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At least 109 records · Page 6

Power assist EVA glove development

Structural modeling of the EVA glove indicates that flexibility in the metacarpophalangeal (MCP) joint can be improved by selectively lowering the elasticity of the glove fabric. Two strategies are used to accomplish this. One method uses coil springs on the back of the glove to carry the tension in the glove skin due to pressurization. These springs carry the loads normally borne by the glove fabric, but are more easily deformed. An active system was also designed for the same purpose and uses gas filled bladders attached to the back of the EVA glove that change the dimensions of the back of the glove and allow the glove to bend at the MCP joint, thus providing greater flexibility at this joint. A threshold control scheme was devised to control the action of the joint actuators. Input to the controller was provided by thin resistive pressure sensors placed between the hand and the pressurized glove. The pressure sensors consist of a layer of polyester film that has a thin layer of ink screened on the surface. The resistivity of the ink is pressure dependent, so an extremely thin pressure sensor can be fabricated by covering the ink patch with another layer of polyester film and measuring the changing resistance of the ink with a bridge circuit. In order to sense the force between the hand and the glove at the MCP joint, a sensor was placed on the palmar face of the middle finger. The resultant signal was used by the controller to decide whether to fill or exhaust the bladder actuators on the back of the glove. The information from the sensor can also be used to evaluate the effectiveness of a given control scheme or glove design since the magnitude of the measured pressures gives some idea of the torque required to bend a glove finger at the MCP joint. Tests of this actuator, sensor, and control system were conducted in an 57.2 kPa glove box by performing a series of 90 degree finger bends with a glove without an MCP joint assembly, a glove with the coil spring assembly, and with the four fingered actuated glove. The tests of these three glove designs confirm the validity of the model.

Main, John A.

Space Station WP-2 application of LDEF MLI results

The Cascaded Variable Conductance Heat Pipe Experiment, which was developed by Michael Grote of McDonnell Douglas Electronic Systems Company, was located in Tray F-9 of the Long Duration Exposure Facility (LDEF), where it received atomic oxygen almost normal to its surface. The majority of the tray was covered by aluminized Kapton polyimide multilayer insulation (MLI), which showed substantial changes from atomic oxygen erosion. Most of the outermost Kapton layer of the MLI and the polyester scrim cloth under it were lost, and there was evidence of contaminant deposition which discolored the edges of the MLI blanket. Micrometeoroid and orbital debris (MM/OD) hits caused small rips in the MLI layers, and in some cases left cloudy areas where the vapor plume caused by a hit condensed on the next layer. The MLI was bent gradually through 90 deg at the edges to enclose the experiment, and the Kapton that survived along the curved portion showed the effects of atomic oxygen erosion at oblique angles. In spite of space environment effects over the period of the LDEF mission, the MLI blanket remained functional. The results of the analysis of LDEF MLI were used in developing the standard MLI blanket for Space Station Work Package-2 (WP-2). This blanket is expected to last 30 years when exposed to the low Earth orbit (LEO) environment constituents of atomic oxygen and MM/OD, which are the most damaging to MLI materials. The WP-2 standard blanket consists of an outer cover made from Beta-cloth glass fiber fabric which is aluminized on the interior surface, and an inner cover of 0.076-mm (0.003-in) double-side-aluminized perforated Kapton. The inner reflector layers are 0.0076-mm (0.0003-in) double-side aluminized, perforated Kapton separated by layers of Dacron polyester fabric. The outer cover was selected to be resistant to the LEO environment and durable enough to survive in orbit for 30 years. This paper describes the analyses of the LDEF MLI results, and how these results contributed to the selection of the WP-2 MLI blanket materials and configuration.

Smith, Charles A.

Mechanical Behavior of Fabric-Film Laminates

Inflatable structures are gaining wide support in planetary scientific missions as well as commercial applications. For such applications a new class of materials made of laminating thin homogenous films to lightweight fabrics are being considered us structura1 gas envelops. The emerging composite materials are a result of recent advances in the manufacturing cf 1ightweight, high strength fibers, fabrics and scrims. The lamination of these load-carrying members with the proper gas barrier film results in wide range of materials suitable for various loading and environmental conditions. Polyester - based woven fabrics laminated to thin homogeneus film of polyester (Maylar) is an example of this class. This fabric/ film laminate is being considered for the development a material suitable for building large gas envelopes for use in the NASA Ultra Long Duration Balloon Program (ULDB). Compared to commercial homogeneus films, the material provides relatively high strength to weight ratio as well as better resistance to crack and tear propagation. The purpose of this papers is to introduce the mechanical behavior of this class of multi-layers composite and to highlight some of the concerns observed during the characterization of these laminate composites.

Said, Magdi S.

Special Considerations in Selection of Fabric Film Laminates for Use in Inflatable Structures

Inflatable structures are gaining wide support in planetary scientific missions as well as commercial applications. For such applications a new class of fabric/film laminates is being considered for use as a structural gas envelope. The emerging composite materials are a result of recent advances in the manufacturing of lightweight, high strength fibers, fabrics and scrims. The lamination of these load-carrying members with the proper gas barriers results in a wide range of materials suitable for various loading and environmental conditions. Polyester-based woven fabrics laminated to thin homogenous film of polyester are an example of this class. This fabric/film laminate is being considered for the development of a material suitable for building large gas envelopes for use in the NASA ultra long duration balloon program (ULDB). Compared to commercial homogenous films, the material provides relatively high strength to weight ratio as well as better resistance to crack and tear propagation, The mechanical, creep and viscoelastic properties of these fabric film laminates have been studied to form a material model. Preliminary analysis indicates that the material is highly viscoelastic. The mechanical properties of this class of materials will be discussed in some details.

Said, Magdi A.

Laboratory Analysis of Polymer Thin Films for Planetary Balloons and Gossamer Structures

Commercially available polymer thin fdms with thickness of 15 microns or less were evaluated for potential application as the gas envelope material of balloons and other inflated vehicles. Films on this thickness scale are of interest for Earth and Mars ballooning as well as many gossamer space structures. Due to the uniqueness of these missions relative to typical uses of these materials, application-specific materials properties measurements were made. We evaluated numerous polymer chemistries, plus a few variations within one chemistry. The data show that there are often trade-offs among the different materials, such as with polyesters and polyimides having greater stiffness (modulus) but lower tear propagation resistance than polyethylene. Sections of polyethylene films can be joined by heat sealing, while adhesives and their accompanying mass penalty must be used with polyesters and polyimides. When the analysis temperature is reduced to 190 K, polyethylenes display dramatically increased stiffness and yield point, while the increase for other materials is more modest. The data also show that manufacturing processes can significantly affect film properties. To emphasize the need for application-specific properties assessment, we discuss two recent applications using these materials.

Sterling, Jerry

Storage, Preservation, and Recovery of Magnetic Recording Tape

During the 1970's, a commercial magnetic recording tape fabricated with magnetic oxide particles, and with oxide and backcoat binders made from polyester urethane was being used for spacecraft tape recorders, and which would periodically manifest operational problems such as layer-to-layer adhesion, stick-slip, and shedding of sticky organic materials. These problems were generally associated with periods of high humidity. An experimental study identified that these problems resulted from hydrolysis of the polyester urethane binders.

Magnetic Recording Tape

Pyrolysis Rate and Yield Strength Reduction Incarbon Fiber and Glass Fiber Composites Underreentry Heating Conditions

The behavior of composite materials, specifically carbon fiber reinforced plastic (CFRP) and glass fiber reinforced plastic (GFRP), under reentry conditions poses a problem for space debris reentry risk modeling. Since these materials pyrolyze rather than melt and their different components demise at different rates, modeling their destruction to determine ground impact risk is complex. Modern spacecraft are using these materials in ever-greater quantities owing to their superior strength-to-weight characteristics, and this has required that the orbital debris community improve its understanding of how these materials demise on reentry. The NASA Orbital Debris Program Office undertook an extensive test campaign to better understand the rate at which several types of GFRP and CFRP materials pyrolyze under reentry heating conditions and how that pyrolysis affects the ultimate strength of the material. GFRP with a polyester resin (G10/FR-4) and CFRP with epoxy, cyanate ester, vinyl ester, and phenolic resins were tested. The test campaign was carried out at the Inductively Coupled Plasma (ICP) Torch Facility at the University of Texas at Austin. Because the ICP facility operates in a shirt-sleeve environment, test samples can be changed within seconds or minutes, allowing many samples to be tested in a short period. Two heat flux rates, 20 W/m2 and 30W/m2, and two oxygen concentration conditions, 0% and 2% of atmospheric, were applied to all five types of material. To measure both the char rate and the effect of pyrolysis on the ultimate material strength, two types of test were carried out for each material: a char rate test on a ~10 mm thick sample of material and an in-situ bending stress test of a ~2 mm thick sample of material. Measurements of the char rate showed very similar average pyrolysis front velocity in epoxy resin CFRP as in G10 at 3.6 mm/min and 3.4 mm/min, respectively. However, the total mass loss rate in theG10 was nearly double that of the CFRP at 3.8 g/min and 2.2 g/min, respectively. This result represented a slow ablation rate of carbon fibers in the CFRP at the temperatures encountered in low Earth orbit reentry and a comparatively rapid removal of the glass fibers in G10 due to melting and spallation. Pyrolysis front velocity was more significantly affected by the type of plastic than the type of fiber, with the cyanate ester CFRP samples displaying an average pyrolysis front velocity of only 1.9 mm/min. Similarly, the effect of thermal exposure on the ultimate strength of the material depended heavily on the type of plastic and very little on the type of fiber in the material. Epoxy, vinyl ester, and polyester resins all behaved very similarly, with complete structural failure at between 400 J/g and 600 J/g of specific absorbed heat. Phenolic and cyanate ester resins, on the other hand, displayed a change in structural properties that was only barely measurable with the current apparatus even after the maximum exposure time tested. These data are being incorporated into a numerical model of the ablation and demise of composite materials that will be used to more accurately calculate the ground casualty risk of future spacecraft.

Benton R. Greene

Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate–co–terephthalate)

Traditionally, most flexible food packaging is made of linear low-density polyethylene (LLDPE) which cannot easily be recycled, nor will it degrade in a reasonable timescale. In this work, a biobased biodegradable polyester alternative was investigated as a possible replacement for LLDPE. High molecular weight poly (pentylene adipate-co-terephthalate) with a 40/60 adipic acid/terephthalic acid mole ratio was synthesized using direct esterification and polycondensation. Glycerol and hexane-1,2,5,6-tetrol were added as branching agents to better match the structure of the LLDPE which in turn might help the ability of these materials in film-blowing. Thermal, mechanical, and rheological properties of the copolyesters were thoroughly investigated. All copolyesters had a weight-average molecular weight of over 140,000 g/mol, which is necessary for proper rheology, and were thermally stable up to 350°C. Here, the addition of branching agents led to a slight decrease in crystallinity, d-spacing, melting temperature, enthalpy of melting, stress at break, and elongation at break. However, an increase in Young's modulus and complex viscosity at high frequency were observed compared to PPeAT60 without branching agent added. Although the improved crystallinity and mechanical properties of the copolyesters made them viable for film-blowing, the slow crystallization rate creates a major challenge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Extraction of high-purity medium-chain-length polyhydroxyalkanoates via combined mechanical treatment and mild oxidation

Polyhydroxyalkanoates (PHAs) are a class of polyester polymers of microbial origin and considered biodegradable alternatives to conventional plastics. To make PHAs cost-competitive with synthetic plastics, their production cost, including extraction cost, should be significantly reduced. Herein, this study aimed to develop an effective extraction method based on combined mechanical disruption and chemical treatment for the recovery of high-purity medium-chain-length PHAs (mcl-PHAs) at a lower cost. mcl-PHAs-accumulating Pseudomonas strains were used for PHA extraction via high-pressure homogenization (HPH) coupled with surfactant treatment and mild alkaline hydrogen peroxide oxidation. The mechanical-chemical method was found to have strong synergy for PHA extraction while minimizing PHA depolymerization. The optimized condition resulted in nearly 90 % mcl-PHA recovery with high purity (>91 %). The extracted high-purity PHAs exhibited thermal and mechanical properties suitable for downstream applications entailing flexible and elastomeric materials.

42 ENGINEERING

Tailoring High Hardness and Rigidity in Biodegradable Thermoplastic Polyurethanes

In response to escalating environmental concerns, there is a pressing demand for materials capable of delivering both sustainability and robust mechanical properties, thereby substituting nonrenewable counterparts in various applications. This study presents a comprehensive investigation into the synthesis and characterization of biobased aliphatic thermoplastic polyurethanes (TPUs) that exhibit impressive mechanical properties, including tensile strength in the range of 48–41 MPa and flexural modulus up to 2.2 GPa. These biodegradable TPUs displayed high shore A and D hardness between 95 and 98 and 51–42, respectively, and thus can be categorized as “extra hard” plastics according to the durometer scale for PUs. Herein, we have prepared a series of four 100% biobased polyester polyols from biobased diacid and chain-extender as precursors with molecular weights varying from 500 to 1400 g/mol. The corresponding TPUs that were prepared by using an aliphatic diisocyanate were evaluated for their thermal stability, microphase separation, mechanical properties, and biodegradation. By leveraging renewable feedstocks, these TPUs offer a sustainable alternative to petroleum-derived materials, with their mechanical performance meeting conventional benchmarks. Furthermore, postcomposting analysis revealed significant surface degradation, affirming their biodegradability and environmental compatibility.

36 MATERIALS SCIENCE

Tunable PA6 Polymer System for Thermoplastic Reinforced Body Panels

Project Goal: Overall, a redesigned polyamide system will combine the ductility and processing of a PA6 matrix, the strength and modulus of CF, and the facile recyclability of esters. Approach: PEA can be synthesized under conventional, industrially relevant pathways. Material properties and processing will be analyzed and compared to commercial PA6 material. Results: Polycondensation, traditional for polyesters, was successful in synthesized a PEA. PEA exhibited fast crystallization and bimodal melting behavior suggesting beneficial crystallization kinetics. PEA exhibit reduced melting temperatures owed to the incorporation of ester units in the polymer structure.

42 ENGINEERING

Stereochemically‐Controlled Fluorinated Copolymers for Selectively Permeable Barrier Applications

Selective oxygen permeability coupled with low water vapor transmission is essential for biomedical and packaging applications requiring controlled oxygen flux under humid conditions. However, most high‐performance barrier polymers depend on perfluoroalkyl substances (PFAS), whose persistence and regulatory restrictions limit their long‐term applicability. We designed a series of stereocontrolled thiol‐yne‐based polyesters, including both fluorinated and non‐fluorinated variants, for selective oxygen permeability with considerable water barrier performance. Tailoring polymer crystallinity and morphology tuned both oxygen transport and mechanical properties. Fluorinated polymers demonstrated enhanced hydrophobicity and water resistance while maintaining oxygen diffusivity within a range relevant to oxygen‐sensing applications. Structure–property relationships were elucidated through small‐ and wide‐angle X‐ray scattering, revealing semi‐crystalline domains influenced by fluorine content and dithiol chain length. Barrier performance was rigorously evaluated via water vapor transmission rate and dynamic vapor sorption, showing reduced water uptake with increasing dithiol monomer length and crystallinity. In conclusion, this work introduces a PFAS‐free alternative to conventional barrier materials and establishes a tunable materials platform with potential relevance for biomedical devices and packaging systems requiring controlled oxygen permeability.

36 MATERIALS SCIENCE

Latent Catalysis as a Platform for Accessing Diverse Material Properties in Vat Photopolymerization 3D Printing

Vat photopolymerization (VP) 3D printing is an attractive strategy to manufacture customized polymer parts. The properties of printed materials are limited by the need to employ a low viscosity liquid resin and achieve rapid polymerization kinetics. To circumvent this limitation, dual‐cure methods have been developed using reagents embedded in the liquid resin formulation; however, the reagent‐based approach requires the discovery and optimization of new chemistry for each desired material. Here, in this work, we demonstrate a catalytic, dual‐cure platform that enables access to both Nylon‐6 and polyester interpenetrating networks through VP 3D printing under a universal approach. Structure–reactivity relationships of the latent NHC catalysts led to the identification of a magnesium chloride–NHC adduct as a latent catalyst that is orthogonal to radical polymerization and can be unmasked at elevated temperatures post‐printing to initiate ring‐opening polymerization of lactones and lactams. This strategy results in access to semicrystalline materials, which are a challenging morphology to access via VP 3D printing, that have attractive mechanical properties and can be printed at high resolution. This work represents the first photochemical‐based 3D printing of Nylon‐based materials and demonstrates the value of catalytic approaches to access new material properties in VP 3D printing.

Colliver, Cali N. [University of North Carolina, C

Closed‐Loop Recycling of Poly(pentylene Adipate‐ co ‐Terephthalate) via Amine‐Catalyzed Methanolysis

Advancing circularity through effective chemical recycling strategies is essential for enabling the sustainable use of emerging biodegradable polyesters in film applications. In this context, poly(pentylene adipate-co-terephthalate) with a 40/60 adipate-to-terephthalate ratio (PPeAT60), a significantly stiffer and partially biobased copolyester recently reported by our team, offers improved mechanical performance and processability compared to commercial poly(butylene adipate-co-terephthalate), while providing a platform to evaluate advanced recycling approaches for film applications. Here, this study describes depolymerization of PPeAT60 through amine-catalyzed methanolysis, followed by the repolymerization of the recovered monomers. The resulting repolymerized material exhibited a molar mass distribution, chemical structure, and thermal stability comparable to the virgin polymer, confirming the technical feasibility of the methanolysis-based recycling route. Both polymers displayed nearly identical melting, glass transition, and decomposition temperatures, crystallinity, and modulus, demonstrating full structural and mechanical reproducibility after recycling. Variations in crystallization kinetics, elongation at break, and barrier properties likely arise from trace impurities (<1%) introduced during processing acting as nucleating and stress-inducing agents. Overall, these results demonstrate that PPeAT60 retains its key properties after chemical recycling, establishing methanolysis as a promising platform for recycling of this partially biobased polymer that may be able to replace both conventional polyolefins and PBAT in flexible packaging applications.

09 BIOMASS FUELS

Hierarchically Structured Vitrimer Biocomposites for Sustainable Manufacturing

Polymers containing dynamic covalent bonds (DCBs) exhibit thermoplastic-like flow above their topology freezing temperature (T v ) while maintaining thermoset-like properties below it, making them promising for sustainable manufacturing. However, their large-scale adoption remains limited due to challenges in accurately determining T v and achieving efficient fiber-matrix bonding in composite applications. Here, hierarchically structured epoxy-anhydride-based polyester vitrimer composites reinforced with cellulosic filaments is demonstrated, where hydroxyl groups on fiber surfaces participate directly in transesterification with the matrix. Further, this dynamic interfacial bonding delivers exceptional mechanical properties, including ≈70 MPa shear strength and >10% strain-to-failure, while enabling thermal malleability. Using a combination of nuclear magnetic resonance and nano-infrared spectroscopies, direct evidence is provided that chemical bond exchange begins well below the conventionally measured T v , supporting the hypothesis that rheologically determined T v reflects a combination of chemical exchange and frictional dynamics rather than a discrete transition. The composites demonstrate excellent processability through vacuum-assisted resin transfer molding and maintain >90% of their mechanical properties after multiple thermal reforming cycles. These findings advance both the fundamental understanding of vitrimeric transitions and the practical development of sustainable, high-performance composite materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Structure-dependent mechanisms for plastic degradation in the marine environment

The visible and invisible accumulation of waste plastic in our oceans is a consequence of rapidly increasing inputs and very slow degradation rates. In general, this combination of effects results in long residence times. Nevertheless, the abiological degradation rate of a specific synthetic plastic varies widely, depending on its structural characteristics at the molecular, mesoscopic, and macroscopic levels. This chapter summarizes factors that determine these rates of degradation, and describes their principal mechanisms, for several of the major types of waste plastic found in the oceans. Mechanical forces cause cracking and flaking that break macroplastics into microplastics and even smaller fragments with increasing surface-to-volume ratios. Chemical degradation rates increase with surface area, influenced by intrinsic variations in crystallinity and the presence of additives, as well as extrinsic factors such as temperature, pH, and UV light intensity. Since polyolefin-based plastics are less dense than seawater and lack hydrolysable bonds in their polymer backbones, they accumulate close to the surface of the ocean where photo-oxidation is the principal cause of C–C bond cleavage in the polymer backbone. In contrast, polyesters and polyamides are denser than seawater and they sink, experiencing less exposure to solar irradiation. However, they can also degrade by slow hydrolysis of the C–O or C–N bonds intrinsic to the polymer structures.

Maciulis, Nicholas A.

Catalytic production of δ-valerolactone (DVL) from biobased 2-hydroxytetrahydropyran (HTHP) – Combined experimental and modeling study

δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO 2 without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH rxn and ΔG rxn ) of each competing reaction using density functional theory (DFT) calculations at the M06-2X/cc-pVTZ level. Finally, by developing a kinetic model of all 8 reactions involved, we have achieved 84% selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.

42 ENGINEERING