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Title: Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films

Abstract

The mesostructure loss kinetics are measured as a function of the orientation of micelles in 2D hexagonal close packed (HCP) columnar mesostructured titania thin films using in situ grazing incidence small angle x-ray scattering (GISAXS). Complementary supporting information is provided by ex situ scanning electron microscopy. Pluronic surfactant P123 acts as the template to synthesize HCP structured titania thin films. When the glass substrates are modified with crosslinked P123, the micelles of the HCP mesophase align orthogonal to the films, whereas a mix of parallel and orthogonal alignment is found on unmodified glass. The rate of mesostructure loss of orthogonally oriented (o-HCP) thin films (~60 nm thickness) prepared on modified substrate is consistently found to be less by a factor of 2.5 ± 0.35 than that measured for mixed orientation HCP films on unmodified substrates. The activation energy for mesostructure loss is only slightly greater for films on modified glass (155 ± 25 kJ/mol -1) than on unmodified (128 kJ/mol -1), which implies that the rate difference stems a greater activation entropy for mesostructure loss in o-HCP titania films. Nearly perfect orthogonal orientation of micelles on modified surfaces contributes to the lower rate of mesostructure loss by supporting the anisotropicmore » stresses that develop within the films during annealing due to continuous curing, sintering and crystallization into the anatase phase during high temperature calcination (>450 °C). Because the film thickness dictates the propagation of orientation throughout the films and the degree of confinement, thicker (~250 nm) films cast onto P123-modified substrates have a much lower activation energy for mesostructure loss (89 ± 27 kJ/mol -1) due to the mix of orientations found in the films. Thus, in conclusion, this kinetic study shows that thin P123- templated o-HCP titania films are not only better able to achieve good orthogonal alignment of 3 the mesophase relative to thicker films or films on unmodified substrates, but that alignment of the mesophase in the films stabilizes the mesophase against thermally-induced mesostructure loss.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [3];  [1]
  1. Univ. of Kentucky, Lexington, KY (United States). Dept. of Chemical & Materials Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States).Chemical Sciences and Engineering Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1248735
Grant/Contract Number:  
AC02-06CH11357; FG02-07-ER46375; IIA-1355438
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 4; Journal ID: ISSN 1463-9076
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

Das, Saikat, Nagpure, Suraj, Garlapalli, Ravinder K., Wu, Qingliu, Islam, Syed Z., Strzalka, Joseph, and Rankin, Stephen E. Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films. United States: N. p., 2016. Web. doi:10.1039/c5cp05178a.
Das, Saikat, Nagpure, Suraj, Garlapalli, Ravinder K., Wu, Qingliu, Islam, Syed Z., Strzalka, Joseph, & Rankin, Stephen E. Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films. United States. doi:10.1039/c5cp05178a.
Das, Saikat, Nagpure, Suraj, Garlapalli, Ravinder K., Wu, Qingliu, Islam, Syed Z., Strzalka, Joseph, and Rankin, Stephen E. Sat . "Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films". United States. doi:10.1039/c5cp05178a. https://www.osti.gov/servlets/purl/1248735.
@article{osti_1248735,
title = {Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films},
author = {Das, Saikat and Nagpure, Suraj and Garlapalli, Ravinder K. and Wu, Qingliu and Islam, Syed Z. and Strzalka, Joseph and Rankin, Stephen E.},
abstractNote = {The mesostructure loss kinetics are measured as a function of the orientation of micelles in 2D hexagonal close packed (HCP) columnar mesostructured titania thin films using in situ grazing incidence small angle x-ray scattering (GISAXS). Complementary supporting information is provided by ex situ scanning electron microscopy. Pluronic surfactant P123 acts as the template to synthesize HCP structured titania thin films. When the glass substrates are modified with crosslinked P123, the micelles of the HCP mesophase align orthogonal to the films, whereas a mix of parallel and orthogonal alignment is found on unmodified glass. The rate of mesostructure loss of orthogonally oriented (o-HCP) thin films (~60 nm thickness) prepared on modified substrate is consistently found to be less by a factor of 2.5 ± 0.35 than that measured for mixed orientation HCP films on unmodified substrates. The activation energy for mesostructure loss is only slightly greater for films on modified glass (155 ± 25 kJ/mol-1) than on unmodified (128 kJ/mol-1), which implies that the rate difference stems a greater activation entropy for mesostructure loss in o-HCP titania films. Nearly perfect orthogonal orientation of micelles on modified surfaces contributes to the lower rate of mesostructure loss by supporting the anisotropic stresses that develop within the films during annealing due to continuous curing, sintering and crystallization into the anatase phase during high temperature calcination (>450 °C). Because the film thickness dictates the propagation of orientation throughout the films and the degree of confinement, thicker (~250 nm) films cast onto P123-modified substrates have a much lower activation energy for mesostructure loss (89 ± 27 kJ/mol-1) due to the mix of orientations found in the films. Thus, in conclusion, this kinetic study shows that thin P123- templated o-HCP titania films are not only better able to achieve good orthogonal alignment of 3 the mesophase relative to thicker films or films on unmodified substrates, but that alignment of the mesophase in the films stabilizes the mesophase against thermally-induced mesostructure loss.},
doi = {10.1039/c5cp05178a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 4,
volume = 18,
place = {United States},
year = {2016},
month = {12}
}

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