Influence of molecular weight and free NCO content on the rheological properties of lithium lubricating greases modified with NCO-terminated prepolymers

In this work, the use of reactive diisocyanate-terminated polymeric materials as rheology modifiers of lubricating greases has been studied. Particularly, the influences that free NCO content, molecular weight and functionality of the reactive prepolymers exert on the rheological response and microstructure of lubricating greases were analyzed. With this aim, NCO-terminated prepolymers were prepared from several di and trifunctional polyols and polymeric MDI. Afterwards, the reaction between terminal isocyanate groups and the hydroxy group located in the hydrocarbon chain of the 12-hydroxystearate lithium soap, used as thickener, was promoted during processing of lubricating greases. Polymeric materials used as additives and final lubricating greases were characterized by FTIR, DSC and GPC techniques. The effectiveness of these reactive additives was tested by performing small-amplitude oscillatory shear (SAOS), as well as standardized mechanical stability tests, on final greases. The rheological response was related to the microstructure of these greases, characterized by means of atomic force microscopy (AFM). From the experimental results obtained, it may be concluded that the effectiveness of these polymeric additives to modify the rheology of greases is due to the progress of the reaction between terminal isocyanate groups and the hydroxy group of lithium soap. However, a large dependence on both free NCO content and prepolymer molecular weight was found. Experimental results confirm that a balance between prepolymer molecular weight and NCO content is necessary to reach an optimal rheological modification of lithium greases. Moreover, this balance is a function of grease ageing, due to the progress of the reaction promoted.     

Steady flow and viscoelastic properties of lubricating grease containing various thickener concentrations

The flow and viscoelastic properties of a lubricating grease formed from a thickener composed of lithium hydroxystearate and a high-boiling-point mineral oil were investigated as a function of thickener concentration. The flow properties of grease were measured using continuous shear rheometry, while the viscoelastic properties were measured using oscillatory shear measurements. The flow properties show that grease is a shear-thinning fluid with a yield stress that increases with thickener concentration. At concentrations of lithium hydroxystearate greater than 5% by volume, the storage modulus, G', was found to be greater than the loss modulus, G", with both moduli increasing with increasing thickener concentration, below this critical concentration G" was greater than G'. Slip at the wall of the measuring platens was a major problem encountered during the rheological measurement of grease, this is hardly surprising, and greases are designed to slip in their lubricating functions. Therefore the measuring platens were roughened by sandblasting and significantly higher yield values were recorded with the roughened geometries. Creep experiments were also performed. In the creep test, yield stresses of greases could be obtained. Zero shear viscosity was also calculated from the creep experiment and as a result viscosities over nine orders of magnitude were obtained. The power law index of the scaling law of the elastic modulus and yield stress with increasing volume fraction was found to be 4.7+/-0.2 suggesting that the flocculation of the particles that compose the grease is likely to be of the chemically limited aggregation variety.     

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.     

Étude des propriétés des mélanges pebd régénéré / pebd vierge

This study is a contribution to the valorization of recycled low-density polyéthyléne (LDPE). First the characterization of five recycled LDPE produced from wastes coming from different sources was performed. The physical properties (density, melt flow index), chemical structure (Fourier transform infra-red spectroscopy) and mechanical properties (tensile strength and hardness) were investigated. The effect of the ratio of virgin LDPE on these physical and mechanical properties was studied in the case of the blends of recycled LDPE / virgin LDPE.     

The effect of gamma irradiation on mechanical, and thermal properties of recycling polyethylene terephthalate and low density polyethylene (R-PET/LDPE) blend compatibilized by ethylene vinyl acetate (EVA)

A study has been made on the compatibility of recycled polyethylene terephthalate (R-PET) and low density polyethylene (LDPE) blend in the presence of ethylene vinyl acetate (EVA) as a compatibilizing agent prepared by extrusion hot stretching process. EVA content in the blend as a compatibilizing agent was an enhancement effect on radiation crosslinking of R-PET/EVA/LDPE blends and the highest radiation crosslinking was obtained when the EVA content was reached at 10 % EVA when irradiated by gamma irradiation. Blends containing different (EVA) ratios were irradiated to different doses of gamma irradiation 25, 50 and 100 kGy. The effect of the compatibilizer and radiation on mechanical, thermal properties of R-PET together with LDPE and morphology has been investigated. It was found that gamma irradiation together with the presence of compatibilizing agent (EVA) has positive effect on the mechanical and thermal properties of R-PET/LDPE blend. The structural properties of R-PET/LDPE modified by gamma irradiation and EVA as compatibilizing agent was examined by SEM. Also, it was found that the optimum concentration of EVA and gamma irradiation dose was found to be 10 % EVA and 100 kGy, respectively.     

Improvement of the resistance to oxidation of the ecological greases by the additives

This article presents the results of research aimed at improving the oxidation stability of the ecological greases addressed toward application in machines working in the food industry. In order to improve the functional properties of grease, additives that modify the thermal stability have been added. Then, the influence of the additive on the grease resistance to the oxidation was examined. The results of tests of lubricants containing different types of additives are presented. The thermal examinations of the greases were carried out with the use of scanning differential calorimetry techniques. The lubricated properties of greases were investigated with the use of a four-ball tribotester. Based on the results, the relationships between the kind of additive, the resistance to oxidation and the lubricated properties of the grease were analysed, and the relationships between thermal and antiwear properties of grease were identified. Based on the results of this research, a new formulation of grease was proposed, which meets both the ecological needs and the working conditions in the food industry.     

Determination of radiolysis products in gamma-irradiated multilayer barrier food packaging films containing a middle layer of recycled LDPE

Volatile and non-volatile radiolysis products and sensory changes of five-layer food packaging films have been determined after gamma irradiation (5–60 kGy). Barrier films were based on polyamide (PA) and low-density polyethylene (LDPE). Each film contained a middle buried layer of recycled LDPE or 100% virgin LDPE (control samples). Data showed that a large number of radiolysis products were produced such as hydrocarbons, alcohols, carbonyl compounds, carboxylic acid. These compounds were detected in the food simulant after contact with all films even at the lower absorbed doses of 5 and 10 kGy. The type and concentration of radiolysis products increased progressively with radiation dose, while no new compounds were detected as a result of the presence of recycled LDPE. In addition, irradiation dose appears to influence the sensory properties of table water in contact with films.     

Recycling of Polyolefins: Part 2: Blends of Several Polymers

Abstract

The aim of the present paper is to study the feasibility of recycling polyolefins with some additives, such as copolymers in order to improve the mechanical properties and increase the useful life of the blends. From analysis of the results of blends of polypropylene(PP) with POD(Blend of recycled Polyolefins), it can be concluded that it is possible to recycle POD up to 20%, the addition of a copolymer to the 12% composition improving the interfacial adhesion. In the case of low density polyethylene(LDPE) mixtures with POD, the optimum improvement in properties is obtained with approximately 10% of POD. The addition of copolymers did not yield any improvement in the properties.     

Modelling relation between oxidation resistance and tribological properties of non-toxic lubricants with the use of artificial neural networks

The lubricants based on vegetable oils, as environmental friendly, are urgently sought. However, in addition to ecological characteristics, the lubricating properties have to be met. To meet these requirements the active additives influencing the lubricating properties and oxidation resistance are used. The useful lifetime of lubricants is determined largely by their abilities to resist oxidation. The article presented the results of new, ecological lubricants development. The oxidation performances of different developed lubricants have been tested. The experimentally determined oxidation stability of the compositions based on vegetable oils are presented. Analysed oxidation onset temperature was obtained from the differential scanning calorimetry (DSC) curves, which provides the rapid prediction of the oxidative stability of lubricants. Besides the lubricating composition based on vegetable oils, the developed greases-based mineral, or synthetic oil were investigated. The properties of these greases were evaluated using the measurement of parameters describing structure (penetration) and resistance to high temperature (dropping point). The lubricating properties of both the greases and vegetable oil compositions were tested on four-ball testing machine. In the results of the modelling of the lubricating properties the neural network models for the both types of the lubricants were developed. A discussion of the research results and analysis of models validity is given below. The experimental results are compared with the calculated using the neural models. An acceptable agreement was achieved.     

Additive‐like amounts of HDPE prevent creep of molten LDPE: Phase‐behavior and thermo‐mechanical properties of a melt‐miscible blend

Low‐density polyethylene (LDPE) is the preferred type of polyolefin for many medical and electrical applications because of its superior purity and cleanliness. However, the inferior thermo‐mechanical properties as compared to, for example, high‐density polyethylene (HDPE), which arise because of the lower melting temperature of LDPE, constitute a significant drawback. Here, we demonstrate that the addition of minute amounts of HDPE to a LDPE resin considerably improves the mechanical integrity above the melting temperature of LDPE. A combination of dynamic mechanical analysis and creep experiments reveals that the addition of as little as 1 to 2 wt% HDPE leads to complete form stability above the melting temperature of LDPE. The investigated LDPE/HDPE blend is found to be miscible in the melt, which facilitates the formation of a solid‐state microstructure that features a fine distribution of HDPE‐rich lamellae. The absence of creep above the melting temperature of LDPE is rationalized with the presence of tie chains and trapped entanglements that connect the few remaining crystallites. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 146–156     

Tribological properties of graphene nanosheets as an additive in calcium grease

The addition of graphene nanosheets (GNSs) in lubricating grease could significantly reduce the interfacial friction and improve the load-bearing capacity of the parts. Therefore, it has been considered as having great potential as lubricant additives. In this study, we synthesized GNSs that are prepared by a modified Hummer method, and investigated the effect of GNS with different concentration (0.5%, 1%, 2%, 3%, and 4?wt%) on the tribological properties of the calcium grease. The friction and wear experiments were performed using a four-ball tribometer. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were employed to examine the GNS and the friction mechanisms. Results indicate that the friction reduction ability and anti-wear property of the base grease can be improved with the addition of GNS. It was also found that the friction reduction decreases by 61%, and the wear scar diameter (WSD) decreases by 45%, and the extreme-pressure (EP) properties increased 60% at 3?wt% GNS. It is clear that the GNS in grease easily forms protective deposited films to prevent the rubbing surfaces from coming into direct contact, thereby improving the entire tribological behavior of the grease.     

Catalytic synthesis of biodiesel from high free fatty acid-containing feedstocks

Recyclable and reusable heterogeneous diarylammonium catalysts are highly effective in catalyzing the esterification of the free fatty acid (FFA) present in greases to methyl esters to reduce the FFA content from 12-40 wt% to 0.5-1 wt%; the resulting ester-glyceride mixture (pretreated grease) could then be readily converted to methyl esters by base-catalyzed transesterification.     

Nuclear magnetic resonance/magnetic resonance imaging on lubricating greases: Observation of bleeding and aging

Lubricating greases were investigated by nuclear magnetic resonance/magnetic resonance imaging (NMR/MRI) to get insight into their structure and into their response to mechanical forces, which is related to bleeding and aging. The investigated greases are based on metallic soaps of fatty acids and oils, whereby LiOH is often used. These organic soaps act as thickeners and provide a network in which oils and their additives are embedded. Lubricating greases can thus be considered as a class of substances similar to oleogels or even hydrogels. Questions arise about translational mobility of guest molecules, mainly base oil, in these networks. Molecular structuring and interactions within the network of thickeners are of interest as they are related to macroscopic stability. Apart from NMR spectroscopy (¹H-, ⁷Li- and ³¹P-NMR), spectrally resolved relaxation and diffusion measurements are used for characterization. In addition, magic angle spinning (MAS)-NMR was combined with ¹H-MRI to investigate the impact of mechanical stress and swelling of lubricating greases.     

Rheological studies of freely suspended soap films

 We have developed an original viscometer that allows the determination of the viscoelastic properties of freely suspended soap films. We have found that soap films have a very high shear viscosity and a small shear modulus that might be associated with a glassy (gel-like) behavior. The incorporation of polymer chains inside the soap films does not change very significantly these viscoelastic properties that are governed by the dense packing of the surfactant in the interfacial films; nevertheless, the role of the polymer can be qualitatively described by scaling laws. Received: 12 July 1999/Accepted in revised form: 7 September 1999     

Mechanical and thermal investigation of thermoplastic nanocomposite films fabricated using micro- and nano-sized fillers from recycled cotton T-shirts

The thermal and mechanical performance of composites with nano-sized cotton fillers embedded in low-density polyethylene (LDPE) is investigated. Microfibrillated cotton was prepared by microgrinding mechanical treatment of pulverized cotton (pCot) derived from waste T-shirts, resulting in nano-sized fibrils of the cellulose that retain high crystallinity. Film composites of LDPE with pCot before and after microgrinding were fabricated through melt extrusion and the effect of filler size on mechanical, thermal and morphological properties of the composite was investigated. Compounding microfibrillated cotton with LDPE resulted in well-dispersed nanocomposites with no discoloration after 10 min of melt extrusion at 170 °C. At concentrations up to 10 % by weight, the composites showed increased modulus, increased tensile strength and a slight decrease in elongation to break. Further improvement in the dispersion and mechanical properties of the cotton-based fillers was realized by the use of LDPE powder instead of polymer pellets fed to the extruder. This research demonstrates the processing and applicability of the use of recycled cotton-based nano-sized fillers in melt-processing.     

Properties of Low Density Polyethylene/Polypropylene Blends

ABSTRACT

The role of di-cumyl peroxide (DCP) as compatibilizer in low density Polyethylene/Polypropylene (LDPE/PP) blends has been explored. Mixtures with varying LDPE/PP ratio were prepared in a Brabender plasticorder and tested for their mechanical properties and calorimetric response. Then peroxide was added at concentrations up to 0.5%, and the mechanical properties of the these new blends were measured. Also, the mixing torque, melt flow index and gel content of the above products were recorded as a function of peroxide concentration. It was found that the incorporation of DCP restricts the thermoplastic characteristics of the melt, which was primarily attributed to branching which occurs in LDPE. This results in an enhancement in the adhesive bonding between the two polymers mainly due to chain entanglements. This was further supported by the fact that mechanical properties of the treated blend were significantly improved.     

Study and characterization of virgin and recycled LDPE/PP blends

Recycling of mixed plastic wastes composed of low-density polyethylene (LDPE) matrix and polypropylene (PP) was carried out by compounding using single-screw or twin-screw extruders. Blends of virgin polymers have been prepared to compare mechanical properties of both virgin and regenerated materials. First, a model composition of virgin LDPE/PP blend was prepared to study the effect of process parameters and that of different types of compatibilizers. Second, the results were applied to plastic wastes coming from industrial post-consumer plastic wastes. By adding compatibilizing agents such as ethylene-propylene-diene monomer, ethylene-propylene monomer, or PE-g-(2-methyl-1,3-butadiene) graft copolymer, elongation at break and impact strength were improved for all blends. The effect of these various copolymers is quite different and is in relation with their chemical structure. The recycled blends exhibit suitable properties leading to applications that require good mechanical properties.     

Effect of organoclay loading and electron beam irradiation on the physico‐mechanical properties of low‐density polyethylene/ethylene‐vinyl acetate blend

The influence of electron beam (EB) irradiation and organoclay (OC) loading on the properties of low‐density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends was investigated. The samples were subjected to the EB irradiation with the dose values of 50 and 250 kGy. X‐ray diffraction (XRD), gel content, mechanical, thermal, and electrical properties were utilized to analyze the characteristics of the LDPE/EVA blends with and without OC at different irradiation dosages. Gel content analysis showed that the OC promotes considerably the insoluble part so that the LDPE/EVA blends filled with OC become fully crosslinked at 250 kGy; possibly through the formation of further crosslinks between OC and polymer chains. The samples irradiated by EB showed enhanced mechanical properties due to the formation of three‐dimensional networks. In addition, thermogravimetric analysis indicated that combined OC loading and radiation‐induced crosslinking improved thermal stability of LDPE/EVA blends considerably. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermal,mechanical and permeation properties of gamma-irradiated multilayer food packaging films containing a buried layer of recycled low-density polyethylene

The effect of gamma radiation (doses 5–60 kGy) on the thermal, mechanical and permeation properties, as well as on IR-spectra of experimental five-layer food packaging films were studied. Films contained a middle buried layer of recycled low-density polyethylene (LDPE) comprising 25–50% by weight of the multilayer structure. Representative films containing 100% virgin LDPE as the buried layer were taken as controls. Results showed that the percentage of recycled LDPE in the multilayer structure did not significantly ($p<0.05$) affect the melting temperature, tensile strength, percent elongation at break, Young's modulus, oxygen, carbon dioxide and water vapour transmission rate values and the IR-spectra of the non-irradiated and irradiated multilayer films. Irradiation (mainly the higher dose of 60 kGy) induced certain small, but statistically significant ($p<0.05$) differences in the mechanical properties of multilayer films (with or without recycled LDPE layer) while no significant differences were observed in the thermal properties and in the gas and water vapour permeability of multilayer films. The above findings are discussed in relation to the good quality of the pre-consumer scrap used in the present study.     

水凝胶流变学研究概况

水凝胶具有良好的生物相容性和生物可降解性,其结构呈三维网状结构,与细胞外基质相似,在药物释放和组织工程等领域具有广阔的应用前景,被广泛地用于生物制药、生物材料和医学等领域。流变学可以描述材料的流动特性和力学性能,水凝胶的粘弹响应对材料内部结构的变化也非常敏感,因此流变行为被视为研究水凝胶的一种重要方法。本文综述了流变学方法在水凝胶研究中的应用,介绍了水凝胶流变学的研究方法,讨论了影响水凝胶流变学特征的因素,并展望了水凝胶流变学的发展前景。