Quantifying the Level of Intermacromolecular Interactions in Ethylene–Propylene Copolymers by Using Pyrene Excimer Formation
Bibliographic record
Abstract
A unique methodology based on fluorescence measurements is introduced to quantitatively measure the actual level of interpolymeric association between ethylene–propylene (EP) copolymers used as viscosity index improvers (VIIs) in engine oils. To this end, two EP copolymers, one amorphous (EP(AM)) and the other semicrystalline (EP(SM)), were maleated and then fluorescently labeled with 1-pyrenemethylamine and 2-(2-naphthyl)ethylamine to yield Py-EP and Np-EP, respectively. Successful maleation and fluorescence labeling were confirmed by Fourier transform infrared (FTIR) spectroscopy. The level of crystallinity of the EP copolymers was inferred from FTIR, carbon nuclear magnetic resonance ( 13 C NMR), and differential scanning calorimetry (DSC) experiments. The solution behavior of the EP copolymers was characterized by conducting intrinsic viscosity measurements as a function of temperature to define the temperature range where fluorescence studies should be conducted. Fluorescence resonance energy transfer (FRET) experiments were used to demonstrate the existence of interpolymeric associations, but a quantitative measure of the actual level of association, such as the molar fraction of interpolymeric interaction ( f inter ) between EP copolymers, could not be determined by FRET. However, taking advantage of the fact that the fluorescence intensity ratio I E / I M of excimer-to-monomer is directly proportional to the local pyrene concentration [Py] loc of a pyrene-labeled polymer, a quantitative measure of the actual level of intermolecular association was obtained by measuring the I E / I M ratio. Results showed that f inter of pyrene-labeled EP(SM) increased upon decreasing the temperature and increasing the polymer concentration as would have been expected from such a polymer. This result suggests that pyrene excimer formation provides a reliable method to quantitatively determine f inter for EP copolymers used as VIIs, an information which is otherwise difficult to extract from standard FRET experiments.
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How this classification was reachedexpand
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".