Enhancement of thermomechanical properties of sulfur-rich polymers by post-thermal treatment

Han, Nara; Cho, Woongbi; Hwang, Jae Hyuk; Won, Sukyoung; Kim, Dong-Gyun; Wie, Jeong Jae

doi:10.1039/d2py01390h

Cited by 5 publications

(7 citation statements)

References 46 publications

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“…(h) Midwavelength IR (MWIR) and long-wavelength IR (LWIR) transmittance of SRP films with a thickness of 165 μm as a function of thermal treatment time at 110 °C. Images adapted with permission from ref . Copyright 2023 Royal Society of Chemistry.…”

Section: Vacuum-assisted Thermal Treatment For Enhanced Thermo-mechan...mentioning

confidence: 99%

“…We first introduce a universal approach to enhance thermo-mechanical properties of SRPs, named vacuum-assisted thermal treatment. 36 Then, for value addition of SRPs, we will explain strategies to achieve a high-performance SRP-based IR polarizer, including the importance of high-fidelity in nanogratings as well as precise tailoring of spacer thickness on the performance of the polarizer. 22…”

Section: Introductionmentioning

confidence: 99%

“…In this Account, we will discuss a new strategy to enhance novel thermo-mechanical properties of SRPs and then focus on promising applications of SRPs including IR polarizers and TENG. We first introduce a universal approach to enhance thermo-mechanical properties of SRPs, named vacuum-assisted thermal treatment . Then, for value addition of SRPs, we will explain strategies to achieve a high-performance SRP-based IR polarizer, including the importance of high-fidelity in nanogratings as well as precise tailoring of spacer thickness on the performance of the polarizer .…”

Section: Introductionmentioning

confidence: 99%

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Value-Addition of Wastes from Petroleum Refining Process: Sulfur-Rich Polymers for Sustainable and High-Performance Optical and Energy Applications

Cho,

Kim,

Wie

2024

Acc. Mater. Res.

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Conspectus The petrochemical industry plays a pivotal role in the manufacturing process of petrochemical products by transforming crude oil into monomers of synthetic polymers used to produce a wide range of commercial products. However, the generation of elemental sulfur, a significant byproduct of the petroleum refining process, has raised substantial environmental concerns as the volume of petroleum refining is increasing to meet rapidly growing energy consumption and demand for petrochemical products. Due to hydrodesulfurization, 7 million tons of elemental sulfur is produced as an annual surplus, which exceeds the amount used for rubber vulcanization, fertilizer production, and sulfuric acid manufacturing. If, however, we can upcycle this abundant resource for high-value applications, the mass production of high-purity elemental sulfur might provide huge economic benefits. In 2013, the first successful research study in synthesizing sulfur-rich polymers (SRPs) with a high sulfur content of up to 90 wt % was reported, employing inverse vulcanization. Unlike carbon-based polymers, SRPs demonstrate remarkable infrared (IR) transparency, which allows us to usher in a new era of polymer-based IR optics. Furthermore, SRPs also show high potential as sustainable and high-performance triboelectric materials due to the highest electron affinity of elemental sulfur excluding halogen atoms. Hence, SRPs have garnered significant interest in practical applications, such as IR thermal imaging and triboelectric energy harvesting. In this Account, we highlight our recent progress in upcycling SRPs into the aforementioned practical applications, such as IR polarizers and triboelectric nanogenerators (TENG) toward value-addition of elemental sulfur. First, we will discuss strategies to enhance thermo-mechanical properties of SRPs such as the glass transition temperature (T g), cross-linking density, and elastic modulus without significant deterioration of IR transparency. Despite these unique advantages, SRPs often suffer from low thermo-mechanical properties, limiting durability and robustness for practical applications. Although numerous research efforts have been devoted to identifying optimal comonomers during the inverse vulcanization process, addressing these issues remains a focus for ongoing investigation. Then, we will explain the strategy to achieve a high-performance IR polarizer in terms of nanoscaled manufacturing. Most studies related to SRPs in the context of IR optics focus on preparing IR windows which are typically utilized as a protective layer of thermal imaging systems. Hence, for value-addition of SRPs, it can be an effective strategy to directly prepare nanostructured SRPs for the IR polarizer. In the last section, we look beyond IR-related applications to introduce new advances for SRPs in sustainable and high-performance triboelectric energy harvesting. We focus on achieving a highly charged surface of SRP film by considering rational design based on electron affinity and hypervalency of sulfur and st...

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Section: Vacuum-assisted Thermal Treatment For Enhanced Thermo-mechan...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Value-Addition of Wastes from Petroleum Refining Process: Sulfur-Rich Polymers for Sustainable and High-Performance Optical and Energy Applications

Cho,

Kim,

Wie

2024

Acc. Mater. Res.

Self Cite

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“…Among rare reports, J. Griebel found that in the inverse vulcanization of DIB, a too-long reaction time at high temperatures would lead to a flow transition of the polymer product, suggesting the breaking of the polymer network 29 . In contrast, D. Kim and his coworkers 30 discovered that the post-thermal treatment at 110 °C and 140 °C will improve the thermomechanical properties of inverse vulcanization products based on divinylbenzene in terms of glass transition temperature ( T g ) and storage modulus. C. Jenkins et al 31 investigated the effects of different reaction conditions, including reaction time, temperatures, scales, and feeding and heating procedures.…”

Section: Introductionmentioning

confidence: 98%

“…Nevertheless, only preliminary explanations were provided to elucidate the evolution of product structures and behaviors. The degradation of polysulfides at long reaction times was usually intuitively ascribed to the break and rearrangement of sulfur chains 28 , 30 . Moreover, most mechanism investigation and thermal treatment investigations were carried out with sole model monomer 20 , 21 .…”

Section: Introductionmentioning

confidence: 99%

Structural evolution during inverse vulcanization

Zheng,

Zhong,

Wang

et al. 2024

Nat Commun

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Inverse vulcanization exploits S8 to synthesize polysulfides. However, evolution of products and its mechanism during inverse vulcanization remains elusive. Herein, inverse vulcanization curves are obtained to describe the inverse vulcanization process in terms of three stages: induction, curing and over-cure. The typical curves exhibit a moduli increment before declining or plateauing, reflecting the process of polysulfide network formation and loosing depending on monomers. For aromatic alkenes, in the over-cure, the crosslinked polysulfide evolves significantly into a sparse network with accelerated relaxation, due to the degradation of alkenyl moieties into thiocarbonyls. The inverse vulcanization product of olefins degrades slowly with fluctuated relaxation time and modulus because of the generation of thiophene moieties, while the inverse vulcanization curve of dicyclopentadiene has a plateau following curing stage. Confirmed by calculations, the mechanisms reveal the alkenyl groups react spontaneously into thiocarbonyls or thiophenes via similar sulfur-substituted alkenyl intermediates but with different energy barriers.

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High‐Performance Yet Sustainable Triboelectric Nanogenerator Based on Sulfur‐Rich Polymer Composite with MXene Segregated Structure

Cho,

Kim,

Lee

et al. 2024

Advanced Materials

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State‐of‐the‐art triboelectric nanogenerators (TENGs) typically employ fluoropolymers, highly negative chargeable materials in triboelectric series. However, many researchers nowadays are concerned about environmental pollution caused by poly‐and per‐fluoroalkyl substances (PFAS) due to their critical immunotoxicity as fluoropolymers are likely to release PFAS into the ecosystem during their life cycle. Herein, a sulfur‐rich polymer (SRP)/MXene composite, offering high‐performance yet sustainable TENG is developed. Value‐addition of sulfur into SRP‐based TENG has huge advantages since sulfur is abundant waste from petroleum refining and possesses the highest electron affinity (−200 kJ mol−1) among polymerizable atoms. MXene segregated structure is introduced into SRP to achieve homogeneous distribution without electrical percolation by utilizing below 0.5 wt% of MXene, resulting in a significantly enhanced dielectric constant without a drastic increase of dielectric loss. Due to homogeneous MXene distribution, SRP/MXene composite‐based TENG demonstrates 2.9 times and 19.5 times enhances peak voltage and peak current compared to previous SRP‐based TENGs. Additionally, it exhibits reusability without critical reduction of modulus and TENG performance due to dynamically exchangeable disulfide bonds. Finally, after the corona discharging and scaling‐up process to a 4‐inch wafer size, SRP/MXene composite‐based TENG exhibits an 8.4 times improvement in peak power density, reaching 3.80 W m−2 compared to previous SRP‐based TENGs.

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Enhancement of thermomechanical properties of sulfur-rich polymers by post-thermal treatment

Abstract: Recently, sulfur-rich polymers have been applied in various fields including energy storage, mercury absorption, and infrared (IR) optics. However, sulfur-rich polymers typically exhibit insufficient thermomechanical properties for practical applications. Herein,...

Cited by 5 publications

References 46 publications

Value-Addition of Wastes from Petroleum Refining Process: Sulfur-Rich Polymers for Sustainable and High-Performance Optical and Energy Applications

Value-Addition of Wastes from Petroleum Refining Process: Sulfur-Rich Polymers for Sustainable and High-Performance Optical and Energy Applications

Structural evolution during inverse vulcanization

High‐Performance Yet Sustainable Triboelectric Nanogenerator Based on Sulfur‐Rich Polymer Composite with MXene Segregated Structure

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