Whilst much is known about the properties of silks, the means by which native silk feedstocks are spun still represent a gap in our knowledge. Rheology of the native silk feedstocks is germane to an understanding of the natural spinning process. Yet, an overview of the literature reveals subtle limitations and inconsistencies between studies, which has been largely attributed to sample-to-sample variation when testing these exquisitely flow-sensitive materials. This ambiguity has prevented reliable, consistent inferences from standard polymer rheology and constitutes an obstacle to further development.To address this challenge, we present the largest study to date into the rheological properties of native silk feedstocks from Bombyx mori larvae. A combination of shear and oscillatory measurements were used to examine in detail the relationships between concentration, low shear viscosity, relaxation times, complex modulus and estimates of the molecular weights between entanglements. The results from this highly detailed survey will provide a sound basis for further experimental or theoretical work and lay the foundations for future bio-inspired processing of proteins
We used two-dimensional infrared spectroscopy to disentangle the broad infrared band in the amide II vibrational regions of Bombyx mori native silk films, identifying the single amide II modes and correlating them to specific secondary structure. Amide I and amide II modes have a strong vibrational coupling, which manifests as cross-peaks in 2D infrared spectra with frequencies determined by both the amide I and amide II frequencies of the same secondary structure. By cross referencing with well-known amide I assignments, we determined that the amide II (N-H) absorbs at around 1552 and at 1530 cm–1 for helical and β-sheet structures, respectively. We also observed a peak at 1517 cm−1 that could not be easily assigned to an amide II mode, and instead we tentatively assigned it to a Tyrosine sidechain. These results stand in contrast with previous findings from linear infrared spectroscopy, highlighting the ability of multidimensional spectroscopy for untangling convoluted spectra, and suggesting the need for caution when assigning silk amide II spectra.
This paper describes research performed on a polymer-bonded sugar (PBS) consisting of 66% caster sugar in a hydroxyl-terminated polybutadiene (HTPB) binder The mechanical response of the PBS and pure HTPB to applied loading at a strain rate of approximately 2000 s −1 at temperatures from −80 to +22°C is presented. The materials were also characterized using dynamic mechanical analysis, X-ray tomography and quasi-static loading. These measurements are required for the development of intermediate strain rate constitutive models of polymer-bonded explosives, for which PBSs are a commonly used mechanical simulant. The current constitutive modelling suffers from a lack of experimental data on well-characterized composites and binders, especially at intermediate strain rates. This is particularly important for understanding the effects of mixing two materials. Applications of such modelling include explosive safety and fundamental understanding of the various deformation mechanisms. In this paper, the dependences of strength and deformation mechanism on temperature, and, in particular, the glass transition temperature of the binder, are shown. Physical damage plays an important role; X-ray tomography scans support debonding as the primary form of damage during room-temperature deformation. These results are in agreement with previous investigations and are discussed in this context.