Thermal annealing is one of the most indispensable polymer fabrication processes and plays essential roles in controlling morphologies and properties of polymeric materials. We here report that thermal annealing also facilitates polymer adsorption from the melt on planar silicon (Si) substrates, resulting in the formation of a high-density polymer nanolayer with flattened chain confirmations. Three different homopolymers (polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate)), which have similar inherent stiffness and bulk glass transition temperature (Tg), but have different affinities with Si substrates, were chosen as models. Spin-cast films (∼50 nm in thickness) with the three polymers were prepared on cleaned Si substrates and then placed in a vacuum oven set at a temperature far above the bulk Tg. In order to monitor the polymer adsorption process at the solid-polymer melt interface during thermal annealing, we used the protocol that combines vitrification of the annealed films (via rapi...

Formation Mechanism of High-Density, Flattened Polymer Nanolayers Adsorbed on Planar Solids

Confined at the nanoscale level, polymers crystallize much slower than in bulk, and in some cases, the formation of ordered structure is inhibited within extremely long experimental time scales. Here, we report on the thickness dependence of the conversion rate of the amorphous fraction of ultrathin films of poly(ethylene terephthalate) during isothermal cold crystallization. We present a new analytical method assessing the impact of irreversible chain adsorption and permitting to disentangle finite size and interfacial effects. From the μm range down to a few tens of nm, we observed an increase in crystallization time scaling with the inverse of the film thickness, which is a fingerprint of finite size effects. Films thinner than ∼20 nm did not crystallize, even after prolonged annealing in the temperature range where the crystallization rate reaches its maximum value. Noticing that this threshold corresponds to the total thickness of the layer irreversibly adsorbed within our investigation time, we expl...

Crystallization of thin polymer layers confined between two adsorbing walls

For almost a decade, growing experimental evidence has revealed a strong correlation between the properties of nanoconfined polymers and the number of chains irreversibly adsorbed onto nonrepulsive interfaces, e.g. the supporting substrate of thin polymer coatings, or nanofillers dispersed in polymer melts. Based on such a correlation, it has already been possible to tailor structural and dynamics properties – such as the glass transition temperature, the crystallization rate, the thermal expansion coefficients, the viscosity and the wettability – of nanomaterials by controlling the adsorption kinetics. This evidence indicates that irreversible adsorption affects nanoconfinement effects. More recently, also the opposite phenomenon was experimentally observed: nanoconfinement alters interfacial interactions and, consequently, also the number of chains adsorbed in equilibrium conditions. In this review we discuss this intriguing interplay between irreversible adsorption and nanoconfinement effects in ultrathin polymer films. After introducing the methods currently used to prepare adsorbed layers and to measure the number of irreversibly adsorbed chains, we analyze the models employed to describe the kinetics of adsorption in polymer melts. We then discuss the structure of adsorbed polymer layers, focusing on the complex macromolecular architecture of interfacial chains and on their thermal expansion; we examine the way in which the structure of the adsorbed layer affects the thermal glass transition temperature, vitrification, and crystallization. By analyzing segmental dynamics of 1D confined systems, we describe experiments to track the changes in density during adsorption. We conclude this review with an analysis of the impact of nanoconfinement on adsorption, and a perspective on future work where we also address the key ideas of irreversibility, equilibration and long-range interactions.

Irreversible adsorption of polymer melts and nanoconfinement effects

We report the structural relaxation process of irreversibly adsorbed polymer chains via thermal annealing that lie flat on a solid (“flattened chains”). Amorphous polystyrene and quartz, which together constitute a weakly attractive system, was used as a model where the local chain conformations of the flattened chains were investigated by sum frequency generation spectroscopy (SFG). Two different film preparation processes (i.e., spin coating and dip coating methods) were utilized to create different initial chain conformations. The spin-coated and dip-coated PS thin films were annealed at a temperature far above the bulk glass transition temperature to reach the “quasiequilibrium” state and subsequently rinsed with chloroform to uncover the buried flattened chains. The SFG results revealed that the backbone chains (constituted of CH and CH2 groups) of the flattened PS chains preferentially orient to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformati...

Flattening Process of Polymer Chains Irreversibly Adsorbed on a Solid

The stability or wettability of thin polymer films on solids is of vital interest in traditional technologies as well as in new emerging nanotechnologies. We report here that nanoscale structures of polymer chains adsorbed onto a solid surface play a crucial role in the thermal stability of the film. In this study, polystyrene (PS) spin-cast films (20 nm in thickness) with eight different molecular weights prepared on silicon (Si) substrates were used as a model. When low molecular weight (Mw≤ 50 kDa) PS films were subjected to thermal annealing at temperatures far above the bulk glass transition temperature, dewetting occurred promptly, while high molecular weight (Mw≥ 123 kDa) PS films were stable for at least 6 weeks at 150 °C. We reveal a strong correlation between the film stability and the two different interfacial structures of the adsorbed polymer chains: their opposing wettability against chemically identical free polymer chains results in a wetting-dewetting transition at the adsorbed polymer-free polymer interface. This is a unique aspect of the stability of polymer thin films and may be generalizable to other polymer systems regardless of the magnitude of solid-polymer attractive interactions.

Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability

We report the structural heterogeneity of recrystallized linear low-density polyethylene (LLDPE) films (25, 50, and 100 nm in thickness) in the direction normal to the surface, based on in situ gra...

Heterogeneous lamellar structures near the polymer/substrate interface

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of <strong>{limit}</strong> columns in the table. Remove at least <strong>1</strong> column to add or create another one.

M. Lee

Author Tools

Chat about Author

Papers

Heterogeneous lamellar structures near the polymer/substrate interface