Shock-wave pressure decay in polycarbonate targets impacted by cylindrical polycarbonate projectiles
Shock wave pressure decay in polycarbonate targets impacted by hypervelocity cylindrical projectile
Di Battista, J. D.↗
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Microwave-Assisted Production of Polycarbonate Diols using Carbon Dioxide
Carbon dioxide (CO2) is a cheap and readily available resource that can be converted to value-added chemicals including fuels, polymers, and other products. One lucrative option is polycarbonate diols, which are the precursor to polyurethanes that find wide applications in automotive and aerospace industries. The traditional process for the synthesis of polycarbonate diols involves using hazardous phosgene and alcohols in a strongly basic medium that generates significant amounts of salt. Alternately, CO2 can be reacted with alkanediols over CeO2 catalysts to produce polycarbonate diols. For the current work, a microwave-assisted atmospheric flow system was investigated for converting CO2 into polycarbonate diols and was compared against a thermal system. Various parameters such as type and ratio of solvents, and the addition of dehydrating agents for the microwave system was tested. The different CeO2 catalysts used were characterized using Brunauer–Emmett–Teller (BET) surface area analysis, Raman spectroscopy, X-ray diffraction, and temperature programmed desorption (NH3-TPD and CO2-TPD).
CO2 utilization↗
Chemically and Mechanically Recyclable Vitrimers from Carbon Dioxide-Based Polycarbonates
Designing thermoset materials with dynamic crosslinks is an important strategy to mitigate rising global carbon dioxide emission levels. The development of polymers from sustainable feedstocks, with efficient manufacturing methods, for high-value applications, and with circular end-of-use solutions is essential for advancing material technologies. One approach involves exploiting carbon dioxide itself as feedstock to create high performance, sustainable materials, by enchaining 50 mol% CO2 via copolymerization with epoxides to yield polycarbonates. This work describes the synthesis, end-functionalization, and curing of poly(propylene carbonate) (PPC) and poly(cyclohexene carbonate) (PCHC) into beta-hydroxy ester vitrimers. These vitrimers demonstrate the ability to be mechanically reprocessed up to 3 times with retention of the material’s properties through dynamic transesterification exchange reactions. The polycarbonate vitrimers with gel fractions exceeding 90 % exhibit high tensile strength (> 50 MPa) and Young’s modulus (> 2 GPa), achieved by varying repeat unit structure in the polymer backbone from the low Tg PPC to the more rigid high Tg PCHC structures. Owing to an entropically favorable chain back-biting mechanism, the network chains can be cleaved and depolymerized into cyclic small molecules. In the case of PCHC, this process enables repolymerization back to polycarbonates with 69 wt.% CO2 retention through life-cycles. The promising mechanical performance and recyclability of these CO2-based polycarbonate vitrimers indicate their potential for sustainable, high-performance materials, paving the way for future innovations in circular polymer technologies and carbon capture utilization.
36 MATERIALS SCIENCE↗
Helmet of a laminate construction of polycarbonate and polysulfone polymeric material
An article of laminate construction is disclosed which is comprised of an underlayer of polycarbonate polymer material to which is applied a chemically resistant outer layer of polysulfone. The layers which are joined by compression-heat molding, are molded to form the shape of a body protective shell such as a space helmet comprising a shell of polycarbonate, polysulfone laminate construction attached at its open end to a sealing ring adapted for connection to a space suit. The front portion of the shell provides a transparent visor for the helmet. An outer visor of polycarbonate polysulfone laminate construction is pivotally mounted to the sealing ring for covering the transparent visor portion of the shell during extravehicular activities. The polycarbonate under layer of the outer visor is coated on its inner surface with a vacuum deposit of gold to provide additional thermal radiation resistance.
Kosmo, Joseph J.↗
Stability of Atmospheric-Pressure Plasma Induced Changes on Polycarbonate Surfaces
Polycarbonate films are subjected to plasma treatment in a number of applications such as improving adhesion between polycarbonate and silicon alloy in protective and optical coatings. The changes in surface chemistry due to plasma treatment have tendency to revert back. Thus stability of the plasma induced changes on polymer surfaces over desired time period is very important. The objective of this study was to examine the effect of ageing on atmospheric pressure helium-plasma treated polycarbonate (PC) sample as a function of treatment time. The ageing effects were studied over a period of 10 days. The samples were plasma treated for 0.5, 2, 5 and 10 minutes. Contact angle measurements were made to study surface energy changes. Modification of surface chemical structure was examined using, X-ray Photoelectron Spectroscopy (XPS). Contact angle measurements on untreated and plasma treated surfaces were made immediately, 24, 48, 72 and 96 hrs after treatment. Contact angle decreased from 93 deg for untreated sample to 30 deg for sample plasma treated for 10 minutes. After 10 days the contact angles for the 10 minute plasma treated sample increased to 67 deg, but it never reverted back to that of untreated surface. Similarly the O/C ratio increased from 0.136 for untreated sample to 0.321 for 10 minute plasma treated sample indication increase in surface energy.
Sharma, Rajesh↗
Femtosecond Laser-Structured Transparent Anti-Fog Polycarbonate for Visor Applications
AlchLight has developed transparent anti-fog superhydrophobic polycarbonates for spacesuit helmets using femtosecond pulsed laser surface patterning technology. In contrast to conventional complex chemical coating processes, our laser patterning permanently alters the intrinsic wetting property of polycarbonate with little change to its transparency. The processing procedure is studied and optimized to produce the ideal superhydrophobic property and transparency. We were able to obtain a high contact angle (>150°), small sliding angle (<10°), and high transmission (>70%) over the visible wavelengths for polycarbonates. The anti-fog effect was also investigated. This technology will have a range of applications in spacesuit, automotive, medical, energy, and sports industries.
Spacesuit↗
Compression molding of anisotropic NdFeB bonded magnets in a polycarbonate matrix
Anisotropic bonded Nd 2 Fe 14 B (NdFeB) magnets in a polycarbonate (PC) binder matrix are fabricated using a compression molding process. The weight fractions (w.f.) of NdFeB in PC on the batch mixer are 20, 50, 75, 85 and 95% compared to the twin screw extruder with 20, 50 and 75% respectively. The density of the 95% batch mixed magnets fabricated was 5.34 g/cm 3 and the magnetic properties are, intrinsic coercivity H ci = 942.99 kA/m, remanence B r = 0.86 T, and energy product (BH) max = 120.96 kJ/m 3 . Furthermore, the measured tensile properties are in the range of 27-59 MPa, comparable to that of polyamide (PA), polyphenylene sulfide (PPS) bonded magnets and demonstrating potential for bonded magnet applications. Scanning electron microscopy showed that the onset of failure occurs in the magnetic particle- matrix interface. This study demonstrates that compression additive molding technique can be used to fabricate high performance NdFeB polycarbonate composite magnets with improved mechanical properties.
36 MATERIALS SCIENCE↗
Fully Recyclable Polycarbonates from Simple, Bio-Derived Building Blocks
Plastic buildup and accumulation in the environment are an increasingly large problem facing civilization. Petroleum-based plastics can exist for hundreds to thousands of years in the environment, destroying habitats and polluting water. Environmentally conscious replacements for plastics are urgently needed. In this publication, we present a biobased alternative to petroleum-based polycarbonates. Using a diol monomer derived from glycerol and glycerol products, we have synthesized aliphatic polycarbonates with comparable physical properties to petroleum-based incumbents. The polymer can be quantitatively depolymerized using warm methanol to recover the monomer which can be repolymerized multiple times, or alternatively, the monomer, which is inherently nontoxic, can slowly break apart to the original components. This provides two end-of-life options for this material recycle or decomposition under environmental conditions to benign building blocks, thus providing a potential pathway to avoid environmental and bioaccumulation of plastics. We also demonstrate the ability to selectively recover the monomer from a simulated mixed-plastic waste environment; the monomer recovered this way functions identically to the virgin monomer after purification. This work represents an important step in the progress toward environmentally conscious polymer design with multiple end-of-life options.
36 MATERIALS SCIENCE↗
Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer
Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO 2 ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL O ), and is also applied to ring‐opening copolymerization with CO 2 , via the epoxide manifold, to yield polycarbonate, PC(BiL O ). Remarkably, a one‐pot recycling process of a BiL O ‐derived PE/PC blend back to the constituent monomer BiL O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.
Shi, Changxia↗
Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer
Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO 2 ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL O ), and is also applied to ring‐opening copolymerization with CO 2 , via the epoxide manifold, to yield polycarbonate, PC(BiL O ). Remarkably, a one‐pot recycling process of a BiL O ‐derived PE/PC blend back to the constituent monomer BiL O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.
Chemistry↗
Strong degradation of polycarbonate and polystyrene by the CO 2 capture solvent diethyl sebacate
Here, we report on observations of strong degradation of a polycarbonate vessel by a solvent being considered for a CO 2 capture process, diethyl sebacate. This degradation led to failure of a polymeric hollow fiber membrane unit. Additional tests showed rapid degradation of polycarbonate safety glasses and polystyrene-based petri dishes by exposure to diethyl sebacate at ambient conditions. We also report on safe operations with diethyl sebacate in extensive experiments studying the corrosion of steel in CO 2 -pressurized reactors lined with PTFE and using PTFE gaskets. Used diethyl sebacate was also stored for long time periods in bottles made from low-density polyethylene bottles without physical deterioration. These observations indicate that care must be taken in development of new contactors and processes for CO 2 capture with diethyl sebacate and related solvents and in the choice of material for storage.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Microwave-Assisted Conversion of 1,6-Hexanediol into Polycarbonate
The conversion of carbon dioxide into higher value chemicals is a viable way to support sustainability and net-zero economy goals. Of the different CO2 conversion routes, direct conversion offers a simplified process, lower reaction temperatures, and thus low energy input. Alcohols can be directly combined with CO2 to produce polycarbonates, e.g., DMC (dimethyl carbonate) formation from methanol and CO2. Recently CO2 and 1,6-hexanediol were shown to convert into poly(hexamethylene carbonate)diol using an atmospheric flow based process in single step. For these conversions, CeO2-based catalysts are widely used due to the abundance of oxygen vacancies that are believed to be the active sites for this reaction. Microwave (MW) heating is a unique approach that can provide selective volume-based heating and enhanced reaction rates and/or selectivities. For the current work, CO2 and diol conversion into polymers were investigated on different CeO2 catalysts under microwave heating and the performance was compared against conventional heating. The reaction products were analyzed using infrared spectroscopy (IR) and nuclear magnetic resonance (NMR) spectroscopy. Preliminary results showed microwaves irradiation produced faster rates of polycarbonate production as evidenced by IR data.
Kanitkar, Swarom↗
Improvement program for polycarbonate capacitors
Hermetically sealed, wound, AC, polycarbonate capacitors incorporating design improvements recommended in a previous study were designed and built. A 5000 hour, 400 Hz ac life test was conducted using 384 of these capacitors to verify the adequacy of the design improvements. The improvements incorporated in the capacitors designed for this program eliminated the major cause of failure found in the preceding work, termination failure. A failure cause not present in the previous test became significant in this test with capacitors built from one lot of polycarbonate film. The samples from this lot accounted for 25 percent of the total test complement. Analyses of failed samples showed that the film had an excessive solvent content. This solvent problem was found in 37 of the total 46 failures which occurred in this test. The other nine were random failures resulting from causes such as seal leaks, foreign particles, and possibly wrinkles.
Bailey, R. R.↗
Plasticized phenolphthalein polycarbonate
Phenolphthalein polycarbonate was successfully plasticized with polychlorinated biphenyls (e.g., Aroclor 1231) or tricresyl phosphate and cast from tetrahydrofuran to give clear films without loss of fire resistance. At loadings of 20 to 30 percent plasticizer the Tg was lowered to approximately 100 C which would render phenolphthalein polycarbonate easily moldable. Although these materials had some mechanical integrity as shown by their film forming ability, the room temperature toughness of the plasticized polymer was not significantly improved over unmodified polymer.
Harrison, E. S.↗
Bisphenol A polycarbonate as a reference material
Test methods require reference materials to standardize and maintain quality control. Various materials have been evaluated as possible reference materials, including a sample of bisphenol A polycarbonate without additives. Screening tests for relative toxicity under various experimental conditions were performed using male mice exposed to pyrolysis effluents over a 200-800 C temperature range. It was found that the bisphenol A polycarbonate served as a suitable reference material as it is available in large quantities, and does not significantly change with time.
Hilado, C. J.↗
Improvement of the mechanical and thermal properties of the metallized polycarbonate capacitor
Changes were studied which enable polycarbonate metallized film capacitors to withstand 500 thermal shock cycles while maintaining electrical characteristic integrity without becoming intermittent, and without losing hermeticity. The task was for metallized polycarbonate film capacitors designed to meet MIL-C-39022/9 and MIL-C-83421/1. The capacitor design improvements implemented were the insertion of a rubber washer between spray cap and end seal and the utilization of a flexible lead assembly. One hundred fifty capacitors incorporating the design improvements were manufactured and subsequently underwent 500 thermal shock cycles. One hundred forty nine capacitors survived the test. Failure analysis revealed that the lone failure was due to a poor solder joint, initially detected in pre-screening tests as having poor dissipation factor and equivalent series resistance measurement readings.
Kellerman, H. J.↗
Nonyellowing Polycarbonate for Outdoor Use
Two-step photochemical process prevents yellowing of polycarbonate plastics. Use of polycarbonate plastics growing in windows, aircraft glazing, and streetlight globes. New photochemical process causes formation of stabilizers bound to polymer chains and therefore cannot be leached out.
Gupta, A.↗
Surface energy changes produced by ultraviolet-ozone irradiation of poly(methylmethacrylate), polycarbone and polytetrafluoroethylene
Contact angles of water and methylene iodide were measured as a function of UV/O3 treatment time for three polymers: poly(methylmethacrylate) (PMMA), polycarbonate, and polytetrafluoroethylene (PTFE). Surface roughnesses were also measured. Surface free energies were then calculated using relationships developed by Kaelble and Neumann. The surface energy of polycarbonate was found to increase (60 percent) during UV/O3 treatment. However, calculations on PMMA were hampered by the formation of a water soluble surface product. On PTFE surfaces, the UV/O3 treatment etched the surface causing large increases in surface roughness, rendering contact angle measurements impossible. It is concluded that care must be taken in interpreting contact angle measurements and surface energy calculations on UV/O3 treated polymer surfaces.
Ponter, A. B.↗