Molecular Entanglement and Electrospinnability of Biopolymers

Summary

Electrospinning is a fascinating technique used to fabricate micro- to nano-scale fibers from a wide variety of materials. Molecular entanglement of the constituent polymers in the spinning dope is essential for successful electrospinning. We present a protocol for utilizing rheology to evaluate the electrospinnability of two biopolymers, starch and pullulan.

Abstract

Electrospinning is a fascinating technique to fabricate micro- to nano-scale fibers from a wide variety of materials. For biopolymers, molecular entanglement of the constituent polymers in the spinning dope was found to be an essential prerequisite for successful electrospinning. Rheology is a powerful tool to probe the molecular conformation and interaction of biopolymers. In this report, we demonstrate the protocol for utilizing rheology to evaluate the electrospinnability of two biopolymers, starch and pullulan, from their dimethyl sulfoxide (DMSO)/water dispersions. Well-formed starch and pullulan fibers with average diameters in the submicron to micron range were obtained. Electrospinnability was evaluated by visual and microscopic observation of the fibers formed. By correlating the rheological properties of the dispersions to their electrospinnability, we demonstrate that molecular conformation, molecular entanglement, and shear viscosity all affect electrospinning. Rheology is not only useful in solvent system selection and process optimization, but also in understanding the mechanism of fiber formation on a molecular level.

Introduction

Electrospinning is a technique that is capable of producing continuous micro- to nano-scale fibers from a wide variety of materials. It has gained increasing academic and industrial interest¹. Though the setup and practice of electrospinning seem straightforward, the ability to predict electrospinnability and control fiber properties remains a challenge. The reason may lie in the fact that there are many factors influencing the electrospinning process² and the process, especially the path travelled by the fiber, is chaotic¹. Often an empirical “cook-and-look” approach is used for screening potential electrospinnable materia....

Protocol

1. Spinning Dope Preparation

1. Prepare a range of biopolymer concentrations to be investigated (0.1% to 30%, w/v) and be sure to consider moisture content of the biopolymer powder in these calculations. For each concentration, weigh the biopolymer (starch or pullulan) powder into a 50 ml test tube. Add aqueous dimethyl sulfoxide (DMSO) solution and a stir bar.
2. Place the tube into boiling water with constant stirring on a magnetic stirrer hotplate.
3. After about 1 hr, turn off heat and allow the dispersion to cool to room temperature. The dispersion is then ready for rheological testing and electrospinning.

2....

Results

Flow curves of the biopolymer dispersions as a function of biopolymer concentration and DMSO concentration in solvent were obtained. Two representative figures show the flow curves of starch (Figure 2A) and pullulan (Figure 2B) as a function of their concentration in pure DMSO solvent. The specific viscosities were plotted against biopolymer concentration (Figure 3A for starch and Figure 3B for pullulan). From these plots, entanglement concentrations wer.......

Discussion

Rheology is an essential tool to study the processing of polymers, including conventional fiber spinning and electrospinning¹³. From the steady shear rheological studies, polymer conformation and their interactions in different solvents can be resolved (Figures 2 and 3). At concentrations not high enough for biopolymer molecules to overlap with one another, their concentration dependence was around 1.4 (Figure 3), which was in good agreement with rep.......

Materials

List of materials used in this article

Name	Company	Catalog Number	Comments
Gelose 80 starch	Ingredion		Used as it is
Pullulan	Hayashibara Co. Ltd		Used as it is
Dimethyl sulfoxide	BDH Chemicals	BDH1115-4LP
Ethanol	VWR International	89125-172	200 proof
Rheometer	TA Instruments	ARES	50 mm cone and plate geometry
Syringe (10 ml)	Becton, Dickinson and Company	309604	Syringe with Luer-Lok® Tip
High voltage generator	Gamma High Voltage Research, Inc.	ES40P
Syringe pump	Hamilton Company	81620
Environmental scanning electron microscope	FEI Company	Quanta 200	for starch fibers
Environmental scanning electron microscope	Phenom-World	Phenom G2 Pro	for pullulan fibers