Direct measurements of the temperature, depth and processing dependence of phenyl ring dynamics in polystyrene thin films by β-detected NMR
Bibliographic record
Abstract
There is indirect evidence that the dynamics of a polymer near a free surface are enhanced compared with the bulk but there are few studies of how dynamics varies with depth. β-Detected nuclear spin relaxation of implanted 8Li+ has been used to directly probe the temperature and depth dependence of the γ-relaxation mode, which is due to phenyl rings undergoing restricted rotation, in thin films of atactic deuterated polystyrene (PS-d8) and determine how the depth dependence of dynamics is affected by sample processing, such as annealing, floating on water and the inclusion of a surfactant, and by the presence of a buried interface. The activation energy for the γ-relaxation process is lower near the free surface. Annealing the PS-d8 films and then immersing in water to mimic the floating procedure used to transfer films had negligible effects on the thickness of the region near the free surface with enhanced mobility. Measurements on a bilayer film indicate enhanced phenyl ring dynamics near the buried interface compared with a single film at the same depth. PS-d8 films annealed with the surfactant sodium dodecyl sulfate (SDS) deposited on the surface show enhanced dynamics in the bulk compared with a pure PS-d8 film and a PS-d8 film where the SDS was washed away. There is less contrast between the surface and bulk in the SDS-treated sample, which could account for the elimination of the Tg confinement effect observed in films containing SDS [Chen and Torkelson, Polymer, 2016, 87, 226].
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".