation of Thermal and Rheological Properties of Lubricating Greases Modified with Recycled LDPE

The influence that recycled low-density polyethylene (LDPE) and lithium thickener concentrations exerts on the thermal and rheological properties of lithium lubricating greases was investigated using different rheological techniques in a temperature range of 25–175°C. In this way, different lubricating grease formulations were manufactured by modifying the concentration of lithium 12-hydroxystearate and content of recycled LDPE. These lubricating greases were rheologically characterized through small-amplitude oscillatory shear (SAOS) and viscous flow measurements. In addition, bomb oxidation tests (BOTs) and thermogravimetric (TGA) analysis were carried out. From the experimental results obtained, it can be deduced that modified lithium lubricating greases can be considered thermo-rheologically complex materials. Different behaviors of the viscoelastic modulus with temperature as a function of thickener and recycled LDPE concentration were found. Two types of viscous flow behavior were observed depending on the grease composition: A plateau region appeared in a wide range of shear rates and, in some cases, a minimum in the flow curve was more pronounced at high temperatures. The modified lubricating greases studied showed lower thermal and oxidation stability than unmodified lithium lubricating greases.

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.

Rheological and Tribological Characterization of a New Acylated Chitosan–Based Biodegradable Lubricating Grease: A Comparative Study with Traditional Lithium and Calcium Greases

This work compares the thermal, rheological, and tribological properties of a new gel-like biodegradable formulation, prepared using an acylated chitosan thickener and castor oil, with properties exhibited by two conventional greases thickened with lithium and calcium soaps, respectively, taken as benchmarks. Thermogravimetric (TGA), rheological (small-amplitude oscillatory shear [SAOS], rheodestruction, and viscous flow) and tribological (friction and wear analysis) tests, as well as roll-stability measurements were carried out to characterize the three grease samples. In addition, infrared spectroscopy and differential scanning calorimetry (DSC) were used to chemically characterize the acylated chitosan thickener agent. From a thermogravimetric point of view, the new formulation displayed better thermal resistance than the calcium and lithium lubricating greases. The evolution of the linear viscoelasticity functions with frequency and viscosity values in the shear rate and temperature ranges studied were similar to those obtained with the commercial lubricating greases. However, the linear viscoelasticity functions of the biodegradable formulation were slightly more affected by temperature. The mechanical stability behavior and recovery of the rheological functions found in the biodegradable formulation were also better than that exhibited by the calcium-based grease. However, the friction coefficient measured at low rotational speed is slightly higher than that obtained with the benchmarks, with similar or lower values obtained at a high rotational speed. Resulting wear marks obtained after the frictional tests using the acylated chitosan–based grease were larger than those obtained with the commercial greases.

Tandem ATRP/Diels–Alder synthesis of polyHEMA-based hydrogels

The efficient, controlled polymerization of a batch of new poly(hydroxyethyl methacrylate-co-furfuryl methacrylate)s, [poly(HEMA-co-FMA)], of various compositions was achieved using atom transfer radical polymerization (ATRP) in methanol. When the FMA composition did not exceed the 10 mol% ratio, the evolution of molecular weight with conversion was linear, and polydispersities were around 1.1 for polymerization reactions at 15 °C and around 1.3–1.4 at 25 °C, indicating good control over the polymerization process. HEMA-based hydrogels were obtained by means of the Diels–Alder reaction between poly(HEMA-co-FMA) and an hydrophilic bisdienophile. Gelification was monitored by diffusion-filtered 1H NMR and solution 1H NMR spectroscopy. Modulated temperature differential scanning calorimetry (MTDSC) suggests the thermo-reversibility of the Diels–Alder coupling reaction of HEMA polymeric networks. Rheological studies showed that the linear viscoelasticity functions of hydrogels were influenced by the chemical composition.