Literatura académica sobre el tema "Epoxy based intumescent"

Purpose. The purpose of this work is to study the thermal degradation of epoxy polymers and nanocomposites based on them in a fire retardant intumescent coating having a composition – ammonium polyphosphate / melamine / pentaerythritol. Methods. Thermogravimetric studies have been performed on the device “Thermoscan-2”, fire tests were performed by the method of “Bunsen burner”. Results. The influence of the structure of epoxy resin as a polymer component of the intumescent system on oxidative thermal destruction and fire retardant efficiency of reactive coating has been researched. The obtained results allow us to state that the best result has been demonstrated by Araldite GY 783 – epoxy resin of bisphenols A/F with a reactive solvent. The thermal properties of various epoxy resins and nanocomposites based on them with organomodified montmorillonite have been studied. It was found that montmorillonite in the nanocomposite increases the decomposition temperature of epoxy resin. Scientific novelty. It has been shown that the variation of the polymer component of the intumescent coating has little effect on the swelling rate, but the fire retardant efficiency of the intumescent composition containing epoxy resin of bisphenols A/F is higher than the same characteristic for the composition based on epoxy resin of bisphenol A. It has been established that the exclusion of pentaerythritol from the formulation of the epoxy intumescent system causes the formation of a more regular and durable char insulation layer. It has been proved that the use of additional, including nanostructured flame retardants, namely, modified montmorillonite, can increase the fire retardant efficiency of the coating. Practical significance. The obtained results are of practical importance for the development of new scientific approaches to the design of fire-fighting materials with improved performance characteristics through the use of polymers that provide the construction of a thermostable thermal insulation char layer. Through a series of systematic tests, it has been demonstrated that the use of nanoclay and nanocomposites based on epoxy resins allows to improve the formulations of intumescent coatings with high performance with the help of budget nanotechnologies.

The object of research is intumescent fire retardant coatings based on epoxy resins. The research is aimed at the development of mathematical models of the dependence of the swelling rate of intumescent fire retardant coatings on their composition. Considering the complexity of the processes during the formation of a protective carbon layer, it is advisable to select the optimal ratio of the components of an intumescent fire retardant coating experimentally, followed by the construction of mathematical dependences of the swelling ratio on the coating composition. Therefore, experimental studies aimed at developing and optimizing the composition of an intumescent fire retardant coating based on epoxy polymers are an important task. The studies were carried out in accordance with the theory of planning experiments with the construction of an orthogonal compositional plan of the second order. A linear swelling factor was chosen as the response function. Compositions based on the ED-20 epoxy oligomer, cured with polyethylene polyamine and filled with ammonium polyphosphate, aluminum hydroxide, and graphite additive were used for the study. Based on the results of processing the experimental results, a regression equation was obtained and response surfaces were constructed that describe the dependence of the linear swelling coefficient Cs of an intumescent composition based on an epoxy oligomer on the content of ammonium polyphosphate, aluminum hydroxide and graphite additive. A complex relationship is shown between the content of components and the linear swelling coefficient Cs with different ratios of the components. The optimum by the linear swelling coefficient (Cs=68.1) content of the components in the epoxy polymer was determined, amounting to 20 wt. including for ammonium polyphosphate, 15 mass parts including for aluminum hydroxide and 3 mass parts for the graphite additive. However, with such a ratio, the «self-extinguishing» condition is not met (Cs=27 %). Filling the composition with ammonium polyphosphate in an amount of 26.3 mass parts including, aluminum hydroxide 25 mass parts and 3.5 mass parts including graphite additives allows to get an intumescent fire retardant coating with a swelling ratio Cs over 63 and a reduced level of flammability (Ci=31 %)

Intumescent fire-retardant coatings based on epoxy resins, compared to traditional fire-retardant compositions, have improved performance properties – high strength, chemical and atmospheric resistance, adhesion to many materials. However, unmodified epoxy polymers are combustible and to obtain IFR based on them, flame retardants and mineral fillers are added to their composition. Intumescent systems for flame retardant coatings based on epoxy oligomers (non-halogen-containing) usually consist of ammonium or ammophos polyphosphate as an acidic agent and a wide range of fillers, both inert and gaseous, or which are an additional source of carbon. Each component of the fire-retardant intimate coating in different ways affects the processes of coke formation, which determines the requirements for their choice. Thus, the aim of this work is to conduct experimental studies of the dependence of the characteristics of the expanded coke layer on the composition of the intumescent epoxyamine composition. The results of experimental studies of the effect of ammonium polyphosphate and binary mixtures of ammonium polyphosphate (APP) with aluminum hydroxide (AH), sodium tetraborate decahydrate (STD), titanium oxide TiO2 (TO), pentaerythritol (P), aerosil (A) and expandable graphite are presented (EG) on the multiplicity of expanding and weight loss of epoxy compositions at study temperatures of 350, 400 and 450°C. Studies have shown that the production of intumescent flame retardant coatings based on epoxy oligomers is possible provided they are filled with ammonium polyphosphate in an amount of more than 20 mass parts. The most effective in terms of expanding are additives titanium oxide and aluminum hydroxide in an amount of 20 mass parts, which allows to obtain intumescent fire-retardant coatings with a linear coefficient of expanding 30-32 and 24-27, respectively, throughout the range of temperatures. The obtained data are useful in the development of fire-retardant coatings based on epoxy oligomers.

Intumescent coating is one of the useful methods to protect steel structures under fire conditions. In this study, the influence of single and hybrid two or three flame-retardant fillers among TiO2, Al(OH)3, and Mg(OH)2 on paints containing ammonium polyphosphate (APP), melamine (MEL), pentaerythritol (PER) based on the epoxy resin was investigated to improve the fire protection performance of the intumescent coatings. The performances of the intumescent coatings were determined by a fire test at 950oC for 1 hour. The coating degradation was characterized by Thermal gravimetric analysis (TGA). The morphology and composition of the char after the fire test were studied by Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), and energy dispersive X-ray spectra (EDS). The results revealed that Al(OH)3 or combination of Al(OH)3 and TiO2 are the effective solution to increase fire protective performances of the epoxy-based intumescent coatings.

Fire protective intumescent coating cannot insulate a base material effectively if its char lacks mechanical strength. This research therefore, studied the effects of fibre reinforcement to epoxy-based intumescent coatings char strength. The fibres used include glass wool fibre, Rockwool fibre and ceramic wool fibre of 10mm length. The three formulations mechanical performances were compared to both, a famous commercial intumescent coating and a control formulation without fibre. These coatings were fire tested up to 800°C in an electric furnace for an hour. Their chars mechanical properties were evaluated for char resistance test using predetermined weight loads. In the test, masses from 100g to 3600g were loaded continuously on top of the chars where the fibre reinforced intumescent coating (FRIC) has shown better strength and resistance to deformation. As a result, they produced lower percentage of height reduction i.e. 34% - 83% different when compared to unreinforced coating. Control char also ruptured at as low as 4N load. It was deduced that fire insulative wool fibres are effective reinforcement for improved char strength of the FRIC.

This study investigates the effectiveness of halloysite nanotube as filler on improvement in thermal performance of epoxy based intumescent fire retardant coating. Several intumescent fire retardant formulations were developed with and without halloysite nanotube. The thermal performance and char morphology of Intumescent fire retardant formulations was studied. Bunsen burner (ASTM E-119) test revealed that incorporation of HNTs (1.5 wt. %) improved flame retardancy by reducing the temperature of steel substrate up to 99 °C when exposed to fire for 1 hour. This study also revealed the physical and chemical mechanisms of action of HNTs in the intumescent systems. Results showed that halloysite improved the growth of the intumescent shield and give better quality of char. HNT formed aluminosilicate network for the phosphocarbonaceous structure by chemical contacts with ammonium polyphosphate. These new chemical species enhanced thermal stabilization of the char at high temperature and offered good structural properties on micro and macro scale. This increased the mechanical strength of the shielding layer during burning and also enhanced the residual weight percentage after thermal degradation as shown in thermal gravimetrical curves.

This article discusses one of the methods of fire protection, namely, the coating of metal structures with fire retardant paints. Intumescent coatings are currently the most widely used. Fire retardant coatings based on epoxy paints have high performance characteristics and are promising. As the foaming component, the system of ammonium polyphosphate - pentaerythritol - melamine (in a ratio of 2: 1: 1) was selected. The fire retardant properties of the developed material were investigated. Coatings on the base of the developed fire retardant paint allow us to increase own level of fire resistance of metal constructions up to three (90 minutes).

A novel intumescent flame retardant system based on shell (S) and histidine diphosphate (HF) was developed and introduced into the epoxy resin in order to verify its effectiveness in the inhibition of the burning process. To confirm the structure of HF, powder X-ray diffraction (XRD) was used. The influence of the flame retardant system on the burning and smoke emission of the resin was assessed based on cone calorimeter (CC) measurements. Moreover, structural evaluation of polymeric materials was carried out using scanning electron microscopy (SEM). It was found that the incorporation of the developed flame retardant system caused the formation of a protective layer in the form of char, which reduced burning process and smoke emission of the epoxy resin. The obtained results were better than those generated by commercial intumescent fire retardant.

Le but de ce travail de thèse est d’obtenir une compréhension des mécanisme d’action des revêtements intumescents à base d’époxy afin de fournir des perspectives pour le développement de nouveaux systèmes de protection contre le feu. La formulation intumescente est un système très complexe. Ce travail se concentre en particulier sur les composants clés dont la compréhension des mécanismes d’action était absente. Tout d’abord, les mécanismes d’action des borates ont été étudiés en incluant des modifications chimiques et thermo-physiques; la combinaison des résultats obtenus sous différents aspects permet de comprendre son mode d’action. D’un côté, les borates en particulier l’acide borique ont été mentionnés comme Cancérogènes, Mutagènes, Reprotoxiques (CMR); la substitution de ces composants est nécessaire. Les résultats soulignent le rôle important et la réactivité élevée du zinc (de borate de zinc), ce qui suggère le développement de nouveaux systèmes en incorporant un composé à base de zinc au lieu du borate du zinc. Deuxièmement, l’effet du CaCO3 sur les propriétés de protection contre le feu et son mécanisme d’action dans le revêtement intumescent ont été examinés. L’ajout de CaCO3 améliore les propriétés de protection au feu et d’adhérence/cohérence du revêtement et son mécanisme d’action était justifié. De plus, plusieurs carbonates (MgCO3, ZnCO3, Na2CO3, K2CO3) en tant qu’ingrédient intumescent ont également été examinés. L’utilisation de MgCO3 comme ingrédient intumescent est favorable pour les propriétés de protection contre le feu du revêtement ainsi que pour l’utilisation de CaCO3. Dans ce travail, les mécanismes d’action des borates et des carbonates ont été étudies. Les résultats suggèrent le développement de nouveaux systèmes utilisant des ingrédients alternatifs tels que le composé à base de zinc ou MgCO3
The goal of this PhD work is to get an insight into the mechanisms of action of epoxy based intumescent coating to be able to provide the outlooks for the development of novel systems of higher protection against fire. The intumescent formulation is highly complex system. This work focuses particularly on the key components of which the understanding of the mechanisms of action is still lacking. Firstly, the mechanisms of action of borates were investigated in both chemical and thermo-physical modifications; the combination of the results obtained from different aspects allows drawing its mode of action. On the one hand, borates in particular boric acid have been mentioned to be Carcinogenic, Mutagenic, Reprotoxic (CMR); the substitution of these important intumescent components are necessary. The results point out the important role and high reactivity of zinc (i.e. from zinc borate), this suggests the development of novel systems by incorporating zinc based compound instead of zinc borate. Secondly, the effect of CaCO3 on fire protective properties and its mechanism of action in intumescent coating were examined. The addition of CaCO3 improves the fire protective properties and adhesion/cohesion of the coating and its mechanism of action was fully justified. Additionally, various carbonates (i.e. MgCO3, ZnCO3, Na2CO3, K2CO3) as intumescent ingredient were also examined. The use of MgCO3 as intumescent ingredient is beneficial for the fire protective properties of the coating as well as the use of CaCO3. In this work, the mechanisms of action of borates and carbonates were fully examined. The results suggest the development of novel systems with using the alternative ingredients such as zinc-based compound or MgCO3

Les matériaux composites à matrice polymère thermodurcissable interviennent dans de nombreux domaines d’application, parmi lesquels le secteur des transports. Ils présentent toutefois une faible tenue au feu qui limite leur utilisation pour des raisons évidentes de sécurité. De par les restrictions de plus en plus exigeantes de la Commission Européenne (REACH), il existe un réel besoin de se tourner vers des solutions alternatives. Des études récentes ont prouvé l’intérêt des Silsesquioxanes Oligomériques Polyhédriques (POSS) comme agents ignifuges, et particulièrement les POSS portant des ligands phenyl. L’objectif de ce travail a été d’étudier comment la tenue au feu de réseaux hybrides époxy-amine pouvait être améliorée par l’ajout de POSS dans ces matériaux. En faisant varier la nature des comonomères époxydes et amines, ainsi que la structure des POSS sélectionnés, des éléments de réponse ont pu être apportés à la question : existe-t-il une relation structure-propriété en ce qui concerne le comportement au feu des réseaux époxydes ? Des POSS fonctionnels et inertes ont été choisis pour cette étude, et une attention particulière a été portée sur le trisilanolphenyl POSS (POSSOH), pour lequel différents procédés de dispersion ont été mis en œuvre. Il a été montré que l’état de dispersion des POSS était significativement influencé par le type de ligands de ces POSS, mais également par le type de prépolymère époxyde utilisé. En particulier, des structures complexes, jamais observées, ont été découvertes dans les réseaux hybrides basés sur la Tétraglycidyl(diaminodiphenyl) méthane (TGDDM). Des études cinétiques visant à comprendre les interactions développées par les POSS au sein des réseaux ont été menées. Un fort pouvoir catalytique de l’association POSSOH avec un composé à base d’aluminium sur les réactions de réticulation a notamment été mis en évidence. D’autre part, les propriétés thermomécaniques des réseaux finals n’ont pas été modifiées de manière significative par l’ajout de POSS. Finalement, une amélioration remarquable de la tenue au feu a été obtenue dans certains cas, notamment par l’ajout de POSSOH en combinaison avec le composé métallique. La tenue au feu des réseaux à base de TGDDM a été identifiée comme étant liée à un mécanisme d’intumescence
Thermoset polymer composite materials are used in a number of application domains, amongst which the transports sector, but they suffer from poor fire resistance which limits their use for obvious safety and security issues. With the increasingly demanding restrictions from the European Commission, there is a real need to seek for alternative solutions. Recent studies have found the Polyhedral Oligomeric Silsesquioxane (POSS) compounds interesting as fire retardant agents, particularly the POSS bearing phenyl ligands. The present work aimed at investigating how the fire retardancy of hybrid epoxy networks can be improved by incorporating Polyhedral Oligomeric Silsesquioxanes (POSS). In this study, the nature of the epoxy-amine comonomers was varied, as well as the POSS structure. An inert POSS and two multifunctional POSS were selected in order to generate various morphologies. The aim was to answer the question: does a structure-property relationship exist as concerns the fire behaviour of epoxy networks? Particular attention was dedicated to systems containing the trisilanolphenyl POSS (POSSOH) for which different processes of dispersion were implemented. The POSS dispersion state was shown to be greatly influenced by the type of POSS ligands, but also by the epoxy prepolymer nature in the case of the versatile POSSOH. In particular, intricate, never-observed morphologies were discovered in the networks based on Tetraglycidyl(diaminodiphenyl) methane (TGDDM) and containing POSSOH. The study of functional POSS-involving interactions and epoxy-amine kinetics in the model systems revealed the high catalytic power of the combined presence of POSSOH and an aluminium-based catalyst in the model epoxy networks, as well as the occurrence of homopolymerisation. The thermo-mechanical properties were not significantly modified by the addition of POSS. Finally, spectacular improvements in fire retardancy were obtained in some cases, in particular when the POSSOH and the Al-based catalyst were introduced in combination. The fire protection mechanism was attributed to intumescence in the TGDDM-based networks. The addition of POSSOH and the Al-catalyst was found to be efficient in all the epoxy-amine network types, which could not be clearly related to the POSSOH structures but was rather attributed to a chemical synergistic effect

La toxicité avérée et le caractère bio-accumulatif des retardateurs de flamme halogénés usuels (PBDE) ont entrainé la mise en place de restrictions d'usage au sein de l'union européenne (REACH). Les retardateurs de flamme phosphorés (RFP) se sont imposés comme alternatives aux solutions halogénées pour leur moindre toxicité et leurs propriétés ignifugeantes adaptées à la composition chimique des résines époxy. Avec l'essor des résines époxy biosourcées, la dépendance aux ressources fossiles pour la synthèse des additifs en tout genre qui entre dans leur composition est devenue problématique. Ainsi, ces travaux s'inscrivent dans une dynamique de développement durable à travers la valorisation d'un composé biosourcé représentatif des structures phénoliques disponibles: le phloroglucinol. La fonctionnalisation directe du phloroglucinol par des groupements phosphates a permis de réaliser une première série d'additifs RFP biosourcés présentant une action ignifugeante prononcée en phase condensée qui réduit le pouvoir calorifique des matériaux ignifugés. A l'échelle macroscopique, une forte intumescence entraîne une décomposition partielle du matériau ignifugé par effet barrière du résidu formé. Cependant, ces additifs réduisent fortement les températures de transitions vitreuse et mécanique par plastification du réseau thermodurcissable. La fonctionnalisation en deux étapes du phloroglucinol a conduit à deux RFP biosourcés additif (P3SP) et réactif (P2EP1SP) de structures comparables. Nous avons ainsi pu mettre en évidence l'intérêt de l'approche réactive qui, en plus de garantir la durabilité des propriétés des matériaux ignifugés, permet une meilleure action en phase condensée qui entraîne une plus forte intumescence. L'approche réactive semblant plus performante, nous avons poursuivi avec la synthèse d'un dernier RFP biosourcé réactif (P2EP1P) dont la structure a été adaptée pour réduire l'effet plastifiant du groupement phosphoré. Enfin, l'étude de différents matériaux 100 % biosourcés contenant le RFP P2EP1P a montré que les inconvénients de l'approche réactive dus à la faible fonctionnalité du RFP réactif peuvent en partie être compensés par l'incorporation d'un co-précurseur époxy de haute fonctionnalité ou d'un agent de réticulation biosourcé aromatique
The toxicity and the bioaccumumulative character of the usual halogenated flame retardants(RFX) lead to uses restrictions of the main FRX (PBDE) in the EU as REACH. The phosphorus-containing flame retardants (FRP) are suitable for the epoxy thermoset because of their action on the hydroxyl groups. Moreover, the FRP are less toxic than the FRX. With the rise of the biobased epoxy thermosets, the dependence on fossil fuels for the additives synthesis has become problematic. Thus, these works are designed in a sustainable development approach through the valorization of a biobased compound which is representative of the biobased phenolic structures. The directe functionalization of the phloroglucinol with phosphate functions has achieved a first generation of biobased additives FRP which exhibit a significant action in the condensed phase and reduce the heat released during the thermal degradation of the fire retarded thermosets. This effect results in a strong intumescence at macroscopic scale and the expanded residue acts as a barrier and leads to a partial degradation of the thermoset. However, these additives plasticize the thermoset network and reduce the glass and the mechanical transition temperatures. A two-steps functionalization of the phloroglucinol leads to two new biobased FRP, an additive (P3SP) and a reactive (P2EP1SP), with similar chemical structures. We were able to highlight the benefit of the reactive approach which favors the condensed phase action and the intumescence. Moreover, the reactive approach ensures the durability of the flame retarded thermoset properties. Since the reactive approach seems more efficient than the additive one, an other reactive FRP was synthesized, whose the structure was optimized to reduce the plasticizing effect of the phosphorus-containing group. Finally, the study of different 100% biobased phosphorus-containing thermosets highlighted that the disadvantages of the reactive approach may be balanced by the incorporation of a high functionality epoxy precursor or an aromatic curing agent

Polyurethanes can be used in many applications by modifying their properties via facile methods. Most of the polyurethanes currently used for industrial applications originated from petrochemical-based chemicals. There is a growing demand in industries to use renewable resources for polyurethanes. Vegetable oil-based polyurethanes have shown properties comparable to that of petroleum-based polyurethanes. In this research, sunflower oil was used as a renewable resource for polyurethanes. Rigid polyurethane foams were prepared using sunflower-based polyols. The polyols were synthesized via epoxidation followed by a ring-opening reaction. Epoxy number, hydroxyl number, viscosity, and spectroscopy characterizations confirm the synthesis of bio-polyol. One of the major issues in polyurethanes is their high flammability which was reduced by using flame-retardants. Two flame-retardants using melamine and diphenylphosphinic acid (DPPMA) and a phosphorous‐nitrogen intumescent flame‐retardant (2,2‐diethyl‐1,3‐propanediol phosphoryl melamine, DPPM) were synthesized and used in bio-based polyurethanes. as used as an additive flame retardant. The foams with DPPMA and DPPM showed high closed cell content ( >90%) with a high compression strength of 217 kPa and 208 kPa, respectively. The microstructure analysis of the foams using scanning electron microscopy revealed an even distribution of the pore size. The addition of DPPMA and DPPM in polyurethane foams results in the formation of a protective char layer during the flammability test and reduces the weight loss from 43% to 2.5% and 1.4% and burning time from 70 seconds to 6 seconds and 4.5 seconds, respectively. Our research suggests that sunflower oil could be a potential candidate for the polyurethane industries and DPPMA and DPPM can be used as an effective flame-retardant in these bio-based polyurethane foams.