Morphology Evolution in Slowly Dip-Coated Supramolecular PS-<i>b</i>-P4VP Thin Films
Bibliographic record
Abstract
Block copolymer films obtained by dip-coating have been much less studied than those obtained by spin-coating, although it is an important industrial process. In our investigations of supramolecular diblock copolymer films of PS–P4VP (∼30 wt % P4VP) dip-coated from THF solutions, we initially found that films containing a monohydroxy-functionalized small molecule (SM), 1-naphthol (NOH), have a dot morphology, whereas those containing a monocarboxylic acid-functionalized small molecule, 1-naphthoic acid (NCOOH), have a stripe morphology. The COOH functionality is known to hydrogen bond more strongly to pyridine than OH. Yet the total amount of SM in the two types of films under given conditions is the same and PS–P4VP/NOH and PS–P4VP/NCOOH (equimolar SM:VP) in THF solution are both micellar, with the same spherical shape and size as PS–P4VP alone. On the other hand, the stripe morphology can be transformed to dot morphology by decreasing the dip-coating rate, the solution concentration or the SM:VP molar ratio, and vice versa. Vertical TEM indicates that the stripes correspond to horizontal cylinders, whereas the dots appear to be essentially spherical micelles. Although the films tend to be subject to terracing or dewetting, the average thickness of the films was observed to decrease toward a minimum with increase in dip-coating rate. This was related to the slow rates used, shown recently in sol–gel films to correspond to the so-called capillarity regime, and never before, to our knowledge, investigated in connection with its influence on block copolymer morphology. The minimum film thickness corresponds to the brush copolymer regime, which can be obtained almost uniformly for NOH-containing films, but is accompanied by stripe regions in the NCOOH-containing films investigated. Possible reasons for the differences in morphology evolution in films containing NOH vs NCOOH are discussed in the light of the experimental findings.
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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) | 0.000 | 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 | 0.000 |
| 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".