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The physicomechanical and operational properties of glass-filled polyurethane obtained by long fiber injection molding (LFI) and fiber composite spraying (FCS) are investigated. It is clear that glass-filled polyurethane may be used in producing components with different surface texture (dashboard, door trim, armrests) in the auto industry.
The movement to transfer from petroleum-based products and materials to renewables does not necessarily have to bypass the use of oil. A new type of "black-gold" is readily abundant from the earth's most abundant source of aromatic carbon: lignin. While fractionation of petroleum yields fuels and chemicals for a diverse set of industries, lignin fractionation using targeted catalysts has demonstrated the ability to generate monomers and oligomers rich in functional groups for polymer synthesis. This study explores the use of lignin-oil, generated from reductive catalytic fractionation of popular wood, to a hydroxyl-rich mixture of aromatics that is used to synthesize a thermoplastic non-isocyanate polyurethane. The lignin-oil is first converted to a cyclocarbonated derivative using a benign synthetic sequence and further polymerized with a diamine to yield the non-isocyanate TPU. While more work is underway to optimize the reaction conditions and meet typical mechanical properties of commercial materials, initial analysis shows thermoplastic behavior and flexible properties consistent with traditional thermoplastic polyurethanes.
The purpose is to determine the mechanical properties of polyurethane foams with the intent of using PU foams to fill large void asymmetrical volumes like a glovebox to fixate transferable radiological material. Testing the resiliency of foam technologies when exposed to physicals stressors will be done. Six COTS PU foams considered will be fabricated and tested (iT 7, iT 8, iT 14, iT 23, 3M Fire Barrier, and Hilti) with and without additives at 12.5% wt (Bi, WO{sub 3}, and Na{sub 2}WO{sub 3}). Polyurethanes (PU) are a special class of polymeric materials that have great potential in many applications. Used in automotive, biomedical, construction, and textiles industries. Sought after due to its versatility and superior properties. PU foams have become one of the most prominent PU-based products. Bench-scale testing by SRNL and FIU-ARC confirmed PU foam technology's superior capabilities: Cured in various and desired volumes; No samples generated heat above 90 deg. C during curing reaction; Incorporation of additives (Bi, WO{sub 3}, BiO{sub 3}, Na{sub 2}WO{sub 3}) led to the following shielding: 98% of Am-241, 16% of Cs-137, 9.5% of Co-60. Proved foams' resistance to thermal stressors: Foams lasted 2 hours of direct flame; Excellent thermal insulation; Maintained structural integrity; No smoke or flame propagation. Experiment 1: A tensile tester (MTS Criterion Series 43) will be utilize to evaluate various properties of different PU rigid and flexible foams with and without additives (at 12.5% wt) under tension at 1 mm/s. Experiment 2: A thermogravimetric analysis (TGA) and Dynamic Mechanical Analyzer (DMA) will be employed to determine PU foams' breakdown of physical properties while under a constant heat rate (10 C/min) and strain rate (1%) under a period of time. Foams with additives showed an increase in stiffness and durability during tensile testing with WO{sub 3} producing the best results for Foam iT 7. All the other foam samples showed similar trends. Glass transition temperature (Tg) range for Foam iT 7 with Na{sub 2}WO{sub 3} ranged from 120-150 C while Foam iT 7 blank Tg range was from 90-110 C with a difference of about 30 C showing improvement with addition of additives.
Fixation of radiological contamination in decommissioning and deactivation can reduce worker risk, and mitigate potentially hazardous conditions; however, nearly every marketed contamination fixative has been found to be flammable, a significant concern in radiological facilities. Coupled with this, industry fixatives are normally used as a thin coating which can present problems when attempting to stabilize irregular void spaces or areas that are difficult to access and ensure full coverage. To this end, Savannah River National Laboratory (SRNL), in conjunction with Florida International University (FIU), have begun investigating the applicability of polyurethane based foaming materials, which will expand to fill a given asymmetric volume and provide fire retardancy to ensure no release of contamination in the event of a facility fire. Commercial foams undergo exothermic reactions resulting in gaseous release that subsequently causes the curing foam material to expand. Heat generation during curing can potentially compromise rubber parts of an enclosure, a significant concern in nuclear facilities. To mitigate large body heat generation, SRNL has also examined multiple layering of the material to ensure compatibility of the curing material with a previously cured body of the same material. Environmental studies were also completed in order to determine the influence on polyurethane based foams curing process. These studies showed that nearly half of the materials tested delaminated from a cured body of the same material, a property not discussed in commercially available documentation on the products. Of note was the compatibility of the foaming material with the substrate, depending on the type material that the foam was cured in/on, significant delamination could occur. Mechanical testing via tensile pull tester, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA) was also performed. (authors)
Abstract Polyurethane foams are widely used materials often chosen for their useful characteristics such as low thermal conductivity, ease of application, and high strength‐to‐weight ratios. Computational models are needed to predict the dynamics of the flow and expansion, and the resulting material properties, to improve manufacturing processes. In this paper, a model for PMDI, a water‐blown polyurethane foam, is presented. By extending a kinetics‐based approach by adding bubble‐scale information via a population balance equation (PBE) using the quadrature method of moments, we can track bubble size distributions during foaming. We present results from a three‐dimensional computational fluid dynamics model using arbitrary Lagrangian–Eulerian interface tracking implemented in finite element software. The model compares favorably with experimental data, including dynamics, bubble distributions measured by both camera and diffusion wave spectroscopy, and post‐test bubble size from scanning electron microscopy and density measurements from x‐ray computed tomography.
Many energy absorption applications utilize flexible polymeric foams for their viscoelastic properties. It is desired that the material will perform consistently across repeated compression cycles. This study examines the effect of fatigue at low strain rates on the viscoelasticity of open-cell polyurethane foam. Six polyurethanes of the same base composition with two porosities (70% and 80%) and three chemical indexes (79i, 100i, and 121i) are tested. Large deformation cyclic compression of the foams is conducted on a universal testing system (UTS). These data are then post-processed leveraging dynamic mechanical analysis Fourier transform rheology to characterize changes in the viscoelasticity of the materials over fatigue cycles. Results show that foams can increase or decrease in stiffness up to 10% over 10 4 cycles. Specifically, higher chemical index, higher excitation frequency, and larger excitation amplitude correlate with a more pronounced decrease in stiffness. Damping can also change by 15% and correlates with chemical index and excitation frequency. Consequently, the findings suggest that internal foam structure and bulk material properties as well as applied loading parameters affect the viscoelastic fatigue response of flexible polymeric foams.
Abstract Polyurethane foam (PUF) can absorb sound by air friction and structural vibrations of cell walls. It is widely used as acoustic material in the automotive industry. According to existing studies, graphene oxide (GO) can improve the acoustic properties of PUF. However, GO tends to coalesce inside PUF. In this paper, straw fibers were modified with different concentrations of GO solution to embed GO on the surface of plant fibers. The GO was dispersed in the PUF using straw fibers. In addition, some studies show that the wrinkled morphology of the GO surface is believed to play a mechanical interlocking role in improving interfacial bonding, thus enhancing the stress transfer between the plant fibers and the polyurethane (PU) matrix and improving the mechanical properties of the PU composites. The acoustic and mechanical properties of the modified PU materials were observed by treating plant fibers with appropriate amounts of GO solution. The experimental study shows that the sample modified with 1 g L −1 GO solution reaches a maximum average sound absorption coefficient of 0.5838 when the straw fiber content reaches 0.5 g, and the sample modified with 2 g L −1 GO solution reaches a maximum transmission loss of 10.5333 when the straw fiber content reaches 1 g. © 2022 Society of Industrial Chemistry.
The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance ({sup 1}HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and {sup 1}HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.
Lignin and castor oil with intrinsic hydroxyl groups are attractive green resources for polyurethane (PU) applications. However, lignin's heterogeneous and highly crosslinked structure, poor processability, as well as the feedstock variability, lead to inconsistent and poor performance of the final foam products. Castor oil-based polyurethane foam (PUF) has a relatively high price and density, which are big hurdles to its practical applications. Here, in this study, we hypothesized that synergistic bio-polyol mixtures composed of lignin and castor oil could balance the drawbacks from individual component. Castor oil could improve the dispersity of lignin, while lignin simultaneously addressed the issues caused by PUF prepared with castor oil, such as its high density and low thermal stability. For a comprehensive understanding of the effects of structural properties of lignin on its PUF processing and applications, various lignin fractions were isolated by co-solvent enhanced lignocellulosic fractionation (CELF) from different species, including hardwood, softwood, and herbaceous plants, and the processed lignins with different molecular weights were applied with castor oil. The lignin fractions with lower molecular weight showed good dispersity in castor oil with a high lignin content (up to 50 wt%) and completely replaced petroleum-based polyols. The produced foam with 50 wt% low-molecular-weight lignin fractions from woody biomass showed comparable/higher compressive strength (up to 20 psi) and thermal insulation performance (up to 5.69 R-value in −1 for 50 % L-Pine foam). In addition, this study revealed the relationship between lignin's structural properties and foam performance, providing insights for practical applications of lignin-based PUF.
Conformal coatings with higher adhesion strength is critical for mitigating the growth of whiskers from the pure tin (Sn) or Sn-rich surfaces of the Pb-free electronics. Silane coupling agents have the ability to form a durable bond between polymeric coatings and metallic materials. The main goal of this paper is to investigate the effect of silane agents on the adhesion behavior of polyurethane (PU), polyurethane acrylate (PUA) and both coatings filled with silicone rubber (SR) nanoparticles on the tin solder pads. It was found that an isocyanate-based silane provided excellent adhesion for PU and PU + SR coatings and an acrylic-based silane for PUA and PUA + SR coatings on the tin surface. This was due to the reaction bond formation between the silane coupling agent and the coating. Hence, the selection of silane coupling agents with the organofunctional group similar to the coating material is crucial to improve the adhesion properties of the coating.
Despite decades of research, connecting the chemical and physical structure of thermoplastic polyurethanes to their mechanical properties remains highly challenging. Of particular note are their large-deformation and rate-dependent behaviors, which vary greatly with molecular chemistry, including the type and relative content of soft and hard segments. In this work, we develop a physically motivated mechanical theory for predicting the behavior of thermoplastic polyurethanes. The theory incorporates a representation of microstructural evolution during mechanical deformation, which captures the signatures of stress softening over cyclic loading (commonly referred to as the Mullins effect). There are only eight physically motivated fitting parameters, including a direct dependence on the hard segment fraction. The model predicts that increasing the hard segment fraction leads to higher stiffness and greater energy dissipation, in quantitative agreement with published experimental data. Furthermore, we provide a comprehensive analysis of the model and validate its predictions across several independent datasets focused on mechanical characterization. Direct comparisons to experimental data demonstrate its predictive capability on the effect of loading rate, cyclic deformations, and applied tension or compression. Altogether, this work establishes a predictive framework that connects polymer chemistry and microstructure to emergent mechanical behaviors.
In the present study, glass-epoxy composites were used as a substrate to study the performance of modified polyurethane coating. Two-layer coating (180–200 µm) wherein the epoxy primer as the first coat and polyurethane as the top coat was applied using an air-assisted spray gun to increase the service life of the composite. The analysis of coating was performed using gloss, contact angle, FTIR, TGA, tensile test and SEM. The bonding strength between coating and substrate was evaluated by cross-hatch cut, 180 deg peel strength and pull-off adhesion tests. Scratch, Taber abrasion and Pin-on-disc tests were also performed to evaluate the wear resistance. In addition, a rain erosion test was performed to check the stability of the coating. From the above tests, it is concluded that the applied coating well adhered to the composite substrate. The data generated from different tests can be used to estimate the service life of polymer composites and coatings.
Polymer-based solid-state electrolytes are promising for next-generation lithium metal batteries, yet their limited ionic conductivity and mechanical stability at ambient conditions remain key challenges. Herein, we report a novel gradient crosslinked polymer electrolyte (PU/PUA/PU) synthesized via a sequential in situ UV-curing process that integrates a mechanically robust polyurethane acrylate (PUA) core with soft linear polyurethane (PU) interfaces. This all-solid membrane operates without any liquid plasticizer and the interfacial PU layers ensure low interfacial resistance and intimate electrode contact, while the PUA core provides enhanced dimensional stability and dendrite suppression. As a result, the gradient electrolyte delivers an impressive ∼2.6 × 10 −4 S cm −1 ionic conductivity at 25 °C (two orders of magnitude higher than conventional PEO) and remains electrochemically stable >5 V (vs Li + /Li). Structural analysis confirms the formation of a well-defined crosslinked network with suppressed crystallinity and expanded interchain spacing. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) further validate these properties. When applied in a Li||NMC811 cell, the PU/PUA/PU electrolyte delivers stable cycling with high capacity at both 60 °C and 25 °C, demonstrating its potential for room-temperature solid-state battery applications without reliance on plasticizers or heating. In conclusion, this gradient design offers a practical path toward ambient-condition operation of solid-state lithium batteries, providing a paradigm for overcoming the traditional trade-off between ionic conductivity and mechanical robustness.
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.
The thermal degradation of two polyurethane elastomers was investigated via thermal gravimetric analysis coupled with gas chromatography/ma ss spectrometry. Decomposition occur s in a multi - step fashion with similar onset temperatures for both materials. Apparent activation energy plots were calculated inside Model - Free Kinetics software and utilized to construct conversion and isothermal conversion tables . These tables predicted material degradation as a function of temperature and time. Isothermal experiments were performed and found to be in good agreement with the predictions made from the Model - Free Kinetic s software package. Volatile products evolved during the multistep decomposition were captured at various times and analyzed using the coupled gas chromatography/mass spectrometry system . This analysis demonstrated strong correlation between the degradation products and known decomposition mechanisms for polyurethanes.
The implementation of polyurethane foams as a permanent fixative for radioactive contamination is currently being examined within the DOE complex for its use in decontamination and decommissioning (D&D) activities. The work involving the implementation of permanent foaming fixatives in a decontamination scenario would include the filling of structures with large voids, such as gloveboxes, pipes, and tanks, where the use of a traditional 2D paint fixative is impractical or unsafe. The mechanical performance of such commercial off the shelf permanent foaming fixatives is uncharacterized with response to harsh environmental conditions often found in nuclear facilities that are undergoing D&D. To this end, SRNL embarked on a mechanical characterization of 6 polyurethane foams, 4 of which were considered flexible and 2 of which were rigid. Two tests were performed on these foams; a tensile tearing test and a compressive test, both of which were strictly guided by ASTM standards. It was found that in both harsh compressive and tensile scenarios, the Hilti brand foam outperformed all other foams, having a peak stress value higher than the closest competitor by a factor of 2.3, and a compressive yield point that was larger than the closest competitor by a factor of 1.4.
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.
Polyurethane foam is used as a thermal insulator, fire protective material, and impact absorber in the 9977 shipping package. The 9977 shipping package is used to transport special nuclear materials (SNM), and store SNM in the K-area complex at the Savannah River Site. The primary fire-retardant mechanism in the foam is that it produces intumescent char when exposed to high temperatures. Intumescence occurs in the direction of heat application and can allow the foam to “repair” cracks in the event of a mechanical impact, in addition to serving as a secondary thermal barrier with decreased heat conductivity. Because the foam is being used for long-term storage applications, it is vital that it retain its physical, thermal, and mechanical properties over the course of time and with the events of exposure of heat and irradiation. The goal of this project was to determine the effects of gamma irradiation on the thermal properties of polyurethane foam, both in terms of cumulative irradiation and rate of irradiation. At the dose rates and cumulative doses of irradiation measured, there was no correlation between higher cumulative irradiation and thermal stability, specific heat capacity, or chemical structure. Based on the results of the experiments, the fire protective properties in the 9977 shipping containers should be retained with the expected amount of radiation exposure.