Influence of hydrophilic groups and metal-ion adsorption on polymer-chain conformation of amidoxime-based uranium adsorbents

Alexander I Wiechert; Wei-Po Liao; Eunice Hong; Candice E Halbert; Sotira Yiacoumi; Tomonori Saito; Costas Tsouris

doi:10.1016/j.jcis.2018.04.021

Influence of hydrophilic groups and metal-ion adsorption on polymer-chain conformation of amidoxime-based uranium adsorbents

J Colloid Interface Sci. 2018 Aug 15:524:399-408. doi: 10.1016/j.jcis.2018.04.021. Epub 2018 Apr 6.

Authors

Alexander I Wiechert¹, Wei-Po Liao², Eunice Hong², Candice E Halbert², Sotira Yiacoumi¹, Tomonori Saito³, Costas Tsouris⁴

Affiliations

¹ School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0373, USA.
² Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.
³ Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA. Electronic address: saitot@ornl.gov.
⁴ School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0373, USA; Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA. Electronic address: tsourisc@ornl.gov.

PMID: 29674284
DOI: 10.1016/j.jcis.2018.04.021

Abstract

This study focuses on the influence of hydrophilic groups and metal-ion loading on adsorbent polymer conformation, which controls access to adsorption sites and may limit adsorption capacity. Gaining a better understanding of the factors that influence conformation may yield higher-capacity adsorbents. Polyamidoxime (PAO), deuterated-PAO polyacrylic acid diblock copolymers (d-PAO-b-PAA), and randomly configured copolymers (PAO-co-PAA) were synthesized and characterized by neutron reflectometry in air and D₂O. For d-PAO-b-PAA, characterization was also performed after alkali conditioning and in simulated seawater. PAO and PAO-co-PAA, with similar molecular weight and grafting density, extended from 95-Å thickness in air to 180 and 280-Å in D₂O, respectively. This result suggests that polymer swelling may cause the additional adsorption capacity observed when polymer hydrophilicity increases. Two d-PAO-b-PAA samples, A and B, with a d-PAO thickness of 55-Å swelled to 110-Å and 140-Å, respectively, with an overall thickness increase of ∼160% in D₂O. After alkali conditioning, molecular interactions increased the density of PAA near the PAO-PAA interface, while the d-PAO thickness only decreased by ∼10 Å. The d-PAO thickness of both samples declined to ∼90-Å after adsorption in simulated seawater due to polymer-chain crosslinking. These results are expected to aid in improving adsorbent synthesis to increase uranium capacity.

Keywords: Amidoxime; Neutron reflectometry; Polymer conformation; Seawater; Uranium.