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Title: Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

Abstract

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

Authors:
 [1];  [1];  [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
  2. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, United States
  3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
  4. Marine Sciences Laboratory, Pacific Northwest National Laboratory, Sequim, Washington, United States
  5. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States; Department of Chemistry, University of Tennessee, Knoxville, Tennessee, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1398202
Report Number(s):
PNNL-SA-128982
Journal ID: ISSN 0888-5885; AF5855000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Industrial and Engineering Chemistry Research; Journal Volume: 56; Journal Issue: 38
Country of Publication:
United States
Language:
English

Citation Formats

Neti, Venkata S., Das, Sadananda, Brown, Suree, Janke, Christopher J., Kuo, Li-Jung, Gill, Gary A., Dai, Sheng, and Mayes, Richard T. Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization. United States: N. p., 2017. Web. doi:10.1021/acs.iecr.7b00482.
Neti, Venkata S., Das, Sadananda, Brown, Suree, Janke, Christopher J., Kuo, Li-Jung, Gill, Gary A., Dai, Sheng, & Mayes, Richard T. Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization. United States. doi:10.1021/acs.iecr.7b00482.
Neti, Venkata S., Das, Sadananda, Brown, Suree, Janke, Christopher J., Kuo, Li-Jung, Gill, Gary A., Dai, Sheng, and Mayes, Richard T. 2017. "Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization". United States. doi:10.1021/acs.iecr.7b00482.
@article{osti_1398202,
title = {Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization},
author = {Neti, Venkata S. and Das, Sadananda and Brown, Suree and Janke, Christopher J. and Kuo, Li-Jung and Gill, Gary A. and Dai, Sheng and Mayes, Richard T.},
abstractNote = {Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).},
doi = {10.1021/acs.iecr.7b00482},
journal = {Industrial and Engineering Chemistry Research},
number = 38,
volume = 56,
place = {United States},
year = 2017,
month = 9
}
  • Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g-U/kg of adsorbent) in laboratory screening testsmore » using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. Here, the modest capacity in 21-days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).« less
  • Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers wasmore » prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.« less
  • In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, whichmore » demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.« less
  • We developed a novel adsorbent preparation method using atom-transfer radical polymerization (ATRP) combined with radiation-induced graft polymerization (RIGP) in order to synthesize an adsorbent for uranium recovery from seawater. Furthermore, the ATRP method allowed a much higher degree of grafting on the adsorbent fibers (595 2818%) than that allowed by RIGP alone. The adsorbents were prepared with varied composition of amidoxime groups and hydrophilic acrylate groups. The successful preparation revealed that both ligand density and hydrophilicity were critical for optimal performance of the adsorbents. Adsorbents synthesized in this study showed a relatively high performance (141 179 mg/g at 49 62more » % adsorption) in laboratory screening tests using a uranium concentration of ~6 ppm. This performance is much higher than that of known commercial adsorbents. However, actual seawater experiment showed impeded performance compared to the recently reported high-surface-area-fiber adsorbents, due to slow adsorption kinetics. The impeded performance motivated an investigation of the effect of hydrophilic block addition on the graft chain terminus. The addition of hydrophilic block on the graft chain terminus nearly doubled the uranium adsorption capacity in seawater, from 1.56 mg/g to 3.02 mg/g. Our investigation revealed the importance of polymer chain conformation, in addition to ligand and hydrophilic group ratio, for advanced adsorbent synthesis for uranium recovery from seawater.« less