Degradable Elastomers: Is There a Future in Tyre Compound Formulation?

Problems related to non-biodegradable waste coming from vulcanized rubber represent one of the pre-eminent challenges for modern society. End-of-life tyres are an important source of this typology of waste and the increasingly high accumulation in the environment has contributed over the years to enhance land and water pollution. Moreover, the release into the environment of non-degradable micro-plastics and other chemicals as an effect of tyre abrasion is not negligible. Many solutions are currently applied to reuse end-of-life tyres as a raw material resource, such as pyrolysis, thermo-mechanical or chemical de-vulcanisation, and finally crumbing trough different technologies. An interesting approach to reduce the environmental impact of vulcanised rubber wastes is represented by the use of degradable thermoplastic elastomers (TPEs) in tyre compounds. In this thematic review, after a reviewing fossil fuel-based TPEs, an overview of the promising use of degradable TPEs in compound formulation for the tyre industry is presented. Specifically, after describing the properties of degradable elastomers that are favourable for tyres application in comparison to used ones, the real scenario and future perspectives related to the use of degradable polymers for new tyre compounds will be realized.     

Structural Effects on the Decomposition Kinetics of EPDM Elastomers by High-Resolution TGA and Modulated TGA

Effects of ethylene content and maleated EPDM content on the thermal stability and degradation kinetics of ethylene propylene diene monomer (EPDM) have been studied using high resolution thermogravimetric analysis (Hi-Res TGA) and Modulated TGA (MTGA). Modulated TGA shows that EPDM degradation is complex, with activation energy of degradation increasing throughout the degradation. Values from both dynamic and constant heating rate experiments are in good agreement with each other and with the literature value. However, the dynamic heating rate experiment shows that if the difference of peak temperature of components in a system is less than 5°C, Hi-Res TGA does not resolve them.This revised version was published online in November 2005 with corrections to the Cover Date.     

Characterisation of polymer masterbatches by modern thermal methods of analysis

Thermoplastic masterbatches are a complex blend of the base thermoplastic resin, a pigment and a range of additive materials. End use applications of masterbatches include agricultural film, packaging film, injection moulding of small and large bottles, boxes and crates and extrusion of pipe and sheet. Thermal analysis is a very useful tool for the characterisation of the physical properties of both masterbatches and finished product. This report will show the use of differential scanning calorimetry (DSC) to identify the melt profiles of masterbatches and to determine oxidative stability. Thermogravimetric analysis (TG) is very useful for the determination of the composition of masterbatches, for the study of batch to batch variability and for a comparison of a material with competitive products. The use of High Resolution TGA (Hi-Res TGA) will be shown to give greater resolution between overlapping weight loss steps leading to better quantification of components within the masterbatch when compared to conventional TG.     

Pyrolysis of waste tyres: The influence of USY catalyst/tyre ratio on products

In this paper, an ultrastable Y-type (USY) zeolite was investigated with two-staged pyrolysis–catalysis of waste tyres. Waste tyres were pyrolysed in a fixed bed reactor and the evolved pyrolysis gases were passed through a secondary catalytic reactor. The main objective of this paper was to obtain high concentration of certain aromatic hydrocarbons suitable to be used as a chemical feedstock rather than a liquid fuel, and the influence of catalyst/tyre ratio on the product yield and composition of derived oils. The light fraction (boiling point < 220 °C) was distilled from the derived oil prior to be analyzed with gas chromatography/mass spectrometry (GC/MS). It showed that the increase of catalyst/tyre ratio resulted in high yield of gas at the expense of the oil yield. The high catalyst/tyre ratio favored to increase the concentration of light fraction (<220 °C) in oil. Increasing the catalyst/tyre ratio resulted in significant changed in the concentration of benzene, toluene, xylenes and the alkyl aromatic compounds. For benzene and toluene, the highest concentration was obtained at the catalyst/tyre ratio of 0.5. The concentration of xylenes increased with the increasing of catalyst/tyre ratio.     

Characterisation of ground tyre rubber by using combination of FT-IR numerical parameter and DTG analysis to determine the composition of ternary rubber blend

Three different batches of ground tyre rubber (GTR), obtained from end of life (EOL) tyres, in the form of powder, were subjected to quantitative analysis using simple non-pyrolytic Fourier Transform Infrared (FT-IR) spectroscopy and derivative thermogravimetric (DTG) analysis. Two batches were based on EOL truck tyres varying in particle size, and one batch was based on EOL passenger car tyres. The focus was to derive a general method for finding multiple polymer blend compositions in different types of GTR for future efficient recycling applications of EOL tyres. The secondary aim was to evaluate the validity of the methodology independent of particle size. IR studies detected the presence of NR, SBR and BR characterized by peaks at 1375, 699 and 738 cm⁻¹, respectively, in all the batches. Each of the blends was ternary, in which the ratio of two rubbers was exactly calculated by combined use of an existing infrared blend parameter (P_IR) and the absorbance ratio of the characteristic peaks of the two rubbers in a baseline corrected IR spectrum. Then, using this calculated ratio on the results obtained from DTG, all three rubbers were quantified.     

Conversion of Waste Tyres into Carbon Black and their Utilization as Adsorbent

Pyrolysis has the potential of transforming used tyres into useful recyclable products. Pyrolytic carbon black is one of the most important products of tyre pyrolysis. Waste tyres were pyrolysed at 450 °C in a batch reactor under atmospheric pressure. The recovered pyrolytic carbon black residues were studied to investigate their characteristics for use as a possible adsorbent. EDX elemental analysis and surface area determinations were used to investigate the distinctive features of pyrolytic carbon black. Due to various inorganic additives of the original tyre that contaminated the carbon black obtained, it was treated with acid for demineralization. The demineralized carbon black was activated at 900 °C in a furnace. It was observed that acid treatment and activation increased the surface areas and decreased the concentration of contaminants. Furthermore, adsorption characteristics of methylene blue on acid‐treated and activated carbon black (prepared via acid treatment) were compared with those of commercial activated carbon in liquid phase adsorption. It was found that adsorption capacity of methylene blue on acid‐treated activated carbon black was greater.     

Thermal and kinetic study of tyre waste pyrolysis via TG-FTIR-MS analysis

The world production of tyre waste amounts to 5·10⁶ ton year^–1, 2·10⁶ tons of which are produced in Europe, but the final destination of nearly 65–70% of them is the landfill, despite the high added value materials lost and the consequent environmental impact. Treatments alternative to landfilling take into account reconstruction and reuse of the tyres or the matter and/or energy recovery by means of thermal treatment processes (incineration, gasification and pyrolysis). Among these, pyrolysis seems to be a promising and realistic alternative to attain the conversion of tyre waste into valuable and reusable products. Present work relates to experimental tests and results obtained for the study of tyre waste pyrolysis, conducted by means of thermo-gravimetric analysis (TG) of the material and the simultaneous determination, through Fourier transform infrared (FTIR) and mass spectrometry (MS), of the decomposition products. The analysis of the volatile fraction allows to isolate, within the thermograms, the evolution of products referable to specific tyre components and therefore it suggests the application of a multi-component decomposition model. The kinetic model consequently developed agrees fairly well with the experimental data.     

Near-infrared transmittance spectroscopy for radiochemical ageing of EPDM

The feasibility of using near-infrared spectroscopy as a sensitive technique to follow the influence of gamma-irradiation upon ageing of different EPDM (ethylene propylene diene monomer) elastomers has been evaluated. Although identification is difficult, differences can be observed between the non-irradiated and irradiated materials for total integrated doses from 50 to 450 kGy using a dose rate of 1 kGy h(-1) under an oxygen flow. The decrease in intensity of bands at 7040, 4610 and 4910 cm(-1) are linked to the disappearance of additives present in the elastomer such as excess of vulcanising or antioxidant agents and occur for the lowest irradiation dose. This disappearance is confirmed by TGA (thermogravimetric analysis). The increase in band intensities assigned to the formation of hydroxyl and carbonyl groups (5100, 4860 and 4670 cm(-1)) irradiation indicates an increase in oxidation with irradiation in the presence of oxygen. No bands linked to the presence of C=C from the diene have been detected, probably owing to the low concentration in the material and the weak intensity in near-infrared region. For strong irradiation doses (450 kGy), the three formulations studied show no difference in their NIR spectra, which is confirmed by the TGA of these irradiated materials. PCA performed at 5000-4600 cm(-1) or 7090-6980 cm(-1) shows efficient discrimination.     

Thermogravimetric analysis of the co-combustion of the blends with high ash coal and waste tyres

Incineration methods are becoming increasingly important from the view point of the need to minimize the environmental impact of waste tyre disposal. Combustion of waste tyre, one high ash coal and tyre-coal blends with 10, 30 and 50% waste tyre were investigated by means of thermogravimetric analysis (TGA) carried out at 20 K min⁻¹ in the temperature range from ambient temperature to 1273 K. And effects of the mixed proportion between coal and waste tyre on the combustion process, ignition and burnout characteristics were also studied. The results indicate that the combustion of waste tyre is controlled by the emission of volatile matter, the regions are more complex for waste tyre (three or more peaks) than for coal (one peak). Also as compared with the case of burning only high ash coal, the incorporation of waste tyre can improve the combustion characteristics of high ash coal, especially the ignition performance and the peak weight loss compared with the separate burning of waste tyre and coal. Moreover, comparisons of the TG-DTG profiles between experimental and calculational results, it is indicate that there is a comparatively important difference, the co-combustion characteristics is the coupling effect between waste tyre and coal. The data resulting also showed that the co-combustion of waste tyre and low quanlitied coal as fuel is feasible.     

Structural and mechanical studies on modified reused tyres composites

Reused tyres powder was used as reinforcement in HDPE-reused tyre composites. In order to improve the compatibility between both components, several pre-treatments performed over the rubber tyres were applied: sulphuric acid etching, use of a silane coupling agent and chlorination with trichloroisocyanuric acid (TCI). Mechanical properties of the resulting materials (e.g. tensile strength, Young’s Modulus, toughness and elongation at break) were studied and compared. Chemical modifications on the surface of reused tyres were monitored by FTIR and physical modifications and behaviour to fracture were followed by means of SEM. The influence of rubber pre-treatment was assessed by comparing the results of treated and untreated composites with those for neat HDPE. Reused tyre rubber, added to the HDPE in small quantities, acts as a filler, improving the stiffness and providing a more brittle behaviour. Pre-treatment with TCI gave poor results in terms of mechanical properties obtaining lower values than neat HDPE in some cases and always worst properties than sulphuric or silane coupling agent. Treatments with H₂SO₄ and silane coupling agent improve the ability of rubber to interact with the HDPE, increasing the material’s stiffness and its tensile strength. Sulphuric acid modificates chemical and physically the particles’ surface improving mainly mechanical adhesion, whereas silane acts as a compatibilizer developing chemical matrix-reinforcement interactions.     

Dehydration and crystallization process in sol-gel zirconia

Sol-gel zirconia was characterized using high-resolution thermogravimetry (Hi-Res TG) and differential scanning calorimetry (DSC) and compared with X-ray diffraction, Raman scattering, and UV-Vis spectroscopy. ZrO_2-x(OH)_2x·yH₂O annealed below 400°C show typical behavior of amorphous material. As the annealing temperature is increased, the tetragonal and monoclinic phases crystallize. Typical Hi-Res TG curve shows that the samples are continuously dehydrated in a long temperature range, between room temperature and 600°C. The total mass loss relative to the initial mass is of about 29%. The DSC analysis coupled with TG and structural information, indicate that the exothermic processes about 355 and 447°C can be related to the nucleation process of the formation of tetragonal zirconia, with bulk crystallization at 447°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

TGA and magnetization measurements for determination of composition and polymer conversion of magnetic hybrid particles

Magnetic hybrid colloidal particles can be characterized using various techniques and numerous tools leading generally to particles size, size distribution, and electrokinetic properties. However, the chemical composition of these hybrid particles can be estimated using thermal gravimetric analysis (TGA). More interestingly, the combination of this quantitative technique with the magnetization measurement leads not only to chemical composition but also to the overall polymerization conversion and more precisely to the polymerization conversion on the seed particles. In fact, the TGA performed on dried magnetic particles leads to exact organic/inorganic chemical composition. Regarding the magnetization, the amount of magnetic material can be deduced, and consequently, the amount of non‐magnetic material can be also estimated. Thus, TGA and magnetization measurements are considered as complementary techniques for characterization of magnetic hybrid colloidal particles. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro- and nanopatterned star poly(ethylene glycol) (PEG) materials prepared by UV-based imprint lithography

A UV-based imprint lithography method is used for the direct surface structuring of hydrogel-based biomaterials, which are prepared from a family of tailor-made star poly(ethylene glycol) formulations. Bulk star poly(ethylene glycol) (PEG) hydrogels are fabricated by cross-linking acrylate-functionalized star PEG macromolecules. Cross-linking is achieved by radical reactions initiated by UV irradiation. This UV-curable star PEG formulation allows templating of mold structures to yield a stable, stand-alone, elastomeric replica of the mold. In particular, when a secondary, soft mold is used that consists of a perfluorinated elastomer with inherent excellent release properties, nanometer-sized features (down to 100 nm) can be imprinted without specialized equipment. The applied UV-based imprint lithography is a fast and simple technique to employ for the direct topographic structuring of bulk PEG-based biomaterials. The UV-based imprinting into the star PEG prepolymer by means of a perfluorinated, soft mold can be carried out on the bench top, while nanoscale resolution is demonstrated.     

Effects of gamma and electron beam irradiation on the properties of calendered cord fabrics

The effects of gamma and e-beam irradiation on mechanical and structural properties of nylon 66 (Ny 66), nylon 6 (Ny 6) and poly(ethylene terephthalate) (PET) fabrics used in tyres were investigated. The untreated (greige), treated cords and calendered fabrics were irradiated at different doses. It is found that the effects of high energy irradiation on greige, treated cords and calendered fabrics are similar. No protective effect of compounds used in calendering was observed against radiation-induced oxidative degradation. The deterioration effect of gamma irradiation on mechanical properties is much higher than that of e-beam irradiation for all types of samples. Limiting viscosity numbers of both gamma and e-beam irradiated nylon 6 and nylon 66 cords were found to decrease with increasing dose. It is concluded that PET calendered fabric has higher resistance to ionizing radiation. Ny 6 and Ny 66 calendered fabrics are more sensitive even at low doses. Therefore, the effects of high energy irradiation on tyre cords have to be taken into consideration during tyre design reinforced with particularly Ny fabrics if pre-vulcanization with high energy radiation is to be applied.     

Optimisation of analytical procedures for the quantification of ionic and carbonaceous fractions in the atmospheric aerosol and applications to ambient samples

In the last decade, our research group set up and optimised analytical techniques for the characterisation of the major components of atmospheric aerosol (i.e. secondary inorganic ions and carbonaceous material) and source markers (e.g. levoglucosan, carbonates). In this study, we present a complete overview on the most problematic aspects that can be encountered during the quantification of the two main components of aerosol, i.e. the ionic and carbonaceous fractions. More in detail, different liquid chromatographic approaches were set up for main ions and anhydrosugars determination. Quality assurance procedures (i.e. tests on data reliability) were applied during the set-up phase and they are presented in this work. As regards the carbonaceous component characterisation, two evolved gas analysis techniques were set up and applied: the thermogravimetric technique coupled to the Fourier transformed infrared spectroscopy (TGA/FTIR) and the thermal–optical transmittance method (TOT). A suitable protocol for organic and elemental carbon separation was set up for the TGA/FTIR system and a comparison with the results obtained by the TOT method was carried out. Studies on the impact of filter load, field blanks, and sample composition on OC/EC quantification by the TOT method were performed. Moreover, approaches for carbonate carbon quantification on different kinds of filters were developed. It was demonstrated that this approach allows to reach the ionic balance in samples impacted by carbonate compounds. The optimised methods have been applied for the analysis of thousands of PM filters allowing the obtainment of reliable results.     

Statistical sampling of carbon nanotube populations by thermogravimetric analysis

Carbon nanotubes are one of the most promising nanomaterials available with applications in electronics devices, sensing, batteries, composites and medicine. Strict control of the carbon nanotube chemistry and properties is necessary as the applications proceed into more specialized areas. Thermogravimetric analysis (TGA) is one analytical method currently utilized for the characterization of carbon nanotubes. Though TGA can provide quantitative measurements of the composition of a sample, many researchers do not ensure the variance of the sample is properly captured. This research demonstrates for four single-wall carbon nanotube (SWCNT) samples how to statistically evaluate the material with TGA to ensure that the variance within the material is represented. SEM results are used to help reach conclusions about purity of the material by providing a visual means for inspection. This data is used to select the SWCNT material with the lowest variability and highest quality, as evaluated by composition and reproducibility.     

ATR-FTIR-MIR Spectrometry and Pattern Recognition of Bioactive Volatiles in Oily versus Microencapsulated Food Supplements: Authenticity,Quality, and Stability

Fourier transform infrared spectroscopy on the middle infrared region (ATR-FTIR-MIR) proved to be a convenient and reliable technique to evaluate foods’ quality and authenticity. Plants’ essential oils are bioactive mixtures used as such or in different oily or microencapsulated formulations, beneficial to human health. Six essential oils (thyme, oregano, juniperus, tea tree, clove, and cinnamon) were introduced in three oily formulations (Biomicin, Biomicin Forte, and Biomicin urinary) and these formulations were microencapsulated on fructose and maltodextrin matrices. To study their stability, the microencapsulated powders were kept under light irradiation for 14 days at 25 °C or introduced in biopolymer capsules. All variants were analysed by ATR-FTIR-MIR, recording wavenumbers and peak intensities (3600–650 cm⁻¹). The data were processed by Unscrambler and Metaboanalyst software, with specific algorithms (PCA, PLSDA, heatmaps, and random forest analysis). The results demonstrated that ATR-FTIR-MIR can be successfully applied for fingerprinting and finding essential oil biomarkers as well as to recognize this pattern in final microencapsulated food supplements. This study offers an improved ATR-FTIR-MIR procedure coupled with an adequate chemometric analysis and accurate data interpretation, to be applied for the evaluation of authenticity, quality, traceability, and stability during storage of essential oils incorporated in different matrices.     

High resolution thermogravimetry

A new thermogravimetric instrument is introduced, Hi-Res^TM TGA 2950. The Hi-Res^TM TQA gives a significant improvement to TG results. The instrument control parameters are varied as a function of the sample's rate of weight change. This novel feature improves resolution and reduces analysis time. The maximum heating rate and resolution index are user selectable.Data presented demonstrate improved resolution for survey TG thermal curves and very high resolution for difficult to resolve complex materials. Results are demonstrated for many types of samples including: homopolymers, polymer blends, inorganic reference materials, and complex organic mixtures.Hi-Res trademark and patent applied for by TA Instruments, Inc.

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Zusammenfassung Es wird das neue thermogravimetrische Gerät Hi-Res^TMTGA2950 vorgestellt. Mit Hilfe von Hi-Res^TMTGA2950 ergibt sich eine eindeutige Verbesserung der TG-Resultate. Die Kontrollparameter des Gerätes werden als eine Funktion der Massenänderungsgeschwindigkeit der Probe geändert. Diese neue Eigenschaft verbessert die Auflösung und verringert die Analysenzeit. Maximale Aufheizgeschwindigkeit und Auflösungsindex können vom Anwender bestimmt werden.Die dargelegten Daten zeigen eine verbesserte Auflösung der TG-Kurven und eine sehr hohe Auflösung für schwer aufzulösende komplexe Substanzen. Es werden Ergebnisse für zahlreiche Beispiele gegeben: Homopolymere, Polymergemische, anorganische Referenzsubstanzen und komplexe organische Gemische.Das Warenzeichen Hi-Res und das Patent wurde von TA Instruments,Inc. beantragt.

     

Characterisation of organoclays and adsorption of p-nitrophenol: environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.     

Shotgun proteomic analytical approach for studying proteins adsorbed onto liposome surface

The knowledge about the interaction between plasma proteins and nanocarriers employed for in vivo delivery is fundamental to understand their biodistribution. Protein adsorption onto nanoparticle surface (protein corona) is strongly affected by vector surface characteristics. In general, the primary interaction is thought to be electrostatic, thus surface charge of carrier is supposed to play a central role in protein adsorption. Because protein corona composition can be critical in modifying the interactive surface that is recognized by cells, characterizing its formation onto lipid particles may serve as a fundamental predictive model for the in vivo efficiency of a lipidic vector. In the present work, protein coronas adsorbed onto three differently charged cationic liposome formulations were compared by a shotgun proteomic approach based on nano-liquid chromatography–high-resolution mass spectrometry. About 130 proteins were identified in each corona, with only small differences between the different cationic liposome formulations. However, this study could be useful for the future controlled design of colloidal drug carriers and possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins into body fluids.