Abstract
Uniaxially oriented, piezoelectric silk films are prepared by a two‐step method that involves first air drying aqueous, regenerated silk fibroin solutions into films, and then drawing the silk films to a desired draw ratio. The utility of two different drawing techniques—zone drawing and water‐immersion drawing—is investigated for processing the silk for piezoelectric studies. Silk films zone drawn to a ratio of λ 5 2.7 display relatively high dynamic shear piezoelectric coefficients of d~14~ 5 –1.5 pC N^21^, corresponding to an increase in d~14~ of over two orders of magnitude due to film drawing. A strong correlation is observed between the increase in silk II, β‐sheet content with increasing draw ratio as measured by FTIR spectroscopy (C~b~ $ \propto $ e^2.5__λ__^), the concomitant increasing degree of orientation of β‐sheet crystals detected via wide‐angle X‐ray diffraction (full width half maximum (FWHM) = 0.22° for λ = 2.7), and the improvement in silk piezoelectricity (d~14~ $ \propto $ e^2.4__λ__^). Water‐immersion drawing leads to a predominantly silk I structure with a low degree of orientation (FWHM 5 75°) and a much weaker piezoelectric response compared to zone drawing. Similarly, increasing the β‐sheet crystallinity without inducing crystal alignment, e.g., by methanol treatment, does not result in a significant enhancement of silk piezoelectricity. Overall, a combination of a high degree of silk II, β‐sheet crystallinity and crystalline orientation are prerequisites for a strong piezoelectric effect in silk. Further understanding of the structural origins of silk piezoelectricity provides important options for future biotechnological and biomedical applications of this protein.