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Title: All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties

Abstract

All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight ( M e) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures ( T gs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the T gs of both segments were observed for the block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly( n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionicmore » polymerization.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1];  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1407777
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Polymer Chemistry
Additional Journal Information:
Journal Volume: 8; Journal Issue: 37; Journal ID: ISSN 1759-9954
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lu, Wei, Wang, Yangyang, Wang, Weiyu, Cheng, Shiwang, Zhu, Jiahua, Xu, Yuewen, Hong, Kunlun, Kang, Nam -Goo, and Mays, Jimmy. All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties. United States: N. p., 2017. Web. doi:10.1039/c7py01225j.
Lu, Wei, Wang, Yangyang, Wang, Weiyu, Cheng, Shiwang, Zhu, Jiahua, Xu, Yuewen, Hong, Kunlun, Kang, Nam -Goo, & Mays, Jimmy. All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties. United States. doi:10.1039/c7py01225j.
Lu, Wei, Wang, Yangyang, Wang, Weiyu, Cheng, Shiwang, Zhu, Jiahua, Xu, Yuewen, Hong, Kunlun, Kang, Nam -Goo, and Mays, Jimmy. 2017. "All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties". United States. doi:10.1039/c7py01225j.
@article{osti_1407777,
title = {All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties},
author = {Lu, Wei and Wang, Yangyang and Wang, Weiyu and Cheng, Shiwang and Zhu, Jiahua and Xu, Yuewen and Hong, Kunlun and Kang, Nam -Goo and Mays, Jimmy},
abstractNote = {All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight (Me) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures (Tgs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the Tgs of both segments were observed for the block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly(n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionic polymerization.},
doi = {10.1039/c7py01225j},
journal = {Polymer Chemistry},
number = 37,
volume = 8,
place = {United States},
year = 2017,
month = 8
}

Journal Article:
Free Publicly Available Full Text
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  • We present the synthesis and characterization of a new class of high temperature thermoplastic elastomers composed of polybenzofulvene–polyisoprene–polybenzofulvene (FIF) triblock copolymers. All copolymers were prepared by living anionic polymerization in benzene at room temperature. Homopolymerization and effects of additives on the glass transition temperature (T g) of polybenzofulvene (PBF) were also investigated. Among all triblock copolymers studied, FIF with 14 vol % of PBF exhibited a maximum stress of 14.3 ± 1.3 MPa and strain at break of 1390 ± 66% from tensile tests. The stress–strain curves of FIF-10 and 14 were analyzed by a statistical molecular approach using amore » nonaffine tube model to estimate the thermoplastic elastomer behavior. Dynamic mechanical analysis showed that the softening temperature of PBF in FIF was 145 °C, much higher than that of thermoplastic elastomers with polystyrene hard blocks. Microphase separation of FIF triblock copolymers was observed by small-angle X-ray scattering, even though long-range order was not achieved under the annealing conditions employed. Additionally, the microphase separation of the resulting triblock copolymers was examined by atomic force microscopy.« less
  • Carburization of high-temperature alloys has been frequently observed during exposure to dry hightemperature gas-cooled reactor (HTGR) helium compositions. Therefore, the influence of carburization on mechanical properties of alloys that may be used for HTGR high-temperature components has been studied. In creep rupture tests on high-temperature alloys for up to 20 000 h, the data in air and in various simulated HTGR heliums lie in the same scatterband irrespective of carburization that has been observed in the contaminated helium atmospheres. The dependence of room temperature tensile properties and the impact strength in the 20 to 800/sup 0/C range on the carburizationmore » level has been measured so that the maximum carbon level for a given room temperature ductility and impact strength could be specified. The results showed that the minimum room temperature elongation fell to below 5% when the carbon content exceeded 0.5 wt% for Incoloy-800H and 0.2 wt% for Inconel-617. At these carbon levels, the alloys have impact strengths (ISO V-notch specimens) of about 50 J or above at temperatures in the 25 to 800/sup 0/C range.« less
  • Nanocomposites based on a thermoplastic elastomer (TPE) (low-density polyethylene (LDPE) and 1,2-polybutadiene in a ratio of 60/40) with functional titanium dioxide nanoparticles of different nature, TiO{sub 2}/TPE, have been prepared and investigated by a complex of methods (X-ray diffraction analysis using X-ray and synchrotron radiation beams, scanning electron microscopy, transmission electron microscopy, and X-ray energy-dispersive spectroscopy). The morphology of the composites is found to be somewhat different, depending on the TiO{sub 2} characteristics. It is revealed that nanocomposites with cellular or porous structures containing nano-TiO{sub 2} aggregates with a large specific surface and large sizes of crystallites and nanoparticles exhibitmore » the best deformation‒strength and fatigue properties and stability to the effect of active media under conditions of ozone and vapor‒air aging.« less