Evolution of Small Molecule Content and Morphology with Dip-Coating Rate in Supramolecular PS–P4VP Thin Films
Bibliographic record
Abstract
In dip-coated thin films of supramolecular block copolymers where a small molecule (SM) preferentially interacts with one of the blocks, an important issue is whether or not the SM content in the films is the same as that in the dip-coating solution. Here, we quantitatively determined the SM content, using infrared spectroscopy in the attenuated total reflection mode (IR-ATR), in films of poly(styrene- b -4-vinylpyridine) (PS–P4VP) dip-coated from THF solutions containing naphthol (NOH) and naphthoic acid (NCOOH). Dip-coating was effected at very slow rates (0.5–6 mm/min), i.e., in the recently described “capillarity regime”, where film thickness decreases with rate. It was found that, for both SMs, the SM/VP ratios in the films are the same under given conditions and evolve identically with dip-coating rate, starting from much less than, and then increasing toward, the SM/VP solution ratio. This behavior was related to THF being a hydrogen-bond competitor and to consequent diffusion of the SM back into solution during the capillarity-dominated dip-coating process. The increase in the SM/VP ratio correlates with a morphology evolution from spherical to (in-plane) cylindrical to lamellar in the NCOOH-containing films. The more limited morphological evolution in the films containing NOH, which forms a weaker H-bond with VP than NCOOH, was attributed mainly to greater partitioning of NOH in the PS phase.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 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) | 0.001 | 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".