Formation of Colloidally Stable Phase Separated Poly(<i>N</i>-vinylcaprolactam) in Water: A Study by Dynamic Light Scattering, Microcalorimetry, and Pressure Perturbation Calorimetry
Bibliographic record
Abstract
The effect of temperature on aqueous solutions of poly( N -vinylcaprolactam) (PVCL) samples of molecular weights ranging from 21 000 to 1.5 × 10 6 g mol -1 was monitored by dynamic light scattering (DLS), high-sensitivity microcalorimetry (HS DSC), and pressure perturbation calorimetry (PPC) from 10 to 80 °C. The polymer was soluble in cold water and underwent phase separation at T CP ∼ 31−38 °C, depending on the molecular weight. The phase transition was endothermic, with an enthalpy change of 4.4 ± 0.4 kJ mol -1 . Stable particles of average diameters 80 nm (high molecular weight PVCL) and ∼ 180 nm (low molecular weight PVCL) formed above the phase transition temperature. The coefficient of thermal expansion of PVCL in water (α pol ), determined by PPC, underwent a sharp decrease at the temperature corresponding to the onset of phase transition, then it passed through a maximum, and decreased continuously with increasing temperature. The stability of the particles formed in PVCL solutions kept at temperatures exceeding T CP suggests that their surfaces possess a hydrophilic character. Results of microcalorimetric measurements carried out with solutions of PVCL in D 2 O add further strength to this conclusion. The thermodynamic and volumetric changes associated with the phase transition of aqueous PVCL solutions are compared to those of aqueous solutions of poly( N -isopropylacrylamide) (PNIPAM), a polymer that also undergoes a phase transition in water at ∼ 31 °C, and of poly(vinylpyrrolidone) (PVP), a polymer structurally related to PVCL, which is soluble in water at all the temperatures investigated here.
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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) | 0.000 | 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".