Rheology and stability of bitumen/EVA blends

Rheological measurements reveal that the viscoelastic properties of a 60/70 penetration grade bitumen are improved when either a virgin EVA or a recycled EVA copolymer of similar vinyl acetate content are mixed with it. Risk of cracking at low temperatures and rutting at high temperatures, are both reduced. Better viscoelastic features are obtained with the bitumen modified with recycled EVA, probably due to the presence of carbon black, which acts like a filler in this material. Stability tests performed combining oscillatory flow and microscopy results disclose that blends with the higher polymer proportion (3%) are susceptible of phase separation after 24 h of storage at 165 °C, but 1% blends are stable for at least 4 days. A general evaluation of the results indicates that the performance of this bitumen as a binder for road pavement, is particularly improved when 1% of recycled EVA or virgin EVA is added.     

A Review of Characteristics of Bio-Oils and Their Utilization as Additives of Asphalts

Transforming waste biomass materials into bio-oils in order to partially substitute petroleum asphalt can reduce environmental pollution and fossil energy consumption and has economic benefits. The characteristics of bio-oils and their utilization as additives of asphalts are the focus of this review. First, physicochemical properties of various bio-oils are characterized. Then, conventional, rheological, and chemical properties of bio-oil modified asphalt binders are synthetically reviewed, as well as road performance of bio-oil modified asphalt mixtures. Finally, performance optimization is discussed for bio-asphalt binders and mixtures. This review indicates that bio-oils are highly complex materials that contain various compounds. Moreover, bio-oils are source-depending materials for which its properties vary with different sources. Most bio-oils have a favorable stimulus upon the low temperature performance of asphalt binders and mixtures but exhibit a negative impact on their high-temperature performance. Moreover, a large amount of oxygen element, oxygen-comprising functional groups, and light components in plant-based bio-oils result in higher sensitivity to ageing of bio-oil modified asphalts. In order to increase the performance of bio-asphalts, most research has been limited to adding additive agents to bio-asphalts; therefore, more reasonable optimization methods need to be proposed. Furthermore, upcoming exploration is also needed to identify reasonable evaluation indicators of bio-oils, modification mechanisms of bio-asphalts, and long-term performance tracking in field applications of bio-asphalts during pavement service life.     

Choice of polymer-bitumen binders for cast asphalt concrete mixes

Modification of bitumen with Kraton D1101 and D1192, Luprene LG 411 and 501, and DST-30-01 polymeric additives and the effect of these additives on the properties of cast asphalt concrete mixes were studied.     

Kinetic parameters of different asphalt binders by thermal analysis

Each year, 100 millions tons of asphalt are manufactured worldwide and 88% of them are designated to act as binder in mineral aggregate producing asphalt mixtures in the paving industry. The present study investigates the kinetics parameters of thermal degradation through thermal analysis behavior of three different asphalt binders’ samples: an asphalt cement C and two asphalt binders modified by polymers: copolymer styrene–butadiene–styrene S and polyphosphoric acid L. By Thermokinetics software a model-free kinetic analysis could be made using two models: Friedman and Ozawa–Flynn–Wall. Kinetic parameters following both models, through Thermogravimetric curves, showed that for the first step, the binder L presented the highest activation energy followed by binder S. Between all simulations, the FnF1 model was the one which best correspond to the experimental data for all samples.     

Biomaterials and Their Potentialities as Additives in Bitumen Technology: A Review

The carbon footprint reduction mandate and other eco-friendly policies currently in place are constantly driving the trend of the synthesis and application of sustainable functional materials. The bitumen industry is not an exception to this trend and, every day, new technologies that facilitate safer, cost effective and more sustainable industrial processes and road paving operations are being researched and brought to light. A lot of research is currently ongoing to improve bitumen’s properties due to its use as a binder in road paving processes. Over the years, the most common method to improve bitumen’s properties has been with the use of additives. The major drawback in the use of these additives is the fact that they are substances of strong chemical nature which are either too acidic, too basic or emit toxic fumes and volatile organic compounds into the environment. In the long run, these chemicals are also toxic to the road pavement personnel that carry out the day to day industrial and paving operations. This led researchers to the initiative of synthesizing and applying biomaterials to be used as additives for bitumen. In this light, several studies have investigated the use of substances such as bio-oils, natural waxes, gum, polysaccharides and natural rubber. This literature review is aimed at classifying the different bio-based materials used to improve bitumen’s properties and to provide a deeper knowledge of the application of these biomaterials in bitumen technology. In general, we highlight how the research efforts elaborated herein could potentially foster safer, sustainable, eco-friendly approaches to improving bitumen’s properties while also promoting a circular economy.     

Waste Cooking Oil-Modified Epoxy Asphalt Rubber Binders with Improved Compatibility and Extended Allowable Construction Time

The application of crumb rubber from end-of-life tires and waste cooking oil (WCO) in road pavements is of significant importance from an economic and environmental viewpoint. However, the incorporation of crumb rubber greatly shortens the allowable construction time of epoxy asphalt binders due to the high viscosity of the epoxy asphalt rubber (EAR) binder and poor compatibility between crumb rubber and asphalt binder. To lower the viscosity of asphalt rubber, extend the allowable construction time and improve the compatibility of EAR binder, waste cooking oil (WCO) was introduced. The effect of WCO on the viscosity–time behavior, thermal stability, dynamic modulus, glass transitions, crosslink density, damping ability, compatibility, mechanical properties and phase separation of WCO-modified EAR binders was investigated by using the Brookfield viscometer, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine and laser confocal microscopy. The test results demonstrated that the incorporation of WCO declined the viscosity and extended the allowable construction time of the unmodified EAR binder. The inclusion of WCO improved the compatibility between asphalt and crumb rubber and the damping ability and elongation at the break of the unmodified EAR binder. The presence of WCO had a marginal effect on the thermal stability of the unmodified EAR binder. Confocal microscopy observation revealed that asphalt rubber particles aggregated in the epoxy phase of the unmodified EAR binder. With the inclusion of WCO, co-continuous asphalt rubber particles became more spherical.     

Burnout of Organic Components of Glass Ceramic Composite Tapes: Thermoanalytical investigations

Glass ceramic composite tapes are composed of inorganic raw materials (borosilicate glasses and inert fillers) and organic additives (polymer binder, plasticizer, dispergent, residues of solvent from the tape casting process). Burnout of organics in air is a complex process of vaporization, depolymerization and oxidation. Conditions of this process can be simulated by thermal analysis of plasticizer, various binders and binder/plasticizer mixtures with alumina, prepared by impregnation of alumina powder with corresponding solutions and subsequent drying. This allows a quantitative interpretation of the results of burnout of tapes.This revised version was published online in November 2005 with corrections to the Cover Date.     

Imaging techniques applied to characterize bitumen and bituminous emulsions

The purpose of this article is to present some important advances in the imaging techniques currently used in the characterization of bitumen and bituminous emulsions. Bitumen exhibits some properties, such as a black colour and a reflecting surface at rest, which permit the use of optical techniques to study the macroscopic behaviour of asphalt mixes in the cold mix technology based on emulsion use. Imaging techniques allow monitoring in situ the bitumen thermal sensitivity as well as the complex phenomenon of emulsion breaking. Evaporation-driven breaking was evaluated from the shape of evaporating emulsion drops deposited onto non-porous and hydrophobic substrates. To describe the breaking kinetics, top-view images of a drying emulsion drop placed on an aggregate sheet were acquired and processed properly. We can conclude that computer-aided image analysis in road pavement engineering can elucidate the mechanism of breaking and curing of bituminous emulsion.     

Multistage thermal decomposition in films of cadmium chloride-doped PVA–PVP polymeric blend

Several reports exist on the use of natural-oil-based materials as rejuvenators to restore the properties of aged binders—more specifically, regarding their ability to enhance the binders’ low-temperature properties and to reduce their stiffness. Rejuvenators are typically made of low molecular weight constituents which could easily volatilize and thus render the rejuvenated binder thermally unstable. Hence, the study of the thermal stability of rejuvenated binders is of paramount importance. In this research, a binder with a performance grade (PG) of PG58-28 modified with a soybean-derived rejuvenator at 12% by mass is added to an extracted reclaimed asphalt pavement (RAP) binder at a ratio of 1:5 resulting in a rejuvenator dosage rate of 2% by total mass of binder. The PG of the rejuvenated RAP binder is determined using both dynamic shear rheometer and bending beam rheometer. The thermal stability of the rejuvenator and the binders is verified using thermogravimetric analysis (TG). The rejuvenator shows good thermal stability up to a temperature of 302 °C. The RAP binder containing the rejuvenator shows similar thermal stability to the unrejuvenated RAP binder. The evolved gases from the TG analysis are analyzed using Fourier transform infrared (FTIR) to chemically characterize the rejuvenator and the binders. The FTIR spectrum of the rejuvenator reveals characteristic peaks. The intensity of these peaks serves as an indication of the rate of mass loss of the rejuvenator within the rejuvenated RAP binder.     

Unlocking the Hidden Potential of Cosmetics Waste for Building Sustainable Green Pavements in the Future: A Case Study of Discarded Lipsticks

This investigation is dedicated to unlocking the hidden potential of discarded cosmetics towards building green sustainable road pavements in the future. It is particularly aiming at exploring waste lipstick (WLS) as a high-quality functional additive for advanced asphalt mix technologies. To fuel this novel innovation, the effect of various WLS doses (e.g., 5, 10, and 15 wt.%) on the performance of base AP-5 asphalt cement was studied in detail. A wide array of cutting-edge analytical lab techniques was employed to inspect in-depth the physicochemical, microstructural, thermo-morphological, and rheological properties of resultant admixtures including: elemental analysis, Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thin-layer chromatography-flame ionization detection (TLC-FID), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), needle penetration, ring and ball softening point, Brookfield viscometer, ductility, and dynamic shear rheometer (DSR) tests. Unlike the unstable response of asphaltenes, the additive/artificial aging treatments increased the fraction of resins the most, and decreased that of aromatics; however, asphaltenes did not impair the saturates portion, according to Iatroscan research. FT-IR scan divulged that the WLS-asphalt interaction was physical rather than chemical. XRD diagnosis not only revealed an obvious correlation between the asphaltenes content and the fresh-binder crystallinity but also revealed the presence of fillers in the WLS, which may generate outstanding technical qualities to bituminous mixes. According to AFM/SEM analyses, the stepwise incorporation of WLS grew the magnitude of the “bee-shaped” microstructures and extended the roughness rate of unaged/aged binders. The prolonged consumption of the high thermal-stable additive caused a remarkable drop in the onset degradation and glass transition temperature of mixtures, thus enhancing their workability and low-temperature performance, according to TGA/DTGA/DSC data. The DSR and empirical rheological experiments demonstrated that the WLS could effectively lower the manufacturing and compaction temperatures of asphalt mixes and impart them with valuable anti-aging/fatigue-cracking assets. In a nutshell, the use of waste lipstick as an asphalt modifier is viable and cost-effective and could attenuate the pollution arisen from the beauty sector, while improving the performance of hot/warm asphalt mixes (HAM/WAM) and extending the service life of roadways.     

Surface microstructure of bitumen characterized by atomic force microscopy

Bitumen, also called asphalt binder, plays important roles in many industrial applications. It is used as the primary binding agent in asphalt concrete, as a key component in damping systems such as rubber, and as an indispensable additive in paint and ink. Consisting of a large number of hydrocarbons of different sizes and polarities, together with heteroatoms and traces of metals, bitumen displays rich surface microstructures that affect its rheological properties. This paper reviews the current understanding of bitumen's surface microstructures characterized by Atomic Force Microscopy (AFM). Microstructures of bitumen develop to different forms depending on crude oil source, thermal history, and sample preparation method. While some bitumens display surface microstructures with fine domains, flake-like domains, and dendrite structuring, ‘bee-structures’ with wavy patterns several micrometers in diameter and tens of nanometers in height are commonly seen in other binders. Controversy exists regarding the chemical origin of the ‘bee-structures’, which has been related to the asphaltene fraction, the metal content, or the crystallizing waxes in bitumen. The rich chemistry of bitumen can result in complicated intermolecular associations such as coprecipitation of wax and metalloporphyrins in asphaltenes. Therefore, it is the molecular interactions among the different chemical components in bitumen, rather than a single chemical fraction, that are responsible for the evolution of bitumen's diverse microstructures, including the ‘bee-structures’. Mechanisms such as curvature elasticity and surface wrinkling that explain the rippled structures observed in polymer crystals might be responsible for the formation of ‘bee-structures’ in bitumen. Despite the progress made on morphological characterization of bitumen using AFM, the fundamental question whether the microstructures observed on bitumen surfaces represent its bulk structure remains to be addressed. In addition, critical technical challenges associated with AFM characterization of bitumen surface structures are discussed, with possible solutions recommended. For future work, combining AFM with other chemical analysis tools that can generate comparable high resolution to AFM would provide an avenue to linking bitumen's chemistry to its microscopic morphological and mechanical properties and consequently benefit the efforts of developing structure-related models for bituminous materials across the different length scales.     

Elastic steric stabilization of polyethylene-asphalt emulsions by using low molecular weight polybutadiene and devulcanized rubber tire

Emulsions containing 3% polyethylene were stabilized against coalescence in an asphalt medium by low molecular weight virgin polybutadiene and recycled styrene-butadiene stabilizers. The recycled styrene-butadiene steric stabilizer precursor was obtained as a thermo-mechanical devulcanized ground rubber tire in asphalt. The low molecular weight butadiene and styrenebutadiene rubbers were in situ reacted with sulfur in order to increase the compatibility of the stabilizer with the asphalt phase.Because of the high molar volume of the asphalt phase and the similarity in contact energy between stabilizer and matrix phase, it is assumed that the stabilization is caused by entropic effects only. The fundamental aspects of elastic stabilization of polyethylene-asphalt emulsions are discussed. The total interaction free energy profile between the polyethylene particles shows that the efficiency of the steric stabilizer formation reaction can be improved significantly.The use of devulcanized rubber tire as a replacement for the virgin polybutadiene precursor in the in situ stabilization process can significantly reduce the cost of the technology.     

Bitumen-rubber composite binders for production of asphalt concretes

The dissolution of vulcanized rubber in bitumen in the presence of a devulcanizing additive and the formation of bitumen-rubber composites, which are promising binders for the production of asphalt concretes, were studied.     

Materiaux composites a base de graves et De liants polymeres—VI. Etude des enrobes a base de liant bitume-polyethylene ozonise et de granulats mineraux

Studies have been made of mixtures consisting of minerals and a binder made of bitumen with polyethylene (pure or recovered; non-ozonized or ozonized). The presence of the polymer leads to materials with better properties, especially compression strength. The bituminous mixtures are less affected by temperature have improved modulus of elasticity and there is better adhesion with the mineral. It is shown that recovered polyethylene, when ozonized, can be useful in bituminous mixtures.     

Modification of Paving Asphalts with Sulfur

Sulfur dissolved in oil components of asphalt is a binder, filler, and chemical co-reagent at once. The structure of sulfur-extended asphalt depends on its formula and heating temperature. Road pavement based on sulfur-extended asphalt demonstrates higher durability as compared to that with the conventional binders.     

Optimization of HDPE direct fluorination conditions by XPS studies

A fluorination reactor was designed and built in the laboratory. The optimal conditions of fluorination within the reactor were selected by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis of fluorinated surfaces of a film and a plaque of pure high-density polyethylene (HDPE). This reactor was used to post-mould fluorinate plaques and films of a range of mixtures of virgin and recycled HDPE with and without (re)introduction of additives. The ability to be fluorinated has shown no dependence on the composition virgin/recycled HDPE.Comparison of in-line and post-mould fluorinated samples showed that fluorine concentration profile in depth is thinner in the in-line fluorinated sample when compared with the post-mould fluorinated sample, though the fluorination degree in the extreme surface is larger in the in-line fluorinated sample. This is attributed to a migration of lower surface energy chain blocks towards the surface in the material at high temperatures, which is the case in the in-line fluorination, hindered in the post-mould fluorination where maximum temperature is below the melting point to keep the macroscopic shape. The additives played a minor role in the ability of the surface to be fluorinated.     

New eco-friendly low-cost binders for Li-ion anodes

In the production of commercial Li-ion batteries, the active materials slurries are generally prepared using polyvinylidene fluoride (PVdF) as binder because of its good adhesion properties and electrochemical stability. Unfortunately, there are some disadvantages related to the use of PVdF: the most important is the use of toxic and environmentally unfriendly solvents, such as N-methyl-pyrrolidone (NMP), and the second is the high costs. In the light of these considerations, it seemed straightforward to investigate the suitability of some water-soluble, inexpensive, and eco-friendly materials to test as alternative binders (sodium alginate, chitosan tragacanth gum, gelatin). The rheological properties of these materials have been investigated in addition to the electrochemical characterization. Furthermore, graphite electrodes with PVdF, carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) binders have been considered for sake of comparison. We found that some of these water-soluble binders, besides good electrochemical performances, showed a high adhesion to the current collector and a good electrochemical stability under the experimental conditions employed, which makes them interesting for the next generation of Li-ion batteries.     

Prediction of the energy of mechanical failure for elastomers filled with solid particles

Prediction (solution of direct problem) of the mechanical characteristics, including the energy of failure under extension, was considered for 3D-cross-linked elastomeric binders, filled with solid particles of polyfractional composition, in relation to the basic structural parameters of the composite material. It was shown that the use of lightly cross-linked highly silica-filled elastomeric binders with the optimal three-fraction composition represents a promising option for development of a frost-resistant waterproofing rolled material intended as a coating for road asphalt.     

Collagen‐based proteinaceous binder‐pigment interaction study under UV ageing conditions by MALDI‐TOF‐MS and principal component analysis

This study focuses on acquiring information on the degradation process of proteinaceous binders due to ultra violet (UV) radiation and possible interactions owing to the presence of historical mineral pigments. With this aim, three different paint model samples were prepared according to medieval recipes, using rabbit glue as proteinaceus binders. One of these model samples contained only the binder, and the other two were prepared by mixing each of the pigments (cinnabar or azurite) with the binder (glue tempera model samples). The model samples were studied by applying Principal Component Analysis (PCA) to their mass spectra obtained with Matrix‐Assisted Laser Desorption/Ionization‐Time of Flight Mass Spectrometry (MALDI‐TOF‐MS). The complementary use of Fourier Transform Infrared Spectroscopy to study conformational changes of secondary structure of the proteinaceous binder is also proposed. Ageing effects on the model samples after up to 3000 h of UV irradiation were periodically analyzed by the proposed approach. PCA on MS data proved capable of identifying significant changes in the model samples, and the results suggested different aging behavior based on the pigment present. This research represents the first attempt to use this approach (PCA on MALDI‐TOF‐MS data) in the field of Cultural Heritage and demonstrates the potential benefits in the study of proteinaceous artistic materials for purposes of conservation and restoration. Copyright © 2012 John Wiley & Sons, Ltd.     

Application of gas chromatography-mass spectrometry analysis to the study of works of art: paint media identification in polychrome multi-material sculptures

A new gas chromatographic-mass spectrometric procedure for characterizing both drying oils and proteinaceous binders in samples of painted artworks has been developed. Furthermore, a new analytical procedure for analysis of polysaccharide materials through identification of the monosaccharide constituents is proposed. The methods have been applied to characterizing binding media of the different layers of the polychrome surface in the multi-material sculptures from the sanctuary of Santa Maria delle Grazie in Mantova, Italy. It was found that animal glue was the main binder in the priming layer of all statues, whereas more complex mixtures were used in the paint layers. Generally, a drying oil was present, most often linseed oil alone or in combination with other organic binders.