As of now, the environmental issue is very topical and there is also an underutilization of different biological material where these can be used in ways that are typically not thought of. One way to increase the degree of utilization is to convert various biomasses such as natural rubber, olive pits, wood chips, and reed pellets into biochar. These biochars can then be added to materials, such as polymers, to improve their reaction-to-fire properties with a low impact on the environment. The process to convert biomasses into biochars, takes place through so-called pyrolysis, i.e., heating under high temperatures and low oxygen concentrations. During pyrolysis, the volatile substances in the biomasses are released and a material is left behind where the compounds that can sustain fire are minimal and a carbon skeleton consisting of strong C-C covalent bonds is prevalent. This biochar then has significantly different material properties compared to its corresponding biomass, where one of the differences is its improved reaction-to-fire properties. This study aims to investigate whether it is possible to determine the final reaction-to-fire properties of different biochars based on the corresponding biomass and its chemical composition. The basis of this study consists of a literature review, laboratory experiments and an analysis. The literature review has been carried out to find the chemical composition of the various biomasses, the laboratory experiments has been carried out to obtain the reaction-to-fire properties of said biomasses and biochars, and the analysis to determine the possibility of predicting the final reaction-to-fire properties of various biochars. The results obtained in this study are that despite the unfavorable reaction-to-fire properties of natural rubber, biochar made from natural rubber had the most desirable reaction-to-fire properties (i.e., fire safe). Of the seven parameters assessed for its reaction-to-fire properties, natural rubber performed worst in five of these compared to the remaining biomasses. However, after conversion to biochar, rubber had the best parameters in three out of five cases where the two additional parameters could not be assessed as these are based on the specimen igniting, which they did not. The parameters in which biochar made from natural rubber obtained the best results were peak heat release rate (PHRR), total heat released per unit area (THRPUA), and maximum average rate of heat emission (MARHE). However, biochar made from natural rubber also obtained the worst results in terms of time to peak heat release rate (TTPHRR) and fire growth rate (FIGRA), where FIGRA is inversely proportional to TTPHRR. Although the lignocellulosic biomasses showed difference in their chemical composition, no major difference in PHRR, THRPUA, and MARHE could be detected between them when their corresponding biochars were tested in the cone calorimeter. The conclusions that can be drawn from this study are that it is possible to predict the final reaction-to-fire properties of the lignocellulosic biochars since they react almost equally when exposed to fire. However, more tests and studies are required to be able to predict the final reaction-to-fire properties of the non-lignocellulosic biochars. This is to understand the chemical compounds and bonds that are formed during pyrolysis, as well as how these affect the biochar’s reaction-to-fire properties.

In recent years, interest in sustainability and being environmentally friendly has increased. Wood is a durable and renewable building material, which is becoming more common in the constructions industry. In 2002, the government in Sweden adopted a national strategy to promote an increased use of wood in buildings. However, the usage of wood in construction has a potential risk – wood is ignitable and has fire-spreading properties.  The aim of this project was to investigate whether a ZnO coating can reduce the risk of ignition on wooden surfaces exposed to a radiative heat source, focusing on the time to ignition of the wood. ZnO possess a wide combination of physical properties, such as ability to reflect infrared radiation and being thermally stable at extremely high temperatures. The study has been carried out through a literature review and laboratory experiments. In the laboratory experiments, a cone calorimeter was used and the tests were performed according to ISO 5660-1. In the cone calorimeter, two different amounts of ZnO applied to the wood surface were tested, 0.5 and 1 g ZnO per dm2 and an untreated piece of wood as a reference. The test was carried out in three different heat fluxes: 20, 35 and 50 kWm-2. After completed tests, the change in the wood’s morphology was examined in a scanning electron microscopy (SEM). The result shows that an application of ZnO on a wooden surface significantly increases the time to ignition for the wood. An application of 0.5 g ZnO per dm2increased the time to ignition by 26-33 % for the three different heat fluxes. On the other hand, 1 g of ZnO per dm2 created an increase of 37-40 %. The trend of the increase of time to ignition was similar for all heat fluxes. The result showed no clear tendency that the smoke production rate was reduced with the application of ZnO. The heat release rate was not affected by the addition of ZnO, which was expected because ZnO delays the time to ignition, but once it catches fire, the wood burns. The SEM images before and after combustion showed that there is no change in the morphology of ZnO, although some ZnO has agglomerated but remains intact after combustion. The conclusion of this study is that ZnO has the potential to protect wood from fireby increasing the time to ignition. But when the wood has ignited, there is no clear tendency for ZnO to affect the growth of the fire. The study has shown that in the future ZnO could be applied to a wooden surface to reduce the risk of fire ignition. Further studies are required to find effective methods to implement the usage of ZnO, as applying ZnO on vertical wooden surfaces.

Les matériaux composites à matrice polymère sont couramment utilisés dans des structures dont la durée de vie peut dépasser la dizaine d’années. En conditions de service, ils peuvent être soumis à des sollicitations thermiques, mécaniques et hydriques, couplées ou non, et subissent également un vieillissement, c’est-à-dire une évolution de leur structure induisant une modification, et souvent une dégradation de leurs performances via divers mécanismes. Ceci est particulièrement vrai pour les propriétés ignifuges et thermomécaniques. Si de nombreuses études traitent de l’impact du vieillissement sur les propriétés mécaniques, peu de travaux mettent en évidence une perte partielle ou totale de résistance au feu de matériaux ignifugés après vieillissement. Par ailleurs, une tendance forte aujourd’hui est le développement de matériaux composites renforcés par des fibres naturelles, susceptibles de remplacer les fibres de verre. Cependant, les fibres naturelles sont sujettes à dégradation en conditions hygrothermiques ou hydrothermiques. De même, les systèmes retardateurs de flamme les plus étudiés aujourd’hui, à base de phosphore, sont sensibles à ce type de vieillissement.Ces travaux de thèses rapportent l’évolution du comportement au feu et thermomécanique d’un composite à matrice époxy renforcé par des fibres de lin et contenant un retardateur de flamme phosphoré face à divers scénarios de vieillissement. Afin de comprendre l’influence des paramètres de vieillissement, des environnements hygrothermiques à 70°C et humidité relative variable mais également hydrothermique ont été imposés aux composites ignifugés avec deux retardateurs de flammes phosphorés différents. L’influence de la température, ainsi que celle d’un séchage, ont également été étudiées. L’évolution des propriétés du biocomposite ignifugé, que ce soit les propriétés mécaniques ou la réaction au feu, a été mise en relation avec la quantité d’eau absorbée par celui-ci lors du vieillissement. Enfin, puisque les composites étudiés peuvent être utilisés pour des applications exigeant un maintien des performances mécaniques en cas d’incendie, ces travaux de thèse ont porté également sur l’évolution des propriétés mécaniques des différents matériaux étudiés vieillis hydrothermiquement après une exposition à un flux de chaleur correspondant à un début d’incendie. / Polymeric materials, especially composites are used for long term applications. When used, those materials can be subjected, for example, to thermic, mechanical or hydric stresses but can also age. Indeed, with time, there will be an evolution of their structure leading, in most cases, to an alteration of their properties via several mechanisms. This is all the more true for their mechanical and fire performances. If many studies analyze the influence of ageing on the mechanical properties of a composite, few highlight a partial or total drop of fire performances of a fire-retarded composite. Moreover, the substitution of glass fibers by natural fibers is a trend in constant evolution but those natural fibers can be easily degraded during a hygrothermal or hydrothermal ageing. Similarly, flame retardant containing phosphorous are more and more studied while being sensitive to those types of ageing.This thesis reports the evolution of a thermoset composite (epoxy matrix) reinforced with natural fibers (UD flax fibers) and containing a phosphorous flame retardant through various ageing scenarios and the impact of ageing on their mechanical properties and their fire performances. In order to understand the influence of the various ageing parameters, hygrothermal and hydrothermal ageings were carried out on flame-retarded composites with two different phosphorous flame retardants. This allowed us to connect the alteration of properties and the amount of water absorbed during ageing. Finally, since sometimes the studied composites must maintain their mechanical properties even exposed to a fire, this thesis also reports the impact of a short exposition to a heat flux similar to small fire on the various studied composites that have been previously subjected to a hydrothermal ageing.

Thermal insulation materials made from natural fibrous materials, such as cellulose fibers, have advantages over others from a sustainability point of view. However, cellulosic materials are generally prone to mold and absorb moisture, and these have negative effects on the insulation properties, the durability of insulation materials, and interior air quality. In this thesis, cellulose-fiber-based insulation foams were prepared from bleached chemithermomechanical softwood pulp, and these foams showed promising thermal insulation properties and fungal resistance. Hydrophobic extractives were isolated from birch (Betula verrucosa) outer bark and used to improve the water resistance of the foams, which were impregnated in solutions of extractives and then dried. The modified foams showed greater water resistance, and the modification had no negative effects on the thermal insulation, fungal resistance, and compressive strength of the foams. Another potential problem with low density cellulosic thermal insulation materials is their poor reaction-to-fire properties. Cellulose-fiber-based insulation foams were prepared from formulations containing bleached chemithermomechanical softwood pulp and commercial fire retardants to improve the reaction of the foams to fire. Single-flame source test results showed that the foams containing 20% expandable graphite (20% EG) or 25% synergetic (25% SY) fire retardant had significantly improved reaction-to-fire properties and passed class E, which reflected that they can resist a small flame attack without substantial flame spreading for a short period according to EN 13501-1. Compared with the reference without any fire retardant, the peak heat release rate (Peak-HRR) of the 20% EG and 25% SY decreased by 62% and 39% respectively when the samples were subjected to a radiance heat flow of 25 kW m-2 in a Cone Calorimeter. The thesis demonstrates that it is possible to produce cellulose-fiber-based insulation materials with improved properties in terms of fungal, improved water resistance and reaction-to-fire properties. / <p>QC 20170428</p> / Energy-efficient cellulosic insulation products/panels for green building solutions

This work is focuses on the modification of organic fiber insulating materials in terms of their reaction to fire after installation into the construction. The target is to find a way to improve the reaction to fire and to at least reach the reaction to fire D.

Tesis por compendio / [ES] El principal objetivo de la presente tesis doctoral se ha centrado en la obtención, desarrollo y optimización de formulaciones de poliamida de origen renovable con aditivos que mejoren las propiedades mecánicas, morfológicas, térmicas, termomecánicas y de comportamiento frente al fuego. En una primera fase se ha trabajado con mezclas de poliamida con un origen parcial biológico obtenido de la reacción del ácido dicarboxílico del aceite de ricino con la 1,6-hexametilendiamina (HMDA) derivada del petróleo mediante policondensación. De esta manera se obtiene una BioPA 610 con un contenido bio entre el 60-63% en peso. Esta PA610 se combinó con nanotubos de Halloysita (HNTs) en diferentes cargas para evaluar su efecto en la matriz y sus propiedades. Se obtuvo un gran aumento de rigidez con la incorporación de carga en la matriz polimérica además de un ligero aumento de la dureza. Las propiedades morfológicas muestran una buena dispersión de los nanotubos en el material. En cuanto a las propiedades térmicas los HTNs no suponen una gran variación de las características con respecto al polímero base. Los resultados termomecánicos muestran un gran aumento en el módulo de almacenamiento. Por otro lado, se estudiaron las propiedades de comportamiento frente al fuego de las mezclas de PA610 y HNTs mediante las técnicas del cono calorimétrico, índice límite de oxígeno (LOI), opacidad y toxicidad de los gases producidos, poder calorífico de combustión y ensayo UL-94. De los resultados obtenidos se aprecia una buena reducción del calor liberado con el aumento de carga de HNTs, una ligera disminución en el valor del LOI. En cuanto a la opacidad del humo desprendido, la presencia de HNTs no afecta demasiado en la liberación del humo, pero sí se obtiene una buena reducción del CO2 desprendido durante la combustión del material. El poder calorífico muestra una disminución de hasta 10 MJ/Kg con respecto a la PA610 sin aditivo. Por último, el ensayo de UL-94 no supone variación de resultados en las diferentes muestras analizadas. En una última fase se trabajó con grafito expandido (EGr) combinado dentro de la matriz polimérica de poliamida 1010 de origen biológico obtenida 100% de fuentes renovables. En esta fase se incorporaron cargas de EGr entre 2,5% y 10% en peso. Se estudiaron propiedades mecánicas, térmicas y termomecánicas, así como el análisis del color, morfología, hidrofobia, captación de agua y su comportamiento frente al fuego. Mecánicamente se apreció una gran mejora en la rigidez del material. En las propiedades térmicas se mejoró el grado de cristalinidad del material. El análisis termomecánico mostró un aumento en el módulo (E) y en el módulo de almacenamiento (E'). El estudio de la hidrofobia y la captación de agua dio como resultado una reducción en la absorción de agua y un aumento de la hidrofobicidad del material. Por último, en cuanto a las propiedades del material frente al fuego, se consiguió reducir en gran medida la liberación de calor emitido. El valor del índice límite de oxígeno se reduce ligeramente y el ensayo de la UL-94 muestra una mejora de V-2 a V-1 en la clasificación del compuesto con la incorporación de EGr frente al polímero sin aditivar. / [CA] El principal objectiu de la present tesi doctoral s'ha centrat en l'obtenció, el desenvolupament i l'optimització de formulacions de poliamida d'origen renovable amb additius que millorin les propietats mecàniques, morfològiques, tèrmiques, termomecàniques i de comportament davant del foc. En una primera fase s'ha treballat amb barreges de poliamida amb un origen parcial biològic obtingut de la reacció de l'àcid dicarboxílic de l'oli de ricí amb la 1,6-hexametilendiamina (HMDA) derivada del petroli mitjançant policondensació. D¿aquesta manera s'obté una BioPA 610 amb un contingut bio entre el 60-63% en pes. Aquesta PA610 es va combinar amb nanotubs de Halloysita (HNTs) en diferents càrregues per avaluar el seu efecte a la matriu i les seues propietats. Es va obtenir un gran augment de rigidesa amb la incorporació de càrrega a la matriu polimèrica a més d'un lleuger augment de la duresa. Les propietats morfològiques mostren una bona dispersió dels nanotubs al material. Quant a les propietats tèrmiques, els HTNs no suposen una gran variació de les característiques respecte al polímer base. Els resultats termomecànics mostren un gran augment en el mòdul d'emmagatzematge. D'altra banda, es van estudiar les propietats de comportament davant del foc de les barreges de PA610 i HNTs mitjançant les tècniques del con calorimètric, índex límit d'oxigen (LOI), opacitat i toxicitat dels gasos produïts, poder calorífic de combustió i assaig UL-94. Dels resultats obtinguts s'aprecia una bona reducció de la calor alliberada amb l'augment de càrrega de HNTs, una lleugera disminució al valor del LOI. Quant a l'opacitat del fum desprès, la presència de HNTs no afecta gaire en l'alliberament del fum, però sí que s'obté una bona reducció del CO2 desprès durant la combustió del material. El poder calorífic mostra una disminució de fins a 10 MJ/Kg respecte de la PA610 sense additiu. Finalment, l'assaig d'UL-94 no suposa variació de resultats a les diferents mostres analitzades. En una darrera fase es va treballar amb grafit expandit (EGr) combinat dins de la matriu polimèrica de poliamida 1010 d'origen biològic obtinguda 100% de fonts renovables. En aquesta fase es van incorporar càrregues d'EGr entre el 2,5% i el 10% en pes. Es van estudiar propietats mecàniques, tèrmiques i termomecàniques, així com l'anàlisi del color, la morfologia, la hidrofòbia, la captació d'aigua i el seu comportament davant del foc. Mecànicament es va apreciar una gran millora en la rigidesa del material. A les propietats tèrmiques es va millorar el grau de cristal·linitat del material. L'anàlisi termomecànica va mostrar un augment al mòdul (E) i al mòdul d'emmagatzematge (E'). L'estudi de la hidrofòbia i la captació d'aigua va donar com a resultat una reducció de l'absorció d'aigua i un augment de la hidrofobicitat del material. Finalment, quant a les propietats del material davant del foc, es va aconseguir reduir en gran mesura l'alliberament de calor emesa. El valor de l'índex límit d'oxigen es redueix lleugerament i l'assaig de la UL-94 mostra una millora de V-2 a V-1 a la classificació del compost amb la incorporació d'EGr davant del polímer sense additivar. / [EN] The main objective of this doctoral thesis has focused on obtaining, developing and optimizing polyamide formulations of renewable origin with additives that improve the mechanical, morphological, thermal, thermomechanical and fire behavior properties. In a first phase, has been carried out an experimental with polyamide mixtures with a partial biological origin obtained from the reaction of the dicarboxylic acid of castor oil with 1,6-hexamethylenediamine (HMDA) derived from petroleum by means of polycondensation. In this way, a BioPA 610 with a bio content between 60-63% by weight is obtained. This PA610 was combined with Halloysite nanotubes (HNTs) at different loadings to evaluate its effect on the matrix and its properties. A large increase in stiffness was obtained with the incorporation of filler in the polymeric matrix in addition to a slight increase in hardness. The morphological properties show a good dispersion of the nanotubes in the material. Regarding the thermal properties, the HTNs do not imply a great variation of the characteristics with respect to the base polymer. The thermomechanical results show a large increase in the storage modulus. On the other hand, the fire behavior properties of the mixtures of PA610 and HNTs were studied using the calorimetric cone techniques, limit oxygen index (LOI), opacity and toxicity of the gases produced, calorific value of combustion and UL-94 test. From the results obtained, a good reduction of the heat released with the increase in the load of HNTs, a slight decrease in the value of the LOI, can be seen. Regarding the opacity of the smoke released, the presence of HNTs does not affect the release of smoke too much, but a good reduction of the CO2 released during the combustion of the material is obtained. The calorific power shows a decrease of up to 10 MJ/Kg with respect to PA610 without additive. Lastly, the UL-94 test does not assume any variation in results in the different samples analysed. In a final phase, expanded graphite (EGr) combined within the polyamide 1010 polymeric matrix of biological origin obtained 100% from renewable sources was worked on. In this phase, EGr loads between 2.5% and 10% by weight were incorporated. Mechanical, thermal and thermomechanical properties were studied, as well as the analysis of color, morphology, hydrophobicity, water uptake and its behavior against fire. Mechanically, a great improvement in the rigidity of the material was appreciated. In the thermal properties, the degree of crystallinity of the material was improved. The thermomechanical analysis showed an increase in the modulus (E) and in the storage modulus (E'). The study of hydrophobicity and water uptake resulted in a reduction in water absorption and an increase in the hydrophobicity of the material. Finally, regarding the properties of the material against fire, it was possible to greatly reduce the release of emitted heat. The value of the oxygen limit index is slightly reduced and the UL-94 test shows an improvement from V-2 to V-1 in the classification of the compound with the incorporation of EGr compared to the polymer without additives. / This research was funded by the Ministry of Science, Innovation, and Universities (MICIU) project numbers MAT2017-84909-C2-2-R and AGL2015- 63855-C2-1-R. Project funded with grant number PID2020-116496RB-C22 funded by the Ministry of Science and Innovation MCIN/AEI/10.13039/501100011033 and grant number AICO/2021/025 funded by Generalitat Valenciana. AITEX wants to thank CDTI (Centro para el Desarrollo Tecnológico Industrial) within the framework of grants for Technological Centres of Excellence “Cervera” (CER- 20211013). The author would like to thank the INTERREG SUDOE NABITEX project (SOE2/P1/P0524) for allowing him to participate in it as part of his training. / Marset Gimeno, D. (2022). Desarrollo y optimización de formulaciones de poliamida de origen renovable con comportamiento ignífugo [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/185134 / Compendio

This diploma thesis is focused on a suitable midification of acoustic and thermal insulation materials from recycled textile fibres of lower quality due to improvement of their reaction to fire. The aim is to find an effective flame retardant and to verify suitable method of flame retardant application onto this type of insulation material.

The thesis discusses possibilities of use new thermal insulation materials based on natural renewable resources (primary technical hemp) in development of the new thermal insulation materials. The main task (in the work) is to find modifications of the thermal insulation mats based on natural fibres by chemicals substances to improve the moisture properties, thermal properties and fire resistance.