Kinetic Modeling of Surface‐Initiated Atom Transfer Radical Polymerization
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Bibliographic record
Abstract
Abstract A kinetic model has been developed using the method of moment for surface‐initiated atom transfer radical polymerization (s‐ATRP) from flat solid surfaces based on a moving boundary physical model. The model is verified with the experimental data of 2‐methacryloyloxyethyl phosphorylcholine from silicon wafer, which were carried out by either adding free initiator (Method I) or excess deactivator (Method II) to the solution. It is shown through the modeling that Method II gives better control over polymer molecular weight and thicker graft layer under similar conditions than Method I. A new mechanism is proposed for the radical termination based on the fact that the rapid activation/deactivation cycle reactions facilitate “migration” of radical centers on the surface. The rate constant of “migration termination” is thus catalyst concentration dependent with higher catalyst concentration resulting in higher termination. Lowering catalyst concentration suppressed migration termination that could improve the control and livingness of s‐ATRP. However, there exists a catalyst concentration for the optimal control performance. magnified image
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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 it