Broad frequency range characterization of molten polymers
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Bibliographic record
Abstract
We report a technique for obtaining the continuous retardation spectrum or relaxation spectrum over a very broad range of relaxation times. The major challenge is to obtain reliable data at the long-time end of the spectrum. It is often not practical to use low-frequency oscillatory shear to obtain the necessary data because of the very long time required for the measurements. Polyolefins pose special problems in long-time characterization, because time-temperature superposition is not very useful. Information about the long-time behavior can be obtained by means of creep experiments, but now another problem arises. If we use a stress sufficiently large to yield precise data, the strain may go beyond the limit of linear viscoelastic behavior before steady state is achieved. This problem can be addressed by eliminating the stress well before nonlinearity becomes a problem and tracking the resulting recovery. Using a method proposed by Meissner, the combined creep and recovery data can be used to construct the entire creep curve. The final challenge is to combine the data from the oscillatory shear and creep experiments to obtain a composite linear spectrum. We propose a new method for accomplishing this. Retardation spectra are inferred from both sets of data and compared to reveal the range of times over which both techniques provide reliable data and the range in which each technique is uniquely reliable. The two spectra can then be combined to form a composite spectrum, which can be used to calculate any linear material function. This procedure is demonstrated for two branched polypropylenes whose terminal zones could not be accessed by means of oscillatory shear. For each of these materials, we found that the spectra obtained by the two experimental techniques superposed perfectly within the region of overlapping experimental windows, making it possible to construct a reliable composite spectrum valid over a wide range of times. The composite continuous spectrum is more directly related to molecular structure than rheological properties, such as the complex modulus, which involve integrals of the spectrum.
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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