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How to manipulate the electrospinning jet with controlled properties to obtain uniform fibers with the smallest diameter?—a brief discussion of solution electrospinning process

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Abstract

Solutions of five different polymers, namely, polystyrene (PS), polyacrylonitrile (PAN), polyhydroxybutrate (PHB), poly(D-L-lactic acid) (PLA), and Nylon6, were used to investigate their rheological properties on the electrospinnability. In order to effectively reduce the diameter of electrospun fibers, polymers with higher molecular weights (MW) were needed to develop entangled solutions at much lower concentrations and with viscosities as low as that of a pure solvent. A minimum polymer concentration 1.0–2.0 times larger than the entanglement concentration was required to prepare the bead-free fibers. Using this strategy, uniform PS fibers with the lowest ever diameter of ∼15 nm were successfully obtained using an MW of 3 × 107 g/mol at a concentration of 0.1 vol.%. For a given electrospinning solution, processing variables of low flow-rate (Q) and high voltage (V) were desirable in obtaining fibers with small diameters. However, Q and V were correlated by a power law relation: V∼Q a, wherein the exponent a had a value of 0.1–0.4, which was relevant with the solution types. Based on the finite element analysis (FEA), a significant measure of electric field (E) occurred around the needle tip used in the experiment, and its magnitude decayed with increasing distance from the needle end (z): E∼z −n. The exponent n was 1.0–2.0, depending on the needle–plate geometry, i.e., needle length, needle diameter (D o ), plate diameter, and tip-to-plate distance (H). According to FEA results, H exhibited negligible effects on the electric field in the region of interest, i.e., z/D o ∼1 to 10. Due to the presence of high measures of E at the needle end, approaches to render a shorter and thinner straight jet issuing from the Taylor cone to yield thinner fibers were sought because a more significant jet stretching in the “jet whipping region” can take place. A feasible route to predict the as-spun fiber diameter produced by the manipulation of the electrified jet is provided by experimentally measuring the jet diameter and numerically calculating the electric field for the jet whipping process.

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Notes

  1. Our Nylon6/FA system is a polyelectrolyte solution, which shows an upturn of η sp/c at low concentrations when the Huggins equation is applied to determine the intrinsic viscosity. At low concentrations, due to the electrostatic charge repulsion along the backbone chains, the typical characteristic for the polyelectrolyte is obtained η sp∼c0.5. According to the classic classification, the entanglement concentration is estimated to be 2 wt% by the concentration at which the exponent change from 0.5 to 1.5 [32]. When the Nylon concentration is high, the electrostatic interactions between backbone chains and solvents are highly screened and neutral solution dynamics are recovered, i.e., η sp∼c3.75 (as shown in Table 2). For a simple comparison with other solutions, we apply a consistent approach (the initial concentration at which the final linear domain is reached) to determine the ϕ e for our Nylon solution. It should be noted that our determined value corresponds to the onset of the concentrated regime defined traditionally for the polyelectrolyte solution [33].

  2. [36] In this paper, a different scaling rule for highly entangled PS in the semi-dilute regime (ϕ < 0.1) is derived to be: \( \phi_e^{1.3} = 20400/{M_w} \) for the UHMWPS, by which the calculated ϕ e is 2.94 and 0.36 vol% for the PS-U2 and PS-U30, respectively. On the other hand, a lower value of ϕ e is obtained using the conventional equation of \( {\phi_e} = 37400/{M_w} \), being 1.87 and 0.12% correspondingly.

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Acknowledgements

The authors are grateful to National Science Council of Taiwan (ROC) for the research grant (NSC92-2216-E-006-016) that supported this work. Financial aids from Taiwan Textile Research Institute (TTRI), Industrial Technology Research Institute (ITRI) and NCKU through the “Landmark Program of the NCKU top University Project” are also highly appreciated.

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  1. Chemical Engineering Department, National Cheng Kung University, Tainan, 701, Taiwan, Republic of China

    Chi Wang, Yong-Wen Cheng, Chia-Hung Hsu, Huan-Sheng Chien & Shih-Yung Tsou

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  1. Chi Wang
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  2. Yong-Wen Cheng
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Correspondence to Chi Wang.

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Wang, C., Cheng, YW., Hsu, CH. et al. How to manipulate the electrospinning jet with controlled properties to obtain uniform fibers with the smallest diameter?—a brief discussion of solution electrospinning process. J Polym Res 18, 111–123 (2011). https://doi.org/10.1007/s10965-010-9397-1

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