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At least 289 records · Page 16

Morphologies, Processing and Properties of Ceramic Foams from Pre-Ceramic Foams from Pre-Ceramic Polymer Routes

The current research is focused on processing ceramic foams that have potential as a thermal protection material. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies will be presented. The presentation will also focus on characterization of these foams in terms of mechanical and thermal properties. Foams processed using these approaches having bulk densities ranging from 0.15 to 0.9 g per cubic centimeter and a cell sizes from 5 to 500 micrometers. Compression strengths ranged from 2 to 7 MPa for these materials.

Stackpoole, Mairead↗

Morphologies, Processing and Properties of Ceramic Foams and Their Potential as TPS Materials

The current research is focused on processing ceramic foams with compositions that have potential as a thermal protection material. The use of pre-ceramic polymers with the addition of sacrificial blowing agents or sacrificial fillers offers a viable approach to form either open or closed cell insulation. Our work demonstrates that this is a feasible method to form refractory ceramic foams at relatively low processing temperatures. It is possible to foam complex shapes then pyrolize the system to form a ceramic while retaining the shape of the unfired foam. Initial work focused on identifying suitable pre-ceramic polymers with desired properties such as ceramic yield and chemical make up of the pyrolysis product after firing. We focused on making foams in the Si system (Sic, Si02, Si-0-C), which is in use in current acreage TPS systems. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies and the characterization of these foams in terms of mechanical and thermal properties are presented. We have conducted preliminary arc jet testing on selected foams with the materials being exposed to typical re-entry conditions for acreage TPS and these results will be discussed. Foams processed using these approaches have bulk densities ranging from 0.15 to 0.9 g/cm3 and cell sizes ranging from 5 to 500 pm. Compression strengths ranged from 2 to 7 MPa for these systems. Finally, preliminary oxidation studies have been conducted on selected systems and will be discussed.

Stackpoole, Mairead↗

Post-processing flame-retardant for polyurethane

Treatment of polyurethane form with elastomer formulation after processing makes foam fire resistant without compromising physical properties. In testing, once ignition source is removed, combustion stops. Treatment also prevents molten particle formation, generates no smoke or toxic gases in fire, and does not deteriorate under prolonged exposure to Sun.

Monaghan, P.↗

Shape‐Stabilization of Phase Change Materials with Carbon‐Conscious Poly(hydroxy)Urethane Foams

Thermal energy regulation is a significant challenge, contributing to over 30% of annual greenhouse gas emission (GHG) emissions. Phase change materials (PCMs) offer a promising solution by storing thermal energy, which can enable the reuse of waste heat for heating and cooling; however, developing materials for shape-stabilized PCMs remains crucial. This work investigates a self-foaming poly(hydroxy)urethane (PHU), derived from a non-isocyanate polyurethane (NIPU), as a porous support for shape-stabilizing paraffinic and salt hydrate PCMs. PHU-encapsulated paraffinic PCMs exhibited excellent thermal stability over repeated cycles. Thermal stability with salt hydrate PCMs, specifically calcium chloride hexahydrate (CaCl 2 •6H 2 O), is achieved by the incorporation of 5 wt.% barium carbonate (BaCO 3 ) into the PHU foam. This enabled stable cycling for over 48 cycles with desirable thermal properties, i.e., a melting point ≈30 °C, high enthalpy (ca. 138 J g −1 per cycle), and a consistent freezing point ≈20 °C, making it suitable for applications in buildings and electric vehicle battery insulation. Also, incorporating graphite (1.5–10 wt.%) into the foam enhanced the thermal conductivity of shape-stabilized CaCl 2 •6H 2 O during heating and cooling cycles. Overall, the approach detailed here offers a carbon-conscious and chemically tunable material for thermal energy storage.

25 ENERGY STORAGE↗

Erosion of polyurethane insulation.

Detailed description of the test program in which erosion of the spray foam insulation used in the S-II stage of the Saturn-V Apollo launch vehicle was investigated. The behavior of the spray foam was investigated at the elevated temperature and static pressure appropriate to the S-II stage environment, but in the absence of the aerodynamic shear stress.

Kraus, S.↗

Coating processes for increasing the moisture resistance of polyurethane baffle material

An investigation was conducted with the objective to improve the hydrolytic stability of reticulated polyurethane baffle material. This material is used in fuel tanks of aircraft and ground vehicles. The most commonly used foam of this type is hydrolytically unstable. Potential moisture barrier coatings which were evaluated include Parylene, epoxy-polysulfide, polyether based polyurethanes, polysulfides, polyolefin rubbers, and several other materials. Parylene coatings of at least 0.2 mil were found to provide the greatest improvement in hydrolytic stability.

Bilow, N.↗

Fractionated and purified hybrid poplar lignins as a polyol replacement in rigid polyurethane/polyisocyanurate foams

This study introduces fractionated lignin as an innovative component in the formulation of rigid polyurethane/polyisocyanurate (PUR/PIR) foams. Low-density PUR/PIR rigid foams were prepared by replacing 80% of the petrochemical-based polyol with a hybrid poplar (HP) lignin, recovered via alkaline pretreatment, and also with a fraction of this lignin, isolated via the Aqueous Lignin Purification with Hot Agents (ALPHA) process. The as-recovered HP and ALPHA-fractionated HP lignins were characterized to determine hydroxyl content, molecular weight (Mw) distribution, and pH. Both lignin-based foams met minimum standard requirements in terms of closed cell content, compression strength, and thermal conductivity. Notably, the foams made with ALPHA-based lignin outperformed the as-recovered lignin-based foams in all measured foam properties. Moreover, the ALPHA-based foam had comparable performance to the control foam (without lignin) except for density and even surpassed the control foam in closed cell content and compressive strength. This investigation of the molecular properties of lignin suggests that significant reductions in lignin average molecular weight and polydispersity (PDI) can positively impact the properties of lignin-based rigid foams.

09 BIOMASS FUELS↗

Materials for foam type insulation

An internal foam fabrication is one of the concepts being considered for cryogenic insulation on the hydrogen tanks of the shuttle vehicle. The three-dimensional polyurethane used on the S-4 B tanks failed to meet the higher temperature requirements of the shuttle vehicle, however, and other foams under consideration include polyisocyanurates, polyphenylene oxides, polyimides, and polybenzimidazoles. Improved adhesive systems for attaching the foams to the interior tank wall are under study.

Hill, W. E.↗

Determining Outgassing of Foam Packaging Material

When transporting highly radioactive material, it is vital to provide a successful delivery. Without proper containment, radioactive materials can become exposed to the surrounding environment and pose a serious threat. To ensure a safe transition of radioactive material, packaging components must be able to withstand high levels of heat during the event of a fire while maintaining the integrity of the structure to safety contain the radioactive material. Various types of polyurethane and silicone have been selected to observe at high temperatures to analyze outgassing characteristics of the materials.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Smoothing tool design and performance during subaperture glass polishing

During subaperture tool grinding and polishing, overlaps of the tool influence function can result in undesirable mid-spatial frequency (MSF) errors in the form of surface ripples, which are often corrected using a smoothing polishing step. Here, in this study, flat multi-layer smoothing polishing tools are designed and tested to simultaneously (1) reduce or remove MSF errors, (2) minimize surface figure degradation, and (3) maximize the material removal rate. A time-dependent convergence model in which spatial material removal varies with a workpiece-tool height mismatch, combined with a finite element mechanical analysis to determine the interface contact pressure distribution, was developed to evaluate various smoothing tool designs as a function of tool material properties, thicknesses, pad textures, and displacements. An improvement in smoothing tool performance is achieved when the gap pressure constant, $\overline{h}$ (which describes the inverse rate at which the pressure drops with a workpiece-tool height mismatch), is minimized for smaller spatial scale length surface features (namely, MSF errors) and maximized for large spatial scale length features (i.e., surface figure). Five specific smoothing tool designs were experimentally evaluated. A two-layer smoothing tool using a thin, grooved IC1000 polyurethane pad (with a high elastic modulus, E pad =360 MPa ), thicker blue foam (with an intermediate modulus, E foam =5.3 MPa ) underlayer, and an optimized displacement (d t =1 mm ) provided the best overall performance (namely, high MSF error convergence, minimal surface figure degradation, and high material removal rate).

47 OTHER INSTRUMENTATION↗

Lignin-Based Low-Density Rigid Polyurethane/Polyisocyanurate Foams

In this paper, unmodified kraft softwood lignin was utilized to fully replace the petroleum-based polyol for the first time in low-density rigid polyurethane/polyisocyanurate (PUR/PIR) foam. The effects of different lignin incorporation levels (0, 25, 50, 75, and 100%) on foam properties were investigated by measuring foam’s reactivity, polyol viscosity (using a rheometer), apparent density, compression strength, closed cell content (using a gas pycnometer), thermal conductivity, fire resistance, and morphology (observed through SEM). All formulated lignin-based foams met the ASTM minimum requirements for type 1 rigid insulation foams. Remarkably, the foam made by replacing 100% of the petrochemical polyol with the commercially available kraft lignin demonstrated outstanding fire resistance performance, reducing the burn length by 127%.

09 BIOMASS FUELS↗

Moisture-resistant baffle material for fuel tanks

Test results indicated superiority of certain polyether-based polyurethanes as protective coatings and suggested that baffle-materials with one of these coatings should have useful life approximately twice that of uncoated foams now in use.

Bilow, N.↗

Foam Degradation Model during Thermal Hypothetical Accident Conditions

Current practice in Safety Analysis Report for Packaging (SARP) thermal analysis for hypothetical accident conditions (HAC) of packages is to not explicitly model the consequence to the foam impact limiting material, but instead to make conservative estimates of those consequences and begin calculations from that point. This approach is typically used for the foam regression distance, which is the thickness of the degraded foam layer after the 30-minute fire event. Estimates for regression distance can come directly from package burn test results or from correlations based on one-dimensional testing by the foam manufacturer. In either case, this is a subjective process, and although it can be used to produce a conservative result, it is a significant approximation in the analysis. This paper describes testing and refinement of a simplified foam regression model. Comparisons are made against available data from laboratory experiments. Model refinements were tested until satisfactory agreement was achieved. The final modeling approach was then compared with post-test inspection results from HAC burn test data. A new model with an effective thermal conductivity based on foam to char density variation was shown successful in representing laboratory-scale foam thermal degradation experiments and full-scale burn tests of a current package. This model offers a technically defensible and predictive approach for modeling thermal degradation of rigid polyurethane insulation in transport packages.

36 MATERIALS SCIENCE↗

Toxicity of pyrolysis gases from some cellular polymers

Various samples of cellular polymers were evaluated for toxicity of pyrolysis gases, using the screening test method developed at the University of San Francisco. The cellular polymer samples included polyimide, polymethacrylimide, polybismaleimide, polyurethane, polyisocyanurate, polyethylene, polychloroprene, polyvinyl chloride, polystyrene, polysiloxane, and polyphosphazene. The cellular polymers exhibited varying levels of toxicity under these test conditions. Among the rigid cellular polymers, times to death were shortest with the imide type foams and longest with polyvinyl chloride and polystyrene. Among the flexible cellular polymers, times to death were shortest with polyimide and polyester, and longest with polychloroprene and polysiloxane. Increased char yield was not necessarily associated with reduced toxicity.

Hilado, C. J.↗

Chapter 6: TEA and LCA of Bio-Based Polyurethanes

For bio-based polyurethane (PU) to replace its conventional petroleum-based counterpart, it must be cost-competitive while providing a positive environmental benefit. Techno-economic analysis (TEA) and life cycle assessment (LCA) provide tools to quantify the economic and environmental viability of bio-based PU and to identify key drivers. Here we describe TEA and LCA methodologies for assessing bio-based PU, including an example case study for producing a flexible PU foam. This process has the potential to be cost-competitive with traditional PU based on a published study using a linseed oil proxy feedstock. Bio-based PU also demonstrates environmental advantages in some categories considered but faces challenges in others compared to petroleum-based PU. Further TEA and LCA beyond the case study may enable assessment for alternative product and process variations that are possible for bio-based PU.

bio-based polyurethane↗

Compressive Response and Energy Absorption of Additively Manufactured Elastomers with Varied Simple Cubic Architectures

Additive manufacturing, and particularly the vat photopolymerization process, enables the fabrication of complex geometries at high resolution and small length scales, making it well-suited for fabricating cellular structures (e.g., foams and lattices). Among these, elastomeric cellular structures are of growing interest due to their tunable compliance and energy dissipation. However, comprehensive data on the compressive behavior of these structures remains limited, especially for investigating the structure-property effects from changing the density and distribution of material within the cellular structure. This study explores how the mechanical response of polyurethane-based simple cubic structures changes when varying volume fraction, unit cell length, and unit cell patterning, which have not been systematically investigated previously in additively manufactured elastomers. Increasing volume fraction from 10% to 50% yielded significant changes in compressive stress–strain performance (decreasing strain at 0.5 MPa by 41.6% and increasing energy absorption density by 3962.5%). Although changing the unit cell length between 2.5 and 7 mm in ~30 mm parts did not result in statistically different stress–strain responses, modifying the configuration of struts of different thicknesses across designs with 30% volume fraction altered the stress–strain behavior (differences of 12.5% in strain at 0.5 MPa and 109.4% for energy absorption density). Power law relationships were developed to understand the interactions between volume fraction, unit cell length, and elastic modulus, and experimental data showed strong fits (R 2 > 0.91). These findings enhance the understanding of how multiple structural design aspects influence the performance of elastomeric cellular materials, providing a foundation for informing strategic design of tailorable materials for diverse mechanical applications.

36 MATERIALS SCIENCE↗

Green Catalysts for Reprocessing Thermoset Polyurethanes

Polyurethane (PU) thermosets are usually landfilled at the end of their service lifetimes and cannot be recycled through conventional means. Although dibutyltin dilaurate (DBTDL) is an effective catalyst for reprocessing PU thermosets, organotins are immunotoxic and teratogenic, which is concerning for catalysts embedded within covalent adaptable networks (CANs). Here, we identify Zr(acac) 4 and Zr(tmhd) 4 as catalysts to reprocess PU CANs more sustainably. Thermoset PU foams containing Zr-based catalysts exhibit characteristic stress relaxation times between 6 and 200 s, similar or faster than DBTDL. These catalysts are capable of reprocessing a PU foam for four or five cycles. Dynamic mechanical thermal analysis indicates that zirconium-based catalysts preserve glass transition temperature and crosslink density between cycles and are promising catalysts for bulk reprocessing of thermoset PUs. Here, a solvent-free reprocessing method was developed by co-milling the PU foam and the Zr catalyst. Ultimately, these reprocessing methods using Zr-based catalysts will impart greater sustainability and circularity to PU plastics.

Catalysts↗

Effect of Part Size, Displacement Rate, and Aging on Compressive Properties of Elastomeric Parts of Different Unit Cell Topologies Formed by Vat Photopolymerization Additive Manufacturing

Due to its ability to achieve geometric complexity at high resolution and low length scales, additive manufacturing (AM) has increasingly been used for fabricating cellular structures (e.g., foams and lattices) for a variety of applications. Specifically, elastomeric cellular structures offer tunability of compliance as well as energy absorption and dissipation characteristics. However, there are limited data available on compression properties for printed elastomeric cellular structures of different designs and testing parameters. In this work, the authors evaluate how unit cell topology, part size, the rate of compression, and aging affect the compressive response of polyurethane-based simple cubic, body-centered, and gyroid structures formed by vat photopolymerization AM. Finite element simulations incorporating hyperelastic and viscoelastic models were used to describe the data, and the simulated results compared well with the experimental data. Of the designs tested, only the parts with the body-centered unit cell exhibited differences in stress–strain responses at different part sizes. Of the compression rates tested, the highest displacement rate (1000 mm/min) often caused stiffer compressive behavior, indicating deviation from the quasi-static assumption and approaching the intermediate rate response. The cellular structures did not change in compression properties across five weeks of aging time, which is desirable for cushioning applications. This work advances knowledge on the structure–property relationships of printed elastomeric cellular materials, which will enable more predictable compressive properties that can be traced to specific unit cell designs.

36 MATERIALS SCIENCE↗