An experimental study has been carried out to investigate the effects of buoyancy on smoldering of polyurethane foam. The experiments are conducted with a high void fraction flexible polyurethane foam as fuel and air as oxidizer, in a geometry that approximately produces a one dimensional smolder propagation. The potential effect of buoyancy in the process is analyzed by comparing upward and downward smolder propagation through a series of normal gravity and variable gravity experiments. Both opposed and forward mixed (free and forced) flow smolder configurations are studied. In opposed smolder the oxidizer flow opposes the direction of smolder propagation, and in forward smolder both move in the same direction. Variable gravity free flow tests are also conducted in an aircraft flying a parabolic trajectories that provides low gravity periods of up to 25 sec. Measurements are performed of the smolder reaction propagation velocity and temperature as a function of the location in the sample interior, the foam and air initial temperature, the direction of propagation and the air flow velocity. This information is used in conjunction with previously developed smolder theoretical models to determine the smolder controlling mechanisms and the effect of gravity. Three zones in the fuel sample with clearly defined smolder characteristics are identified. A zone close to the igniter where smolder is affected by the external heat, a zone at the end of the sample where smolder is affected by the environment, and a zone at the end of the sample where smolder is affected by the environment, and a zone, in the middle of the foam, that is free from external effects. This last zone is the most characteristic of one dimensional, self-supported smolder, and the one that is studied in greater detail. In mixed flow convection buoyancy induced flows together with the forced flow are the primary mechanism of oxidizer transport to the reaction zone, while diffusion has a secondary importance. In natural convection, downward smoldering is of the opposed type while upward smoldering resembles more the forward type. For opposed flow smoldering, both natural and forced, the smolder propagation velocity is found to increase with the oxidizer mass flux reaching the reaction zone. This result confirms predictions from previously developed theoretical models that the smolder velocity is proportional to the oxygen mass flow. The experimental data is correlated in terms of a non-dimensional smolder velocity derived from these models, the results show very good agreement between theory and experiments for strong smolder. To implement the models, an analysis of the gas flow field is developed where the effect of significantly different permeabilities between char and foam is been Extinction is observed for very low and for very high flow rates, which shows that smolder is controlled by a sensitive competition between oxygen supply and heat losses to and from the reaction zone. Under these conditions the models do not describe the experiments well. The forward flow smolder experiments show that forward smoldering is controlled not only by the competition between oxygen supply and heat losses to and from the reaction zone but also by the competition between pyrolysis and oxidation. For low flow velocities a regime resembling the opposed flow is observed. As the air flow velocity is increased, foam pyrolysis followed by char oxidation is the controlling smolder mechanism. For both these conditions the theoretical models describe the experiments well. Increasing the flow velocity further results in a smolder propagation velocity controlled by total fuel consumption, in downward burining. For upward burning transition to flaming is observed for very high air flow velocities. This last regime is not well predicted by the theoretical models. The results from the experiments in variable gravity environment conducted in the KC-135A and Leajet airplanes confirm the normal gravity observations that the competition between heat losses and oxidizer transport is the major mechanism controlling smolder. The absence of convective flow in low gravity results in higher temperature in the unburnt fuel and char due to smaller heat losses to the surroundings. However, the oxidizer transport to the reaction zone also decreases and as a result the temperature at the reaction zone decreases indicating a weakening of the eaction, The presence of pyrolytic reactions in foward smolder and their capability to inhibit smoldering complicates the above described smolder mechanisms.

This study examined several structure-property features of flexible polyurethane foams that are important aspects of foam production. AFM and WAXS were used to demonstrate the existence, for the first time in typical polyurethane foam systems, of lamellae-like polyurea structures ca. 0.2 mm long and ca 5-10 nm across. Aggregations of these lamellae-like hard domains may be the polyurea balls typically observed via TEM. Diethanolamine, a widely used cross-linking agent in molded foams, was shown to disrupt ordering in the polyurea hard domains and alter the interconnectivity of hard domains by preventing the formation of lamellae-like structures. These changes were shown to lead to softening of the foam. Copolymer polyol is frequently applied as reinforcing filler in foams. It was found that a common method of adding this component alters the hard segment/soft segment (HS/SS) ratio, thus increasing the load bearing capacity of the foam. It was observed in this report that at constant HS/SS ratio, the copolymer polyol only increased load bearing under humid conditions. It was also shown that the collapse of the cellular structure of a foam prior to the point of urea precipitation alters the aggregation behavior of the hard domains and alters solid-state properties. Surfactant is thus suggested to play a secondary role in the development of the hard domains by maintaining the cellular structure in the foam as the phase separation occurs and at least until the polyurethane foam has more fully organized hard segment domains. It was found that cure temperature could be manipulated to predictably change interdomain spacings and hydrogen bond development in the polymer. Curing above 100°C was found to lower hard segment content for plaques of the same formulation possibly as a result of water and isocyanate vaporization. Apart from polyurethane materials, structure-property relationships were examined in cast blends based on poly(tetrafluoroethylene) (PTFE) and the terpolymer poly(tetrafluoroethylene-co-vinylidene fluoride-co-hexafluoropropylene) (FKM). This revealed that tensile and dynamic moduli could be predictably altered by controlling the degree of FKM cross-linking or by varying PTFE content in the film. Inducing PTFE fibrillation was found to yield higher modulus films without increasing PTFE content. / Ph. D.

A computational study has been carried out to investigate smoldering ignition and propagation in polyurethane foam. The onedimensional, transient, governing equations for smoldering combustion in a porous fuel are solved accounting for improved solid-phase chemical kinetics. A systematic methodology for the determination of solid-phase kinetics suitable for numerical models has been developed and applied to the simulation of smoldering combustion. This methodology consists in the correlation of a mathematical representation of a reaction mechanism with data from previous thermogravimetric experiments. Geneticalgorithm and trail-and-error techniques are used as the optimization procedures. The corresponding kinetic parameters for two different mechanisms of polyurethane foam smoldering kinetics are quantified: a previously proposed 3-step mechanism and a new 5-step mechanism. These kinetic mechanisms are used to model one-dimensionalsmoldering combustion, numerically solving for the solid-phase and gasphase conservation equations in microgravity with a forced flow of oxidizer gas. The results from previously conducted microgravity experiments with flexible polyurethane foam are used for calibration and testing of the model predictive capabilities. Both forward and opposed smoldering configurations are examined. The model describes well both opposed and forward propagation. Specifically, the model predicts the reaction-front thermal and species structure, the onset of smoldering ignition, and the propagation rate. The model results reproduce the most important features of the smolder process and represent a significant step forward in smoldering combustion modeling.

This study addresses the flexural performance of sandwich panels composed of a polyurethane foam core and glass fibre-reinforced polymer (GFRP) skins. Panels with and without GFRP ribs connecting the skins have been studied. While the motivation of the study was to develop new insulated cladding panels for buildings, most of the work and findings are also applicable to other potential applications such as flooring, roofing and light-weight decking. The study comprises experimental, numerical, and analytical investigations. The experimental program included three phases. Phase I is a comprehensive material testing program of the polyurethane core and GFRP skins and ribs. In Phase II, six medium size (2500x660x78 mm) panels with different rib configurations were tested in one-way bending. It was shown that flexural strength and stiffness have increased by 50 to 150%, depending on the rib configuration, compared to a panel without ribs. In Phase III, two large-scale (9150x2440x78 mm) panels, representing a cladding system envisioned to be used in the field, were tested under a realistic air pressure and discrete loads, respectively. The deflection under service wind load did not exceed span/360, while the ultimate pressure was about 2.6 times the maximum factored wind pressure in Canada. A numerical study using finite element analysis (FEA) was carried out. The FEA model accounted for the significant material nonlinearities, especially for the polyurethane soft core, and the geometric nonlinearity, which is mainly a reduction in thickness due to core softness. Another independent analytical model was developed based on equilibrium and strain compatibility, accounting for the core excessive shear deformation. The model also captures the localized deformations of the loaded skin, using the principals of beam-on-elastic foundation. Both models were successfully validated using experimental results. Possible failure modes, namely core shear failure, and compression skin crushing or wrinkling were successfully predicted. A parametric study was carried out to explore further the core density, skin thickness, and rib spacing effects. As the core density increased, flexural strength and stiffness increased and shear deformations reduced. Also, increasing skin thickness became more effective as the core density increased. The optimal density was 95-130 kg/m3. Reducing the spacing of ribs enhanced the strength up to a certain level; It then stabilized at a spacing of 2.9 times the panel thickness. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2010-09-21 16:29:00.315

abstract: Over the past couple of decades, quality has been an area of increased focus. Multiple models and approaches have been proposed to measure the quality in the construction industry. This paper focuses on determining the quality of one of the types of roofing systems used in the construction industry, i.e. Sprayed Polyurethane Foam Roofs (SPF roofs). Thirty seven urethane coated SPF roofs that were installed in 2005 / 2006 were visually inspected to measure the percentage of blisters and repairs three times over a period of 4 year, 6 year and 7 year marks. A repairing criteria was established after a 6 year mark based on the data that were reported to contractors as vulnerable roofs. Furthermore, the relation between four possible contributing time of installation factors i.e. contractor, demographics, season, and difficulty (number of penetrations and size of the roof in square feet) that could affect the quality of the roof was determined. Demographics and difficulty did not affect the quality of the roofs whereas the contractor and the season when the roof was installed did affect the quality of the roofs. / Dissertation/Thesis / M.S. Construction 2013

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This research investigates the decomposition and burning behaviours of polyurethane foams experimentally and compares the experimental results obtained with the numerical results from the pyrolysis model of Fire Dynamics Simulator, Version 5 (FDS 5). Based on the comparison of model and experimental heat release rates, the accuracy of the pyrolysis model is quantified. In total, this research tested seven polyurethane foams consisting of three non-fire retardant (NFR) and four fire retardant (FR) foams. According to the simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) experiments, the decomposition behaviour of polyurethane foams under nitrogen environment is represented by two pyrolysis reactions. The first reaction consists of foam decomposition into melts and gases while the second reaction consists of the decomposition of the remaining melts into gases. The kinetic properties which govern the rate of decomposition are the activation energy (E), pre-exponential factor (A), reaction order (n) and heat of reaction (Δhr). Using graphical techniques, E, A and n of the first and second reactions are determined from the thermogravimetric analysis (TGA) results. Through analysing the differential scanning calorimetry (DSC) results, Δhr is determined from the changes in heat flow and sample mass. The thermophysical properties govern the heat transfer through material and these are the thermal conductivity (λ) and specific heat (cp) which are measured experimentally at ambient temperature through the Hot Disk method. Through the Sample Feeding Vertical Cone, the decomposition and melting behaviours of polyurethane foams in a vertical orientation are investigated and the foams tested can be categorised into those which produce melts only after ignition and those which produce melts and char after ignition. The 1-dimensional burning behaviour of foams is obtained from the cone calorimeter experiments. The NFR foams show a change from plateau burning behaviour at low heat flux to two stage burning behaviour at high heat flux while the FR foams consistently show two stage burning behaviour. The combustion property governs the amount of heat released when fuel combusts and this is the effective heat of combustion (Δhc,eff) which is determined from the heat released and mass consumed in the cone experiment. The 1-dimensional burning behaviour is simulated using the pyrolysis model of FDS 5 and two different modelling approaches are considered. The direct method uses the material properties determined experimentally as FDS 5 inputs while the refined method uses the genetic algorithm of Gpyro to refine the kinetic properties which are later used as FDS 5 inputs. The heat release rate of the model and experiment are compared through linear regression analysis which quantifies the accuracy of both methods. The accuracy is defined as the percentage of data points within the boundary of acceptance which is bounded by 25 % of the greatest experimental heat release rate. This assessment method places greater emphasis on the accuracy of developed burning phases and lesser emphasis on the accuracy of initial growth and final decay. The accuracy of the direct method is found to be 56 % while the refined method with estimated kinetic properties achieves a higher accuracy of 75 %. The 2-dimensional burning behaviours are investigated in the foam slab experiments for two different slab thicknesses, 120 and 100 mm. The opposed-flow spread of 120 mm slab is more intense and rapid while for the 100 mm slab, the flame spread is less intense and slow. FDS 5 is used to simulate the experimental results but when the material properties either developed experimentally or refined by Gpyro are used as inputs, the model fails to produce flame spread. This is because FDS 5 does not yet have the features which address the dynamics of foam melting and the reactive nature of the flame. In order to produce flame spread in the model, E of the reactions have been reduced to increase the decomposition rate.

En vanligt förekommande laminering är polyuretanskum, som används för att ge egenskaper som mjukhet, komfort och flexibilitet till textiler. Ett användningsområde som tillverkaren och leverantören Borgstena Group Sweden AB använder polyuretan till är lastbilars väggpaneler. De vill dock ersätta den polyuretanskumlaminerade dubbeljerseytrikån som används idag med endast en ren trikåkonstruktion för att slippa problem som dellaminering och minskade töjegenskaper. Dessutom så har den kemiska sammansättningen av polyuretan som används i lamineringen visat sig vara belastande för både miljö och människor. I denna rapport klargörs varför polyuretanskum behöver ersättas och vilka möjligheter som finns i dagsläget för att göra detta. En praktisk produktutveckling för ett potentiellt ersättningsmaterial, alltså en konstruktion med 3D-effekt utforskas på tvåbäddsrundstick. Resultatet av denna produktutveckling visar att garnernas skillnad i dtex (tjocklek) och maskininställningen relief tillsammans med mönstrets storlek och komposition ärav betydelse i att skapa 3D-struktur. Utav provstickningarna som gjorts görs ett flertal tester på en slutgiltig konstruktion med partier av olika masklängder, detta i avseende på töjegenskaperna för att därmed se hur konstruktionen når upp till töjkraven som krävs för denna produkt.A common laminate is polyurethane foam which is used to provide textile properties such assoftness, comfort and flexibility. Borgstena Group Sweden AB is an active company and serves asboth manufacturer and supplier for the automotive industry. The Company uses laminates ofpolyurethane foam and double jersey knits to make truck-wall panels, however they wish to replacethis group of merchandise with only a clean knit construction design to avoid problems asdelamination and decreased tensile properties. In addition, the chemical composition ofpolyurethane foam used in the process of lamination has been known for causing malicious damagefor humans as well as the global environment. This case study clarifies why polyurethane foamshould be replaced and what types of methods are available within the current demarcation in orderto do this. An empirical process of product development for a potential replacement material, thus a construction with a 3D-effect is explored on a two-bed circular knitting machine. The result of thiscase study's prototype shows that the yarn difference in dtex (thickness) and the setting of the machine together with the composition and pattern size, are of great importance when creating a 3D-structure.From several knit sessions that took place in this study tests were done on a final pattern that wastested with different mesh lengths and a special test concerning the tensile strength, to examine howthe construction reaches the settled quality standards required for this field of application. / Program: Textilingenjörsutbildningen

[pt] Este trabalho apresenta um estudo sistemático da sorção de índio de meio iodeto, utilizando espuma de poliuretano à base de poliéter comercial como extrator em fase sólida, visando à pré-concentração e/ou separação de índio de diferentes matrizes de amostras. As características físico-químicas de sorção do sistema foram investigadas por processo em batelada, apresentando rápida cinética e máxima sorção numa faixa significativa de meio ácido ou básico, com coeficientes de distribuição acima de 104 L kg-1 ([KI] maior ou igual 0,6 mol L-1). A análise do equilíbrio de sorção indicou o tetraiodo- indato (MinI4) como a principal espécie sorvida na matriz da espuma; os mecanismos de sorção mais prováveis foram discutidos. A isoterma de Langmuir foi ajustada com êxito sendo obtido um valor de (1,55 mais ou menos 0,02)x10-1 mol kg-1 para a capacidade de saturação. O efeito da temperatura foi avaliado indicando um processo espontâneo e exotérmico caracterizado por sorção química. A reextração do índio da espuma com solução de HCl 1,0 mol L-1 em meio etanol 50% apresentou rápida cinética (10 minutos) e eficiência (97%). O sistema pode ser utilizado para a separação de traços de índio de grandes quantidades de Al, Fe, Zn, Ni, Co, Mn e Ga. Cd e Pb são co-extraídos. Ácido cítrico, F- e EDTA interferem na sorção do índio; tiosulfato de sódio (menor 0,1 mol L-1) e ácido ascórbio (até 0,8 mol L-1) não interferem. O sistema foi avaliado na determinaço de In na presença de 105 vezes Zn, Al, Fe pelo método de adição e recuperação de índio. Os elementos determinados por ICP- OES apresentaram fatores de separação, da ordem de 7,0 x 102 para Zn/In, 1,0x105 para Fe/In e de 5,5x104 para Al/In, com eficiente recuperação de índio. A metodologia desenvolvida foi aplicada para determinar índio por ICP- OES em material de referência padrão de zinco metálico (NIST), apresentando concordância compatível com o valor certificado, para um nível de confiança de 95%. / [en] This work shows a systematic study on indium iodide sorption using commercial polyether-based polyurethane foam as a solid phase extractor in order to preconcentrate and/ or separate indium from different sample matrices. The physico-chemical characteristics of the system sorption were investigated for the batch process. The system has shown rapid kinetic and maximum sorption from a meaningful range of either acid or basic medium and achieves distribution ratios above 104 L kg-1 ([KI] maior ou igual 0.6 mol L-1). Sorption equilibrium analysis indicates the tetraiodo- indate (MInI4) as the main species sorbed on the foam matrix; the more probable mechanisms of sorption were discussed. Langmuir isotherm was successfully fitted and a value of (1.55 mais ou menos 0.02)x10-1 mol kg-1 was obtained for the saturation capacity. The temperature effect was evaluated and indicates a spontaneous and exothermic chemisorption process favored at low temperatures. The indium reextraction from the foam using a HCl 0.1 mol L-1 in ethanol 50% medium solution has also shown a rapid kinetic (10 minutes) and efficiency (97%). The system should be used to separate large quantities of Al, Fe, Zn, Ni, Co, Mn and Ga from trace indium. Cd and Pb are coextracted with indium. Citric acid, F- and EDTA interfere on indium sorption; sodium thiosulfate (menor ou igual 0.1 mol L-1) and ascorbic acid (up to 0.1 mol L-1) do not interfere. The system was evaluated in the determination of indium in the presence of 105 times Zn, Al and Fe by indium addition and recovery technique. The elements determination by ICP-OES showed separation factors around 7.0x102 for Zn/In, 1.0X105 for Fe/In and of 5.5x104 for Al/In, with an efficient recovery of indium. The developed methodology was applied to determine indium in metallic zinc standard reference material (NIST) by ICP-OES and has shown compatible agreement with the certified value at a 95% confidence level.