Solvent Influence on Thickness, Composition, and Morphology Variation with Dip-Coating Rate in Supramolecular PS-<i>b</i>-P4VP Thin Films
Bibliographic record
Abstract
Recent literature has shown that the thickness of dip-coated films has a V-shaped dependence on dip-coating rate when very slow rates are included. For supramolecular block copolymer films, small molecule (SM) uptake and film morphology are also rate-dependent, as shown previously for a poly(styrene- b -4-vinylpyridine) (PS–P4VP) block copolymer in THF solutions containing naphthol (NOH) and naphthoic acid (NCOOH). Here, these investigations are extended to p -dioxane, toluene, and CHCl 3 solutions. The V-shaped thickness dependence is validated for each solvent, but with the V minimum displaced to lower dip-coating rates and thicknesses for the solvents with lower vapor pressures ( p -dioxane, toluene), thereby decreasing the dip-coating rate range of the “capillarity regime” (slow side of the V) and consequently extending that of the “draining regime” (fast side of the V). The SM/VP uptake ratio varies with the nature of the solvent, particularly in the capillarity regime, where it is higher for solvents that are weak SM-VP hydrogen-bond competitors (toluene, CHCl 3 ). The draining regime generally shows greater SM uptake than the capillarity regime, in some cases reaching the solution ratio, with higher uptake observed for the SM with greater hydrogen-bond strength (NCOOH > NOH). The variation in film morphology with solvent and dip-coating rate (spherical for toluene; spherical and cylindrical for p -dioxane; spherical, cylindrical, and lamellar for THF; and lamellar only for CHCl 3; for a block copolymer whose equilibrium morphology in the bulk is near the cylindrical/lamellar phase boundary) depends on the initial solution state (whether micellar or not and hardness of micelles) and the SM uptake ratio. These factors, along with solvent evaporation rate and film thickness, influence the kinetics of morphology development in the drying films, the point at which the kinetics are frozen in, the effective block ratio, and the orientation of the morphological structures.
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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 | 0.000 |
| 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".