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[ES] Agregados fluorescentes de poli(tereftalato de ciclohexilendimetileno), procedimiento de obtención y uso como etiqueta físicamente no clonable para identificar y/o trazar envases para productos cosméticos y/o perfumes. La presente invención se refiere a unos agregados esféricos del poliéster termoplástico semicristalino poli(tereftalato de ciclohexilendimetileno) con una distribución de tamaños de entre 160 nm y 200 nm que emiten fluorescencia en el espectro del visible y que se encuentran depositados sobre un sustrato de poliéster aromático termoplástico o una poliolefina termoplástica. La presente invención además se refiere al proceso de obtención de dichos agregados y al uso de dichos como etiqueta físicamente no clonable, para identificar y/o trazar envases para productos cosméticos y/o perfumes. Por tanto, la presente invención se podría encuadrar en el área de las antifalsificaciones de envases, particularmente en el área de las antifalsificaciones de envases para productos cosméticos y/o perfumes., [EN] Fluorescent aggregates of poly (terephthalate of cyclohexilendimethylene), procedure of obtaining and use as a physically non -clonable label to identify and/or draw containers for cosmetic products and/or perfumes. The present invention refers to spherical aggregates of the polyester polyester semicristaline polycryn thermoplastic or a thermoplastic polyolefin. The present invention also refers to the process of obtaining said aggregates and to the use of said as a physically non -clonable label, to identify and/or draw containers for cosmetic products and/or perfumes. Therefore, the present invention could be framed in the area of containers antifalsifications, particularly in the area of containers of containers for cosmetic products and/or perfumes.

Poly(hydroxyurethanes) (PHUs) have been suggested as isocyanate-free, low-toxicity alternatives to polyurethanes (PUs). However, PHUs present low mechanical properties due to the presence of side reactions that limit the production of high-molar mass polymers. Here, we present the synthesis under mild conditions and atmospheric pressure of bi-cyclic carbonate monomer for the production of PHU nanocomposites with good physical properties. The kinetics of the bi-cyclic carbonate synthesis and its complete conversion to urethane were followed by FTIR. The addition of functionalized boron nitrate (f-BN) with sucrose crystals improved the thermal degradation temperature as well as the glass transition by approximately 20 °C and 10 °C, respectively. The storage modulus of PHU films gradually increases with the concentration of f-BN in the composite.

The dichotomy between mechanical performance and repairability is a well-known fact in the self-healing field. One alternative to overcome this trade-off is the inclusion of reinforcing fillers. In this research, hybrid reinforced self-healing styrene-butadiene rubber (SBR) composites are developed by combining mechano-chemically modified ground tire rubber (mGTR) with carbon black (CB). The SBR matrix is systematically analyzed by means of dynamic mechanical analysis and broadband dielectric spectroscopy. The SBR composite reinforced with 20 phr mGTR and 20 phr CB maintains the healing efficiency of the unfilled SBR (80%) and improves its tensile strength by 300%, balancing perfectly well both properties. The healing efficiency is determined at different damage levels. The damage at the microscopic scale is easier to recover and does not depend on the presence of fillers, while the recovery at the macroscopic level clearly relies on the addition of filler, with more demanding healing conditions.

The circular economy requires that we know what a product is made of, that we can control that it is not a fake, and that we know how to recycle it. This requires a digital twin of each product where the information is stored and that we can access using a smartphone. The creation of digital twins requires a connection between the physical and digital worlds, which in turn requires that all objects have a unique identifier valid in both domains. The realization of the intrinsic potential of creating digital twins of individual products that link physical and digital identities in turn requires that the physical identifier is truly unique and that it cannot be copied. Furthermore, the physical identifier should not interfere with the product lifecycle, in particular recyclability, as this would be a potential blocker in a circular economy. Here, we present a physical identifier on the basis of a physical unclonable function (PUF) made from polymer nanoparticles and imbedded in a polymer laminate, where all components can be made from the same recyclable material. Such materials are commonly used for packaging in the fragrance and cosmetics industry. The development of the PUF system is presented, and each PUF was validated using a proprietary smartphone application with a QR code as a common pattern defining the PUF canvas. The functionality of the PUF was demonstrated across product types as diverse as lateral flow assays and construction materials. We conclude that polymer nanoparticle PUFs are a viable and directly recyclable solution to document authenticity and inform on recyclability of polymers in the circular economy.

[ES] La presente invención se refiere a la fabricación de materiales compuestos poliméricos reforzados con fibras (FRP) basados en matrices termoplásticas (FRTP), en estado líquido, que permiten almacenar los preimpregnados entre los 10-15 ºC sin que polimerice el material durante más de seis meses., [EN] The present invention relates to the manufacture of polymeric composite materials reinforced with fibers (FRP) based on thermoplastic matrices (FRTP), in a liquid state, which allow to store the prepreg between 10-15ºC without polymerizing the material for more than six months.

It is impossible to describe the recent progress of our society without considering the role of polymers; however, for a broad audience, “polymer” is usually related to environmental pollution. The poor disposal and management of polymeric waste has led to an important environmental crisis, and, within polymers, plastics have attracted bad press despite being easily reprocessable. Nonetheless, there is a group of polymeric materials that is particularly more complex to reprocess, rubbers. These macromolecules are formed by irreversible crosslinked networks that give them their characteristic elastic behavior, but at the same time avoid their reprocessing. Conferring them a self-healing capacity stands out as a decisive approach for overcoming this limitation. By this mean, rubbers would be able to repair or restore their damage automatically, autonomously, or by applying an external stimulus, increasing their lifetime, and making them compatible with the circular economy model. Spain is a reference country in the implementation of this strategy in rubbery materials, achieving successful self-healable elastomers with high healing efficiency and outstanding mechanical performance. This article presents an exhaustive summary of the developments reported in the previous 10 years, which demonstrates that this property is the last frontier in search of truly sustainable materials.

Los polímeros reforzados con fibra (FRP) se han posicionado como elementos estructura- les en sectores tan diversos como el transpor- te, la construcción, o el deportivo, entre otros. En este artículo se describen las pautas para desarrollar FRP autorreparables como una estrategia para aumentar su ciclo de vida. Se muestran las estrategias de autorreparación más comunes, así como las herramientas que se utilizan para evaluar y calcular la eficiencia de autorreparación. Por último, se muestra un ejemplo de un FRP autorreparable desa- rrollado en el grupo de investigación, a tra- vés de la incorporación de termoplásticos a un material compuesto de fibra de carbono y matriz epoxi., Fiber-reinforced polymers (FRP) have become the material of choice as structural elements in sectors as diverse as transport, construc- tion and sports, among others. This article outlines a current development to increase their life cycle: self-healing FRPs. The most common self-healing strategies are shown, as well as the tools used to evaluate and calcu- late healing efficiency. Finally, we present an example of a self-healing FRP developed in the research group, through the incorporation of thermoplastics into a carbon fiber and epo- xy matrix composite materia.

New bio-thermoplastic elastomer composites with self-healing capacities based on epoxidized natural rubber and polycaprolactone blends reinforced with alginates were developed. This group of salts act as natural reinforcing fillers, increasing the tensile strength of the unfilled rubber from 5.6 MPa to 11.5 MPa without affecting the elongation at break (~1000% strain). In addition, the presence of ionic interactions and hydrogen bonds between the components provides the material with a thermally assisted self-healing capacity, as it is able to restore its catastrophic damages and recover diverse mechanical properties up to ~100%. With the results of this research, an important and definitive step is planned toward the circularity of elastomeric materials.

Inspired by some of the mechanisms that occur in nature, self-healing materials are characterized by the ability to recover, partially or totally, their initial properties after suffering damage. These materials constitute an efficient alternative for extending the lifecycle of products, as well as for reducing the amount of waste generated. At the same time, they reduce maintenance and repair costs. In this work, examples of recent developments in the field of elastomeric composite materials are presented, studying different matrices, natural rubber (NR), epoxidized natural rubber (ENR), styrene-butadiene rubber (SBR) and nitrile rubber (NBR), and using diverse repair strategies, hydrogen bonds, disulfide exchange reactions, Diels-Alder chemistry and ionic interactions. The effect of adding carbon-derived reinforcing fillers (graphene oxide) and sustainable alternative fillers (ground tire rubber) is also analyzed. It is studied how the presence and type of filler influences the healing capacity of elastomeric matrices, reaching repair efficiencies of up to ~80%, without detriment to their mechanical performance.

The present study investigates the mechanical and tribological properties of an epoxy matrix filled with different graphitic particles deposited on an aluminum substrate by the electrostatic spray technique. Three different particles added to the epoxy matrix were the received graphite, the crushed graphite obtained by crushing the natural flake graphite particles using a ball mill, and graphite oxide obtained by oxidation treatment. Nanoindentation tests were conducted on the different coatings in order to evaluate the surface hardness and the contact elastic modulus. The effect of the oxidation treatment and the loading content on the tribological behavior of the above composites were also evaluated under dry-friction conditions. As expected, the smaller the particle size, the greater the reduction in the dynamic friction. The experimental findings showed that adding 5 wt % of crushed graphite (10 µm) provided a similar dynamic friction as the addition of 10 wt % of received graphite (20 µm). The epoxy filled with received graphite showed a lower wear rate than that filled with graphite oxide and crushed graphite. Moreover, both hardness and elastic modulus increased in the case of the epoxy filled with graphite oxide and crushed graphite.

To overcome the limitation of traditional photoluminescent materials, a cost-effective photoluminescence polymer was synthesized by a simple and one-step technique using benzyl alcohol as the starting material and aqueous sulfuric acid as the catalyst. The synthesized photoluminescent polymer showed photoluminescence properties independent of the excitation wavelength together with high thermal stability and excellent mechanical properties. The synthesized photoluminescent polymer was incorporated into different polymers viz. thermoplastic as well as thermoset polymers by melt and solution processes, respectively, to achieve photoluminescent polymer blends. The thermal, mechanical, and photoluminescent properties of the fabricated blends were improved or remained almost the same with the photoluminescence polymer contents, strongly proving that the photoluminescent polymer was well dispersed in the polymeric matrix. The potential applications of the photoluminescence polymer blends were investigated for 3D printing and a fluorescent ink. The study paves a way for the development of photoluminescent materials for various applications.

Los materiales compuestos poliméricos reforzados con fibra continua (FRP) se utilizan cada vez más como elementos estructurales en una gran variedad de sectores, como el transporte, energía, civil, marina, deporte, entre otros, gracias a sus excelentes propiedades mecánicas, alta resistencia y rigidez, buen comportamiento a fatiga, buena resistencia a la corrosión y bajo peso. Sin embargo, las demandas tecnológicas actuales exigen mejorar sus propiedades para ampliar su aplicación a condiciones más severas o extremas o aumentar su ciclo de vida. De este modo, en esta conferencia, se describen algunos de los avances realizados en el desarrollo de nuevos FRP con propiedades avanzadas. En concreto, en tres líneas de investigación: 1. Materiales compuestos jerárquicos, en los que se incorporan un refuerzo en dimensiones nanométricas, como nanotubos de carbono y grafeno para mejorar sus propiedades interlaminares, una de las principales debilidades de los FRP. Además, con la incorporación de estas nanopartículas de carbono se consigue dotar al FRP de multifuncionalidad como conductividad térmica o eléctrica. 2. Materiales compuestos con capacidad autorreparadora. Los FRP son vulnerables a accidentes de baja energía que generan fallos visibles sobre la superficie o interlaminares, que reducen la resistencia del material y terminan provocando su fallo. La tecnología actual requiere del desarrollo de FRP con capacidad autorreparadora, de manera que se pueda ampliar el tiempo de vida del material y abaratar los procesos de reparación del material. 3. Materiales compuestos sostenibles. Uno de los grandes problemas de los FRP es que no se pueden ni termoconformar ni reciclar por lo que al llegar al final de su vida útil terminan enterrados o almacenados en vertederos. Con objeto de cumplir con una economía 100% circular, es necesario desarrollar nuevos FRP sostenibles basados en resinas termoplásticas, en los que es posible recuperar los dos componentes mayoritarios, la fibra

Foam products are one of the largest markets for polyurethane (PU) and are heavily used in many sectors. However, current PU formulations use highly toxic and environmentally unfriendly production processes. Meanwhile, the increasing environmental concerns and regulations are intensifying the research into green and non-toxic products. In this study, we synthesized flexible polyurethane foam (PUF) using different weight percentages (0.025%, 0.05% and 0.1%) of a non-toxic bismuth catalyst. The bismuth-catalyzed foams presented a well evolved cellular structure with an open cell morphology. The properties of the bismuth-catalyzed flexible PUF, such as the mechanical, morphological, kinetic and thermal behaviors, were optimized and compared with a conventional tin-catalyzed PUF. The bismuth-catalyst revealed a higher isocyanate conversion efficiency than the stannous octoate catalyst. When comparing samples with similar densities, the bismuth-catalyzed foams present better mechanical behavior than the tin-catalyzed sample with similar thermal stability. The high solubility of bismuth triflate in water, together with its high Lewis acidity, have been shown to benefit the production of PU foams.

The influence of 0.5, 0.75, and 1 wt.% of graphene oxide (GrO) in nanocomposite coating on scratch behavior and tribological performance was analyzed. Graphite was oxidized using the Marcano and Tour method to obtain graphite oxide, which is thermally exfoliated at 700°C getting graphene oxide. The transformation of graphite to graphene oxide was evaluated via Raman spectroscopy and X-ray diffraction. Effects of graphene oxide content on the friction and wear behavior of polyester composite coatings were evaluated under dry sliding conditions. Experimental findings showed that the addition of 0.5 wt.% GrO was effective in reducing the friction coefficient of polyester coating. Meanwhile, under the same sliding conditions, the wear results revealed that the polyester coating filled with 1 wt.% GrO has better antiwear ability compared to those filled with 0.5 and 0.75 wt.% GrO. From the scratch analyses, we deduced that coating scratch behavior was highly affected by the amount of fillers inside the polyester matrix. In fact, the best friction characteristic and scratch resistance were observed in the case of polyester coatings filled with the lower amount of GrO, namely 0.5 wt.%.

[EN] The present invention relates to an electrochemically active nanoparticulate polymer material comprising methylcellulose, sulfonated lignin and polypyrrole with a hierarchical structure and method of obtaining thereof, for use as an electrochemical material dispersed in an aqueous medium. The present invention belongs to the field of sustainable electrochemical systems mainly for converting and storing energy from renewable sources and capturing and transporting CO2 gas from the combustion of fossil fuels in the industry sector, [FR] La présente invention concerne un matériau polymère nanoparticulaire électrochimiquement actif comprenant de la méthylcellulose, de la lignine sulfonée et du polypyrrole avec une structure hiérarchique et son procédé d'obtention, destiné à être utilisé en tant que matériau électrochimique dispersé dans un milieu aqueux. La présente invention concerne le domaine des systèmes électrochimiques durables principalement pour convertir et stocker de l'énergie provenant de sources renouvelables et capturer et transporter du CO2 gazeux issu de la combustion de combustibles fossiles dans le secteur de l'industrie

The combination of vulcanizing agents is an adequate strategy to develop multiple networks that consolidate the best of different systems. In this research, sulfur (S), and zinc oxide (ZnO) were combined as vulcanizing agents in a matrix of carboxylated nitrile rubber (XNBR). The resulting dual network improved the abrasion resistance of up to ~15% compared to a pure ionically crosslinked network, and up to ~115% compared to a pure sulfur-based covalent network. Addition-ally, the already good chemical resistance of XNBR in non-polar fluids, such as toluene and gasoline, was further improved with a reduction of up to ~26% of the solvent uptake. A comprehensive study of the molecular dynamics was performed by means of broadband dielectric spectroscopy (BDS) to complete the existing knowledge on dual networks in XNBR. Such analysis showed that the synergistic behavior that prevails over purely ionic vulcanization networks is related to the restricted motions of rubber chain segments, as well as of the trapped chains within the ionic clusters that converts the vulcanizate into a stiffer and less solvent-penetrable material, improving abrasion resistance and chemical resistance, respectively. This combined network strategy will enable the production of elastomeric materials with improved performance and properties on demand.

Herein, a study is presented, addressed to understand the influence of the terbium (III) species contained in a thermoplastic polyurethane (TPU) matrix. The studied terbium (III) species were terbium (III) nitrate, Tb(NO)·5HO, and a terbium (III) complex, [TbL (NO)](NO) (HO), where L is a macrocyclic ligand derived from 2,6-pyridinedicarboxyaldehyde and ethylenediamine. SEM-EDXS showed that in both films the terbium (III) species were homogeneously distributed in the polymer matrix. The film doped with the nitrate salt displayed different physical properties, in comparison to the pristine TPU and the film containing the terbium (III) complex. Both TPU/Tb films, exhibiting a green color emission, with a G/B ratio being temperature independent. By comparison of the emission of both films containing terbium (III) species, the TPU/Tb complex film presented a more intense luminescence due to the antenna effect. TPU doped with the nitrate salt showed weak emission, indicating the lack of sensitizing groups.

This work reports the synthesis of poly (monomethyl itaconate) grafted multi-layer graphene oxide (PMMI-g-GO) by atom transfer radical polymerization using activators regenerated by electron transfer (ARGET-ATRP). PMMI-g-GO presents outstanding properties, such as a high electrical conductivity (5.04 S m), low number of stacked graphene layers (6) and I/I ratio of 2.05 estimated from Raman spectrum, which indicates the high quality of PMMI-g-GO as a graphenic material. In addition, polymer brushes based on PMMI represent a new green alternative for the development of polymer composite materials, since the monomer used for their production is obtained from a renewable source. Interestingly, the PMMI-g-GO nanomaterial is also capable of storing Li ions without the need of using electron conductive additives that are usually employed in the electrode's composition of conventional lithium ion batteries.

A semicontinuous emulsion copolymerization via redox initiation (tetramethylenediamine with potassium persulfate) is used to show how, by variations in the comonomers feeding profile, substantial modifications can be obtained in the composition of the copolymer chains that are formed along the reaction, which in turn modifies in a significant manner the morphology and mechanical properties of the materials. That is, changing the comonomers feeding profile and building a histogram for the composition distribution of the synthesized copolymer chains, changes in mechanical properties can be explained along with changes in morphology. Styrene and n-butyl acrylate 50/50 w/w were used to prepare the copolymers. To study the effect of the aforementioned changes caused by the feeding profiles, three pairs of feeding profiles were considered; the “A profiles” were selected to promote different composition histograms, whereas the “B profiles” represent modified “A profiles”. Global conversion was determined by gravimetry and the global copolymer composition along conversion by H NMR. Stress–strain tests and dynamic-mechanical analysis were performed to evaluate their mechanical properties. An equivalent statistical copolymer was the reference material. Using redox initiation, the results show for a semicontinuous process, that a fast reaction at low temperature is very convenient. In addition, the interrelation analysis for feeding profiles-histogram-morphology-mechanical properties performance, allows for the first time, the understanding of copolymers mechanical performance as a whole, which can be used as a basis to ease their tailored design.