id ndltd-OhioLink-oai-etd.ohiolink.edu-akron1249315424
record_format oai_dc
collection NDLTD
language English
sources NDLTD
topic Analytical Chemistry
Materials Science
Optics
Physics
Polymers
scanning probe microscopy
SPM
AFM
modified probe
tip enhanced Raman spectrocopy
TERS
nanoRaman
plasmonics
ultrathin
dielectric
SERS
acrylic block copolymer
surface segregation
latex films
fluorosurfactant
SAM
scanning probes
spellingShingle Analytical Chemistry
Materials Science
Optics
Physics
Polymers
scanning probe microscopy
SPM
AFM
modified probe
tip enhanced Raman spectrocopy
TERS
nanoRaman
plasmonics
ultrathin
dielectric
SERS
acrylic block copolymer
surface segregation
latex films
fluorosurfactant
SAM
scanning probes
Barrios, Carlos A.
Modified Scanning Probes for the Analysis of Polymer Surfaces
author Barrios, Carlos A.
author_facet Barrios, Carlos A.
author_sort Barrios, Carlos A.
title Modified Scanning Probes for the Analysis of Polymer Surfaces
title_short Modified Scanning Probes for the Analysis of Polymer Surfaces
title_full Modified Scanning Probes for the Analysis of Polymer Surfaces
title_fullStr Modified Scanning Probes for the Analysis of Polymer Surfaces
title_full_unstemmed Modified Scanning Probes for the Analysis of Polymer Surfaces
title_sort modified scanning probes for the analysis of polymer surfaces
publisher University of Akron / OhioLINK
publishDate 2009
url http://rave.ohiolink.edu/etdc/view?acc_num=akron1249315424
work_keys_str_mv AT barrioscarlosa modifiedscanningprobesfortheanalysisofpolymersurfaces
_version_ 1719420037149753344
spelling ndltd-OhioLink-oai-etd.ohiolink.edu-akron12493154242021-08-03T05:25:56Z Modified Scanning Probes for the Analysis of Polymer Surfaces Barrios, Carlos A. Analytical Chemistry Materials Science Optics Physics Polymers scanning probe microscopy SPM AFM modified probe tip enhanced Raman spectrocopy TERS nanoRaman plasmonics ultrathin dielectric SERS acrylic block copolymer surface segregation latex films fluorosurfactant SAM scanning probes Scanning probe microscopies (SPMs) allow the observation and measurement of surface properties on a highly local level based on the interaction between a very sharp probe and the surface. Interaction stability and probe integrity, at least during the scanning time, are necessary, but still a challenge. Conventional scanning probes have been used for revealing morphological features connected with macroscopic properties of complex latex films. These films, when dry, are sufficiently hard to be studied with minimal distortion of the surface by the probe. By comparing formulations with various fluorosurfactant concentrations, it was demonstrated how the fluorosurfactant, which is known heuristically to improve leveling, gives the system more mobility before drying. Specifically, in styrene-butadiene copolymer formulations, sub-micrometer differences in surface morphology, observed as a function of fluorosurfactant concentration, correlated with differences in gloss. In some cases, surfaces are too soft or too adhesive to be studied by conventional probes. Modification of scanning probes with hydrophobic layers having methyl or fluorinated end groups has been used to weaken the probe-surface interaction to study model adhesive surfaces. Acrylic block copolymers with well-defined molecular weight and composition were synthesized by controlled radical polymerization to create models of pressure sensitive adhesives to evaluate performance after aging or humidity exposure.Macroscopically, tack measurements demonstrated that blending a triblock copolymer with a homopolymer of the midblock polymer can be used to tailor the tack value. Microscopically, force-penetration curves of the acrylic blends showed a superficial phase separation into two mixed phases as homopolymer content was increased. Hydrophobic modification made it possible to measure these surfaces that would otherwise be too adhesive to study with conventional probes. Modification of scanning probes has also been used to bring robustness to high resolution chemical imaging. Addition of a 2-3 nm Al2O3 protective layer on silver-coated scanning probes dramatically reduced degradation of the probes with time, without sacrificing initial probe efficiency. In addition, the protective layer improved markedly the wear resistance of the probes. The surface morphology of the silver structure was not altered and the signal enhancement decay was completely stopped. These results agree with the conjecture that an ideal dielectric coating shifts the epicenter of the electromagnetic field enhancement in plasmonic structures, a behavior previously simulated, but not demonstrated. New types of plasmonic structure fabrication were also explored as means to surpass currently available signal enhancements by controlled size and shape, increased roughness or higher crystallinity. A single metal nano-pillar deposited by electron beam induced deposition (EBID), crystalline dendritic structures deposited by metal replacement reactions, and layers with sharper asperities deposited by ion sputtering were all fabricated on conventional scanning probes. The last produced a significant enhancement. In addition, strong signal fluctuations in Raman band intensity (“blinking”), similar to those seen in single molecule surface enhanced Raman spectroscopy, were also observed. This approach opens exciting new possibilities. 2009-09-01 English text University of Akron / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=akron1249315424 http://rave.ohiolink.edu/etdc/view?acc_num=akron1249315424 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.