An official website of the United States government
Abstract This work utilizes frustrated Lewis pairs consisting of tethered bis‐organophosphorus superbases and a bulky organoaluminum to furnish the highly efficient synthesis of well‐defined triblock copolymers via one‐step block copolymerization of lignin‐based syringyl methacrylate andn‐butyl acrylate, through di‐initiation and compounded sequence control. The resulting thermoplastic elastomers (TPEs) exhibit microphase separation and much superior mechanical properties (elongation at break up to 2091 %, tensile strength up to 11.5 MPa, and elastic recovery up to 95 % after 10 cycles) to those of methyl methacrylate‐based TPEs. More impressively, lignin‐based tri‐BCPs can maintain TPEs properties up to 180 °C, exhibit high transparency and nearly 100 % UV shield, suggesting potential applications in temperature‐resistant and optical devices.
more »
« less
Supersoft Norbornene‐Based Thermoplastic Elastomers with High Strength and Upper Service Temperature
Abstract With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio‐interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene‐basedABAtriblock copolymers, this gap is filled. Ring‐opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin‐like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high‐performance plastics (≈260 °C). Furthermore, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next‐generation TPEs that are both biologically soft yet thermomechanically durable.
more »
« less
- Award ID(s):
- 2045336
- PAR ID:
- 10640900
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 36
- Issue:
- 30
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Poly(methyl methacrylate) (PMMA) is an important commodity polymer having a wide range of applications. Currently, only about 10% of PMMA is recycled. Herein, a simple two‐stage process for the chemical upcycling of PMMA is discussed. In this method PMMA is modified by transesterification with a bio‐derived, olefin‐bearing terpenoid, geraniol. In the second stage, olefin‐derivatized PMMA is reacted with sulfur to form a network composite by an inverse vulcanization mechanism. Inverse vulcanization of PGMA with elemental sulfur (90 wt.%) yielded the durable compositePGMA‐S. This composite was characterized by NMR spectrometry, IR spectroscopy, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry. Composite water uptake, compressional strength analysis, flexural strength analysis, tensile strength analysis, and thermal recyclability are presented with comparison to current commercial structural materials.PGMA‐Sexhibits a similar compressive strength (17.5 MPa) to that of Portland cement.PGMA‐Sdemonstrates an impressive flexural strength of 4.76 MPa which exceeds the flexural strength (>3 MPa) of many commercial ordinary Portland cements. This study provides a way to upcycle waste PMMA through combination with a naturally‐occurring olefin and industrial waste sulfur to yield composites having mechanical properties competitive with ecologically detrimental legacy building materials.more » « less
-
Abstract Graphene holds promise for thin, ultralightweight, and high‐performance nanoelectromechanical transducers. However, graphene‐only devices are limited in size due to fatigue and fracture of suspended graphene membranes. Here, a lightweight, flexible, transparent, and conductive bilayer composite of polyetherimide and single‐layer graphene is prepared and suspended on the centimeter scale with an unprecedentedly high aspect ratio of 105. The coupling of the two components leads to mutual reinforcement and creates an ultrastrong membrane that supports 30 000 times its own weight. Upon electromechanical actuation, the membrane pushes a massive amount of air and generates high‐quality acoustic sound. The energy efficiency is≈10–100 times better than state‐of‐the‐art electrodynamic speakers. The bilayer membrane's combined properties of electrical conductivity, mechanical strength, optical transparency, thermal stability, and chemical resistance will promote applications in electronics, mechanics, and optics.more » « less
-
Abstract Climate warming is expected to increase respiration rates of tropical forest trees and lianas, which may negatively affect the carbon balance of tropical forests. Thermal acclimation could mitigate the expected respiration increase, but the thermal acclimation potential of tropical forests remains largely unknown. In a tropical forest in Panama, we experimentally increased nighttime temperatures of upper canopy leaves of three tree and two liana species by on average 3 °C for 1 week, and quantified temperature responses of leaf dark respiration. Respiration at 25 °C (R25) decreased with increasing leaf temperature, but acclimation did not result in perfect homeostasis of respiration across temperatures. In contrast, Q10of treatment and control leaves exhibited similarly high values (range 2.5–3.0) without evidence of acclimation. The decrease inR25was not caused by respiratory substrate depletion, as warming did not reduce leaf carbohydrate concentration. To evaluate the wider implications of our experimental results, we simulated the carbon cycle of tropical latitudes (24°S–24°N) from 2000 to 2100 using a dynamic global vegetation model (LM3VN) modified to account for acclimation. Acclimation reduced the degree to which respiration increases with climate warming in the model relative to a no‐acclimation scenario, leading to 21% greater increase in net primary productivity and 18% greater increase in biomass carbon storage over the 21st century. We conclude that leaf respiration of tropical forest plants can acclimate to nighttime warming, thereby reducing the magnitude of the positive feedback between climate change and the carbon cycle.more » « less
-
Thermal interface material (TIM) that exists in a liquid state at the service temperature enables efficient heat transfer across two adjacent surfaces in electronic applications. In this work, the thermal conductivities of different phase regions in the Ga-In system at various compositions and temperatures are measured for the first time. A modified comparative cut bar technique is used for the measurement of the thermal conductivities of GaxIn1−x (x = 0, 0.1, 0.214, 0.3, and 0.9) alloys at 40, 60, 80, and 100 °C, the temperatures commonly encountered in consumer electronics. The thermal conductivity of liquid and semi-liquid (liquid + β) Ga-In alloys are higher than most of the TIM’s currently used in consumer electronics. These measured quantities, along with the available experimental data from literature, served as input for the thermal conductivity parameter optimization using the CALPHAD (calculation of phase diagrams) method for pure elements, solution phase, and two-phase region. A set of self-consistent parameters for the description of the thermal conductivity of the Ga-In system is obtained. There is good agreement between the measured and calculated thermal conductivities for all of the phases. Due to their ease of manufacturing and high thermal conductivity, liquid/semi-liquid Ga-In alloys have significant potential for TIM in consumer electronics.more » « less
