Determination of the Mode of Free Radical Termination from Pulsed Laser Polymerization Experiments
Bibliographic record
Abstract
Abstract The molecular‐weight distribution (MWD), obtained by pulsed laser polymerization (PLP) at the high termination rate limit has been considered for investigating termination kinetics. The proposed methodology takes into account both the composite model for termination and the chain‐length dependencies of propagation for short‐chain and long‐chain radicals. Power‐law expressions are used to represent propagation $[k_{\rm p}^L = k_{\rm p}^0 (L)^{ - \alpha } ]$ and termination $[k_{\rm t}^{L,L} = k_{\rm t}^0 (L)^{ - \beta } ]$ of long‐chain radicals (where k and k represent the maximum “virtual” rate coefficients for monomeric radicals, and α and β capture the chain‐length dependencies for propagation and termination), with the combined value of (β − α) evaluated from the MWD, after correcting for the influence of the kinetics of short‐chain radicals. A novel method is also developed for determining the mode of termination, δ, from MWDs produced by PLP at the high termination rate limit. Simulations for methyl methacrylate (MMA) polymerization at 25 °C confirm that the method can be applied robustly in the presence of complicating factors such as chain transfer to monomer and SEC broadening. The analysis of an experimental MWD obtained for MMA polymerization at 25 °C results in estimates of 0.14 ± 0.03 for (β − α) and 0.75 ± 0.04 for δ. magnified image
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 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 | 0.001 |
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".