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The kinetics of polyurethane structural foam formation: Foaming and polymerization

AIChE Journal

Rao, Rekha R.; Mondy, L.A.; Long, Kevin N.; Celina, Mathias C.; Roberts, Christine C.; Soehnel, Melissa M.; Wyatt, Nicholas B.; Brunini, Victor B.

Kinetic models have been developed to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI-10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, although it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transition temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. The kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent articles. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2945–2957, 2017.

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Physical Properties of Low-Molecular Weight Polydimethylsiloxane Fluids

Roberts, Christine C.; Graham, Alan; Nemer, Martin N.; Phinney, Leslie M.; Garcia, Robert M.; Soehnel, Melissa M.; Stirrup, Emily K.

Physical property measurements including viscosity, density, thermal conductivity, and heat capacity of low-molecular weight polydimethylsiloxane (PDMS) fluids were measured over a wide temperature range (-50°C to 150°C when possible). Properties of blends of 1 cSt and 20 cSt PDMS fluids were also investigated. Uncertainties in the measurements are cited. These measurements will provide greater fidelity predictions of environmental sensing device behavior in hot and cold environments.

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Modeling Manufacturing Impacts on Aging and Reliability of Polyurethane Foams

Rao, Rekha R.; Roberts, Christine C.; Mondy, L.A.; Soehnel, Melissa M.; Johnson, Kyle J.; Lorenzo, Henry T.

Polyurethane is a complex multiphase material that evolves from a viscous liquid to a system of percolating bubbles, which are created via a CO2 generating reaction. The continuous phase polymerizes to a solid during the foaming process generating heat. Foams introduced into a mold increase their volume up to tenfold, and the dynamics of the expansion process may lead to voids and will produce gradients in density and degree of polymerization. These inhomogeneities can lead to structural stability issues upon aging. For instance, structural components in weapon systems have been shown to change shape as they age depending on their molding history, which can threaten critical tolerances. The purpose of this project is to develop a Cradle-to-Grave multiphysics model, which allows us to predict the material properties of foam from its birth through aging in the stockpile, where its dimensional stability is important.

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Bubble-Size Evolution during Polyurethane Foam Expansion

Mondy, L.A.; Roberts, Christine C.; Soehnel, Grant H.; Brady, Casper; Shelden, Bion; Soehnel, Melissa M.; Garcia, Robert M.

We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane (PMDI) foam used to encapsulate electronic components or to produce lightweight structural parts. The polyurethane of interest is a chemically blown foam, where carbon dioxide is produced via the reaction of water, a blowing agent, and isocyanate. Here, we take a careful look at the evolution of the bubble sizes during blowing. This information will help the development of subgrid models to predict bubble formation, growth, coalescence and collapse, drainage, and, hence, eventually the development of engineering models to predict foam expansion into a mold. Close-up views of bubbles at a transparent wall of a narrow, temperature-controlled channel are recorded during the foaming reaction and analyzed with image processing. Because these bubbles are pressed against the wall, the bubble sizes in the last frames after the expansion has stopped are compared to scanning electron microscope (SEM) images of the interior of some of the cured samples to determine if the presence of the wall significantly changes the bubble sizes. In addition, diffusing wave spectroscopy (DWS) is used to determine the average bubble sizes across the width of a similar channel as the bubbles change with time. DWS also gives information about microstructural changes as bubbles rearrange upon bubble collapse or coalescence. In this paper we conclude qualitatively that the bubble size distribution is heavily dependent on the formulation of foam being tested, temperature, the height in the foam bar, the proximity to a wall, and the degree of over-packing.

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A kinetic approach to modeling the manufacture of high density strucutral foam: Foaming and polymerization

Rao, Rekha R.; Mondy, L.A.; Noble, David R.; Brunini, Victor B.; Roberts, Christine C.; Long, Kevin N.; Soehnel, Melissa M.; Celina, Mathias C.; Wyatt, Nicholas B.; Thompson, Kyle R.

We are studying PMDI polyurethane with a fast catalyst, such that filling and polymerization occur simultaneously. The foam is over-packed to tw ice or more of its free rise density to reach the density of interest. Our approach is to co mbine model development closely with experiments to discover new physics, to parameterize models and to validate the models once they have been developed. The model must be able to repres ent the expansion, filling, curing, and final foam properties. PMDI is chemically blown foam, wh ere carbon dioxide is pr oduced via the reaction of water and isocyanate. The isocyanate also re acts with polyol in a competing reaction, which produces the polymer. A new kinetic model is developed and implemented, which follows a simplified mathematical formalism that decouple s these two reactions. The model predicts the polymerization reaction via condensation chemis try, where vitrification and glass transition temperature evolution must be included to correctly predict this quantity. The foam gas generation kinetics are determined by tracking the molar concentration of both water and carbon dioxide. Understanding the therma l history and loads on the foam due to exothermicity and oven heating is very important to the results, since the kinetics and ma terial properties are all very sensitive to temperature. The conservation eq uations, including the e quations of motion, an energy balance, and thr ee rate equations are solved via a stabilized finite element method. We assume generalized-Newtonian rheology that is dependent on the cure, gas fraction, and temperature. The conservation equations are comb ined with a level set method to determine the location of the free surface over time. Results from the model are compared to experimental flow visualization data and post-te st CT data for the density. Seve ral geometries are investigated including a mock encapsulation part, two configur ations of a mock stru ctural part, and a bar geometry to specifically test the density model. We have found that the model predicts both average density and filling profiles well. However, it under predicts density gradients, especially in the gravity direction. Thoughts on m odel improvements are also discussed.

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Rheological and Mechanical Property Measurements of PMDI Foam at Elevated Temperatures

Nemer, Martin N.; Brooks, Carlton F.; Shelden, Bion; Soehnel, Melissa M.; Barringer, David A.

A study was undertaken to determine the viscosity of liquefied 20 lb/ft3 poly methylene diisocyanate (PMDI) foam and the stress required to puncture solid PMDI foam at elevated temperatures. For the rheological measurements the foam was a priori liquefied in a pressure vessel such that the volatiles were not lost in the liquefaction process. The viscosity of the liquefied PMDI foam was found to be Newtonian with a power law dependence on temperature log10(μ/Pa s) = 20.6 – 9.5 log10(T/°C) for temperatures below 170 °C. Above 170 °C, the viscosity was in the range of 0.3 Pa s which is close to the lower measurement limit (≈ 0.1 Pa s) of the pressurized rheometer. The mechanical pressure required to break through 20lb/ft3 foam was 500-800 psi at temperatures from room temperature up to 180 °C. The mechanical pressure required to break through 10 lb/ft3 was 170-300 psi at temperatures from room temperature up to 180 °C. We have not been able to cause gas to break through the 20 lb/ft3 PMDI foam at gas pressures up to 100 psi.

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Experiments to populate and validate a processing model for polyurethane foam. BKC 44306 PMDI-10

Mondy, L.A.; Bauer, Stephen J.; Hileman, Michael B.; Thompson, Kyle R.; Smith, David M.; Rao, Rekha R.; Shelden, Bion S.; Soehnel, Melissa M.; O'Hern, Timothy J.; Grillet, Anne M.; Celina, Mathias C.; Wyatt, Nicholas B.; Russick, Edward M.

We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane foam, PMDI. The polyurethane of interest is chemically blown, where carbon dioxide is produced via the reaction of water, the blowing agent, and isocyanate. The isocyanate also reacts with polyol in a competing reaction, which produces the polymer. Here we detail the experiments needed to populate a processing model and provide parameters for the model based on these experiments. The model entails solving the conservation equations, including the equations of motion, an energy balance, and two rate equations for the polymerization and foaming reactions, following a simplified mathematical formalism that decouples these two reactions. Parameters for the polymerization kinetics model are reported based on infrared spectrophotometry. Parameters describing the gas generating reaction are reported based on measurements of volume, temperature and pressure evolution with time. A foam rheology model is proposed and parameters determined through steady-shear and oscillatory tests. Heat of reaction and heat capacity are determined through differential scanning calorimetry. Thermal conductivity of the foam as a function of density is measured using a transient method based on the theory of the transient plane source technique. Finally, density variations of the resulting solid foam in several simple geometries are directly measured by sectioning and sampling mass, as well as through x-ray computed tomography. These density measurements will be useful for model validation once the complete model is implemented in an engineering code.

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Results 26–50 of 55
Results 26–50 of 55