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At least 307 records · Page 17

Fundamentals of Polymer Crystallization in Laser Powder Bed Fusion for New Material Screening

Although laser powder bed fusion (PBF/LB) was one of the first industrially viable additive manufacturing (AM) methods for end-use part production, polyamides remain grossly dominant at both the commercial- and researchscale. The research community continues to develop and refine “rapid screening” methods for evaluating the suitability of a new polymer for PBF/LB. The so-called “SLS Process Window,” which is the difference between melting and crystallization temperature measured at 10 K min-1 as originally outlined in the patent literature, is perhaps the most often reported screening method. Although perhaps appropriate as part of a larger study, the simplistic guidelines put forth by the “SLS Process Window” are not sufficiently scientifically rigorous to understand how crystallization kinetics affects successful 3D printing. The common understanding of the SLS Process Window omits details from published theories of polymer crystallization. as evidenced by published assumptions and methods in PBF/LB process modeling papers. The authors explain polymer crystallization in the PBF/LB process context and propose replacing the “process window” with crystallization halftime and physical gelation for new material screening. These measurements better represent behavior critical for ensuring a lengthy coexistence of solid powder and molten polymer affecting warp-free parts.

CHATHAM, CAMDEN A.↗

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

36 MATERIALS SCIENCE↗

Challenges in Laser Sintering of Thermoset Imide Resin

Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.

Additive Manufacturing↗

Tailoring the Properties of Chemically Recyclable Polyethylene‐Like Multiblock Polymers by Modulating the Branch Structure

Abstract Developing plastics that fill the need of polyolefins yet are more easily recyclable is a critical need to address the plastic waste crisis. However, most efforts in this vein have focused on high‐density polyethylene (PE), while many different types of PE exist. To create broadly sustainable PE with modular properties, we present the synthesis, characterization, and demonstration of materials applications for chemically recyclable PE‐like multiblock polymers prepared from distinct hard and soft blocks using ruthenium‐catalyzed dehydrogenative polymerization. By altering the branching pattern within the soft blocks, a series of PE‐like multiblock polymers were synthesized with tunable glass transition temperatures ( T g ) while maintaining consistent high melting temperatures ( T m ). A clear U‐shape trend between T g and mechanical properties was found, showcasing their potential as sustainable materials with tailored properties spanning commercial linear low‐density polyethylene (LLDPE) and low‐density polyethylene (LDPE). These materials offer adjustable adhesive strength to metal and demonstrate chemical recyclability and selective depolymerization in mixed plastic streams, promoting circularity and separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isomeric bismaleimides and polyaspartimides

The properties of a series of bismaleimides and polyaspartimides synthesized from the 3,3', 3,4', and 4,4' isomers of diaminodiphenylmethane are described and compared. The effects of the amine isomerism on the characteristics of bismaleimides and their polymers are investigated. It is observed that the 3,3'-bismaleimide had the highest crystalline melting point, the 4,4' isomer the lowest, and the 3,4'-bismaleimide was slightly above the all-para compounds; for the polyaspartimides, the all-para combinations had the highest glass transition temperature (218 C) and the all-meta the lowest (168 C). The data reveal that strong, flexible films were obtained only from the polyaspartimides made from the 4,4'-diamine/4,4'bismaleimide and the 3,4'-diamine/3,4'bismaleimide combinations; and the tensile properties of the 3,4'polymer films were as good as those of the 4,4 'polymer.

Bell, Vernon L.↗

An Approach to Processable Polyimides

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Gariepy, Christopher A.↗

Self-healing polymers

A three dimensional structure fabricated from a self-healing polymeric material, comprising poly(ester amides) obtained from ethylene glycol, azelaic acid and 1,1-aminoundecanoic acid, wherein polymeric material has a melt index above 2.5 g/10 min. as determined by ASTM D1238 at 190.degree. C. and 2.16kg, impact resistance and ductility sufficient to resist cracking and brittle fracture upon impact by a 9 mm bullet fired at a temperature of about 29.degree. C. at subsonic speed in a range from about 800 feet/sec to about 1000 feet/sec. It has been determined that the important factors necessary for self-healing behavior of polymers include sufficient impact strength, control of the degree of crystallinity, low melting point and the ability to instantly melt at impacted area.

Klein, Daniel J.↗

Polyimidazopyrrolone model compounds.

Study of model reactions between phthalic anhydride and o-phenylenediamine under conditions analogous to the polymerization and post cyclization of dianhydrides with bis(o-diamines) to form polyimidazopyrrolones (Pyrrones). Solid-state thermal conversion of the amide-acid-amine affords a unique dimeric species containing amide, imide, and benzimidazole functions. It was confirmed that melt techniques lead to disproportionation products. The application of these findings to related polymer syntheses is discussed.

Young, P. R.↗

Polyimidazopyrrolone model compounds.

The model reactions between phthalic anhydride and o-phenylenediamine were studied under conditions analogous to the polymerization and post-cyclization of dianhydrides with bis(o-diamines) to form polyimidazopyrrolones (Pyrrones). The route from the initial amide-acid-amine to the tetracyclic Pyrrone model when the reactions are conducted in aprotic solvents is highly competitive between isolatable benzimidazole-acid and imide-amine intermediates. Solid-state thermal conversion of the amide-acid-amine affords a unique dimeric species containing amide, imide, and benzimidazole functions. It was confirmed that melt techniques lead to disproportionation products. The application of these findings to related polymer synthesis is discussed.

Young, P. R.↗

Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

Chuang, CHun-Hua↗

Neutron Reflectometry Reveals Diffusion in Contrast-Matched Brush Particle Bilayers

A material system for performing layer-spread experiments on brush particle bilayers is presented and used to determine the diffusion constant of brush particles in the melt state. Selective deuteration of the core and shell of organo-silica nanoparticles grafted with poly(methyl methacrylate) was used to match the scattering length density of the core and the polymer canopy layer. This subdued the scattering of particle cores (i.e., formfactor scattering) and enabled the analysis of the interdiffusion kinetics using neutron reflectivity. For low molecular grafts, i.e., grafts with a molecular weight below the entanglement limit, the interdiffusion kinetics revealed both a sub- and Fickian diffusion regime. The former was attributed to the local dynamics that was constrained by the slow-moving cores of neighboring brush particles that acted as long-lived physical cross-links. No transition to Fickian diffusion was observed for entangled systems, even at prolonged annealing times. This suggested a higher level of kinetic restraint in entangled brush particle melts as compared to, for example, star polymers with a comparable chain length for which Fickian diffusion has been reported under similar conditions.

Diffusion, Polymer Grafted Nanoparticles, Neutron ↗

Determinations of molecular weight and molecular weight distribution of high polymers by the rheological properties

Several methods are reviewed by which the molecular weight (MW) and the molecular weight distribution (MWD) of polymeric material were determined from the rheological properties. A poly(arylene ether) polymer with six different molecular weights was used in this investigation. Experimentally measured MW and MWD were conducted by GPC/LALLS (gel permeation chromatography/low angle laser light scattering), and the rheological properties of the melts were measured by a Rheometric System Four rheometer. It was found that qualitative information of the MW and MWD of these polymers could be derived from the viscoelastic properties, with the methods proposed by Zeichner and Patel, and by Dormier et al., by shifting the master curves of the dynamic storage modulus, G', and the loss modulus, G'', along the frequency axis. Efforts were also made to calculate quantitative profiles of MW and MWD for these polymers from their rheological properties. The technique recently proposed by Wu was evaluated. It was found that satisfactory results could only be obtained for polymers with single modal distribution in the molecular weight.

Huang, J. Y.↗

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal fields in the Bridgman-Stockbarger technique

Temperature measurements were made throughout a naphthalene melt and solid in a simulated Bridgman-Stockbarger apparatus. Heating and cooling were provided by agitated baths separated by a polymer diaphragm. While agitation was sufficient to give uniform temperatures in the baths, the level of agitation in the heater strongly influenced the results. Unlike theoretical results for high thermal conductivity materials, natural convection in the melt had a strong influence on interface position and on the temperature distribution. Isotherms were relatively flat in the solid and both curved and erratic in the melt. The interface became more convex as it was moved higher into the heating bath by raising either the heating bath or cooling bath temperatures. Using a one-dimensional model, the Biot number in the cooler was determined to be 0.03, that for the solid in the heater 0.008, and for the molten region in the heater 0.3. Biot numbers for two or three dimensional models would be significantly different.

Potts, H.↗

Hydrogen-Bonding Bottlebrush Networks: Self-Healing Materials from Super-Soft to Stiff

The impact of polymer architecture on network dynamics and self-healing is presented using bottlebrushes containing side chains that are end-functionalized with 2-ureido-4[1H]-pyrimidinone (UPy). The synthesis of these materials is straightforward through a three-step process: (1) synthesizing rubbery poly(4-methylcaprolactone) macromonomers (p4MCL–OH) with a norbornene-based initiator, (2) functionalizing the terminal hydroxyl group with UPy–isocyanate (p4MCL–UPy), and (3) statistically copolymerizing p4MCL–OH and p4MCL–UPy via ring-opening metathesis polymerization (ROMP) to form hydrogen-bonding bottlebrushes having a fraction (p) of side chains functionalized with UPy. Attaching UPy to the free end of bottlebrush side chains dilutes the impact of friction from complementary UPy interactions on segmental dynamics, leading to a much weaker dependence of the glass-transition temperature (T g ) on p than observed in linear analogues, while the activation energy to dissociate UPy–UPy bonds (41–47 kJ/mol) remains mostly unchanged. Longer side chains result in a competition between reducing T g and inducing entanglements that influence hydrogen-bonded network dynamics. Increasing the backbone length extends the sticky Rouse region without affecting the network modulus (G x ) or UPy–UPy dissociation time (τ s ). Gx scales linearly with p and ranges from 27 kPa to 1.6 MPa, while τs remains nearly constant in contrast to linear telechelic ionomers, implying a similar self-healability across bottlebrush networks containing different amounts of UPy. Furthermore, these stretchable networks with p ≤ 0.25 undergo self-healing upon repeated rupture and melt pressing at ≤100 °C while retaining similar tensile properties. In summary, decorating bottlebrush polymers with hydrogen bonds creates opportunities to independently manipulate associative network dynamics and mechanical moduli.

36 MATERIALS SCIENCE↗

Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability

Aliphatic polyamides, or nylons, are typically highly crystalline and thermally robust polymers used in high-performance applications. Nylon 6, a high-ceiling-temperature (HCT) polyamide from e-caprolactam, lacks expedient chemical recyclability, while low-ceiling temperature (LCT) nylon 4 from pyrrolidone exhibits complete chemical recyclability, but it is thermally unstable and not melt-processable. Here, we introduce a hybrid nylon, nylon 4/6, based on a bicyclic lactam composed of both HCT ..epsilon..-caprolactam and LCT pyrrolidone motifs in a hybridized offspring structure. Hybrid nylon 4/6 overcomes trade-offs in (de)polymerizability and performance properties of the parent nylons, exhibiting both excellent polymerization and facile depolymerization characteristics. This stereoregular polyamide forms nanocrystalline domains, allowing optical clarity and high thermal stability, however, without displaying a melting transition before decomposition. Of a series of statistical copolymers comprising nylon 4/6 and nylon 4, a 50/50 copolymer achieves the greatest synergy in both reactivity and polymer properties of each homopolymer, offering an amorphous nylon with favorable properties, including optical clarity, a high glass transition temperature, melt processability, and full chemical recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copolyimides With Flexibilizing Groups

Copolymers improved flexibility, processability and melt-flow characteristics. Copolyimide of new type exhibits synergistic improvements in flow properties due to flexibilized diamine-derived units incorported into polymer backbone. Technique produces copolyimides with combination of flexible linkage that cause polymers to exhibit flow properties particularly well suited for use in wide range of products including adhesives, molding resins, laminating resins, dielectric and protective coatings. Improved properties make copolymers especially useful as thermoplastic hot-melt adhesives.

St. Clair, Terry L.↗