title: Solvent removal during synthetic and Nephila fiber spinning.
abstract: The process by which spiders make their mechanically superior fiber involves removal of solvent (water) from a concentrated protein solution while the solution flows through a progressively narrowing spinning canal. Our aim was to determine a possible mechanism of spider water removal by using a computational model. To develop appropriate computational techniques for modeling of solvent removal during fiber spinning, a study was first performed using a synthetic solution. In particular, the effect of solvent removal during elongational flow (also exhibited in the spinning canal of the spider) on fiber mechanical properties was examined. The study establishes a model for solvent removal during dry spinning of synthetic fibers, assuming that internal diffusion governs solvent removal and that convective resistance is small. A variable internal solvent diffusion coefficient, dependent on solvent concentration, is also taken into account in the model. An experimental setup for dry (air) spinning was used to make fibers whose diameter was on the order of those made by spiders (approximately 1 microm). Two fibers of different thickness, corresponding to different spinning conditions, were numerically modeled for solvent removal and then mechanically tested. These tests showed that the thinner fiber, which lost more solvent under elongational flow, had 5-fold better mechanical properties (elastic modulus of 100 MPa and toughness of 15 MJ/m3) than the thicker fiber. Even though the mechanical properties were far from those of dragline spider silk (modulus of 10 GPa and toughness of 150 MJ/m3), the experimental methodology and numerical principles developed for the synthetic case proved to be valuable when establishing a model for the Nephila spinning process. In this model, an assumption of rapid convective water removal at the spinning canal wall was made, with internal diffusion of water through the fiber as the governing process. Then the diffusion coefficient of water through the initial spinning solution, obtained ex vivo from the Nephila clavipes major ampullate gland, was determined and incorporated into the numerical procedure, along with the wall boundary conditions and canal geometry. Also, a typical fiber reeling speed during web making, as well as the assumption of a dry exiting fiber, were included in the model. The results show that a cross-section of spinning solution (dope), which is initially 70% water, spends 19 s in the spinning canal in order to emerge dry. While the dope cross-section traverses the canal, its velocity increases from 0.37 mm/s at the entrance to 12.5 mm/s at the canal exit. The obtained results thus indicate that simple diffusion, along with the dry wall boundary condition, is a viable mechanism for water removal during typical Nephila fiber spinning.
authors.affiliation: Harvard-MIT Division of Health Sciences and Technology, Cambridge, Massachusetts 02139, USA. kojic@mit.edu
authors.forename: Nikola
authors.initials: N
authors.lastname: Kojic
authors.forename: Milos
authors.initials: M
authors.lastname: Kojic
authors.forename: Sauri
authors.initials: S
authors.lastname: Gudlavalleti
authors.forename: Gareth
authors.initials: G
authors.lastname: McKinley
mesh_terms: D000818:Animals; D005260:Female; D011506:Proteins / Q000032:analysis / Q000737:chemistry*; D011994:Recombinant Proteins / Q000032:analysis / Q000737:chemistry; D012997:Solvents / Q000032:analysis / Q000737:chemistry*; D013112:Spiders; D013784:Textiles / Q000032:analysis
chemical_list: D011506:Proteins; D011994:Recombinant Proteins; D012997:Solvents