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Review
Blowspinning: A new choice for nanofibers
Jianan Song, Ziwei Li, and Hui Wu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c05740 • Publication Date (Web): 06 Jul 2020
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Page 1 of 52 ACS Applied Materials & Interfaces
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Blowspinning: A new choice for nanofibers
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Jianan Song, † Ziwei Li,† Hui Wu⁎, †
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† State Key Laboratory of New Ceramics and Fine Processing, School of
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Materials Science and Engineering, Tsinghua University, Beijing 100084,
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China
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18 KEYWORDS: blowspinning, nanofibers, equipment, structures,
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20 applications
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25 ABSTRACT
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28 Blowspinning is a new technique that enables the large-scale
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30 production of fibers with diameters ranging from micrometer to nanometer,
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32 which is more like a combination of melt-blown and electrospinning but
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34 has its own characteristics. This method can be used to deposit fibers in
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36 situ and produce various fibrous materials, such as coating, nonwoven and
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38 sponge. These characteristics provide a new strategy for nanofiber
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40 application and attract the interest of many researchers. Enclosing
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42 blowspinning technique, systematical researches have been carried out,
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44 involving in basic principle, empirical studies, spinning equipment and
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46 application. This review is intended to emphasize trends and gaps in the
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48 form of a concise illustration of various research direction.
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ACS Applied Materials & Interfaces Page 2 of 52
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1. INTRODUCTION
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Fibers have been used for thousands of years in human history.1 Most
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of the time, their applications were limited to some traditional fields, such
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as clothing, yarns and fabric due to traditional production methods.
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However, the manufacturing technique of fiber have experienced a
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15 remarkable progress in the past 50 years.2-7 Now, fibers are widely used in
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17 new application such as biomedical engineering, filtration, water treatment
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19 and electronics. Meantime, fibers are undergoing a revolution of thinning.
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21 A large number of synthetic and fabrication methods are still being
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23 researched for ultrathin fibers.8-13 Among these methods, blowspinning is
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25 an emerging method.13 Unlike other methods, it utilizes a high-speed
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27 airflow to stretch the polymer solution along the airflow direction (Figure
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29 1a).14 This technique is similar to the melt-blown process for drawing
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31 molten polymer except for the use of polymers solution to continuously
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33 reduce the diameter of liquid jet due to lower viscosity (Figure 1b).15
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35 Compared with melt-blown, blowspinning is better suited for fabricating
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37 fibers with much thinner diameters, since the drafting process is also
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39 accompanied volume reduction through evaporation of solvents. Like melt-
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41 blown, blowspinning is also a continuous process and therefore should
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43 work well for large scale production.
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Figure 1. (a) Schematic of a blowspinning. Adapted with permission from ref 14.
29 Copyright 2017 American Association for the Advancement of Science. (b) Schematic
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31 illustration of the setup for melt-blown. Adapted with permission from ref 15.
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33 Copyright 2012 Elsevier. (c) Schematic illustration of the electrospinning setup.
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Adapted with permission from ref 16. Copyright 2004 Wiley-VCH. (d) Demonstrating
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36 how blowspinning can “paint” nanofibers onto irregularly shaped objects made from
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38 wide range materials (rubber hand, steel bolt, and wooden tongue depressor). Adapted
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40 with permission from ref 17. Copyright 2013 Elsevier.
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The blowspinning technique may be considered as a variant of a well-
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known method, electrospinning technique.18-20 Both techniques mainly
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stretch and refine polymer solution and obtain fibers as the solvents
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evaporate. In electrospinning, the jet is continuously stretch due to
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electrostatic force in high voltage electric field and become the solid fiber
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before depositing the metal collector (Figure 1c).16 In blowspinning, a
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55 pressurized gas is utilized to both drive the polymer solution jet and cause
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57 solvent evaporation. Electrospinning has been widely adopted in academic
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59 and industry. But the use of high voltage electric fields as driving force
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make it several limitations in safety, stability and scalability.21 Instead,
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blowspinning has fewer process requirements and variables. A wide range
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of solution systems and collector without conductivity requirement can be
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used. Fibrous materials, such as coating, nonwoven and sponge can be
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quickly manufactured and deposited in each target area (Figure 1d).17 These
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14 unique characteristics provide a new path to explore the utilization of
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16 fibrous materials.
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19 Our group mainly focus on the application and large-scale production of
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21 blowspinning and always concern about exploration work by our
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23 counterparts. It is notable that the number of publications in this field is
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25 sustained growing in the past 5 years (Figure 2). Examination of past
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27 research make us realize that many fundamental studies have laid the
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29 foundation of today 's result and more journeys need to be explored.
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31 Therefore, the aim of this review is to emphasize trends and gaps in the
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33 form of a concise illustration of various research direction. The main text
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35 of this article is organized into six sections: the first section give a brief
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37 introduction to the basic principle and theoretical background for
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39 blowspinning; the second section demonstrate comprehensive progress in
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41 setups for blowspinning; the third section provide strategy for choice of
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43 system and parameter. the fourth section summarizes feature of blowspun
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45 fibers. The fifth section discuss recent developments in application for
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47 blowspinning. Finally, a personal perspective on the futures of this
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22 Figure 2. Graph showing research articles of blowspinning published in recent years.
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24 These numbers were obtained from the Web of Science SCI Core Collection in
25 2020/03/13. Blowspinning research has been denoted “solution blow spinning”
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27 “solution blowing” “air-jet spinning”and “airbrushing”, but these techniques share the
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29 same governing principles. Thus, we retrieve all these names in the statistic.
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2. BLOWSPINNING PROCESS
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2.1 Basic principle
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The whole process of blowspinning to produce fibers is
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straightforward. Initially, the precursor solution must be formed. Polymer
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is dissolved into the volatile solvent to form a homogeneous solution.
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Several materials, such as ceramics, metal, and certain metal salts, can also
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be selected as additives to be dissolved into the polymer solution and form
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the spinnable solution. And then the precursor solution is squeezed into a
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fine needle tip by employing a pump. The internal diameter of the needle
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is usually 0.1–0.3 mm. A high-speed airflow (10–200 m/s) is provided
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along the direction of the needle and thereby the precursor solution focus
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into a thin liquid jet. After the evaporation of the solvent, the resulting fiber
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can be collected as various fibrous materials.
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During the blowspinning process, any change in the air pressure is
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converted into the kinetic energy of the solution according to Bernoulli
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principle.22 As the high-pressure gas is sprayed from the nozzle tip, the air
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15 pressure is converted into kinetic energy and the flow speed of the gas rises.
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17 Figure 3a shows a schematic diagram of the air pressure distribution during
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19 the blowspinning process.13 The high-speed airflow flows through the area
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21 surrounding the solution and this generates a reduction in the pressure (P2)
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23 in the internal zone of the liquid jet flow. This constitutes the driving force,
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25 which drafts the solution to form the fiber. At the same time, the high-speed
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27 airflow generates a shearing force on the gas-liquid surface, which deforms
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29 the solution at the needle tip and forms a liquid cone. When the shearing
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31 force overcomes the surface tension of the solution, the jet flow emerges
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33 from the end of the liquid cone and it is sprayed out of the needle along the
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35 direction of the airflow. Then, the jet flow solvent completely volatilizes
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25 Figure 3. (a) Schematic illustration of the pressure distribution around the nozzle: high
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27 pressure flows through an outer nozzle (P1). The nozzle geometry creates a region of
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low pressure around the inner nozzle (P2), which shapes the polymer solution into a
30 cone. Adapted with permission from ref 13. Copyright 2009 Wiley-VCH. (b1, b2)
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32 High-speed photograph of a polymer solution cone at the tip with a small air-flow speed,
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34 (b3) with the correct air-flow speed, and (b4) at high air-flow speed. (c) Contours of the
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velocity field below the nozzle during blowspinning. Adapted with permission from ref
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37 22. Copyright 2014 American Chemical Society.
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In experiments, the shape of the liquid cone changes with the
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experimental conditions. If the speed of the airflow is too small and the
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liquid is constantly supplied (Figure 3b1 and b2), a small jet flow sprays out
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from the front end of liquid cone. In this case, the liquid cone cannot
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maintain a stable shape due to the insufficient tensile force and a
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53 continuous spinning cannot be achieved. The liquid cone becomes stable
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liquid cone disappears, the solution will break into many small droplets at
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the vent and no liquid jet can be observed. The speed of the airflow should
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match the speed of the liquid supply and this is key to form the liquid cone.
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Actually, the stable shape of the liquid cone is affected by the airflow field.
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Figure 3c shows the CFD (Computational Fluid Dynamics) simulation
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16 end of the needle tip when a high-speed airflow is employed.22 The high-
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18 speed airflow creates a negative pressure zone, which induces a gradual
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45 Figure 4. Microphotographs of blowspun fibers taken by a high-speed camera. (a1-a3)
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Jets of polymer solution formed near the cone tip stream toward the collector. Adapted
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48 with permission from ref 13. Copyright 2009 Wiley-VCH. (b1-b3) Bending instability
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50 and flapping motion in blowspinning under either a low to a high air-flow speed.
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52 Adapted with permission from ref 22 Copyright 2014 American Chemical Society.
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When the shear force is larger than the surface tension of the solution
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at the liquid-gas boundary (Figure 4a) the front end of the liquid cone
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breaks and multiple jet flows are obtained under the action of the high-
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speed airflow.13 The high-speed camera images show that the jet flow
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initially maintains a straight-line trajectory and then, the path of the jet
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liquid starts bending. Figure 4b shows that the liquid jet swings up and
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down along the central position under the action of the airflow turbulence.
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A lower airflow speed reduces such swing behavior.22 During the drafting
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21 As result, the blowspinning technique consists of three processes: 1) A
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23 stable liquid cone forms; 2) A jet flow emerges from the liquid cone via
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37 2.2 Theoretical background
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40 Due to the enough mass, the jet initially maintained a linear motion,
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48 high-speed airflow, which can refer to a general theory about the behavior
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53 Sumit et al attempted to describe the straight-line motion and the
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(Equation 1)25, 26 The following expression can be used to describe the
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distribution of a liquid jet of cross section (𝑓) that travels along the x-
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d ( fV )
8  hm CS ,eq (T )  CS ,  2 a
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15 Reference to the description of the linear motion of momentum conservati
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17 on and the rheological behavior of uniaxial elongation fluid by the upper-
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linearly moving jet can be described by the following formula:
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dV V -  xxV  (  f /  )  q
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 2 ( xx   /  )   xx /  
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39 general quasi-one-dimensional theory of free liquid jets.27, 28 Due to the jet
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one-dimensional equations with momentless approximation. Finally,
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Sumit solved this system of equations and compared it with the
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experimental results. Figure 5 shows the simulation results of the jet-flow
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swing area.24 The diameter of the liquid jet bending area measures 0.38 cm,
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which is nearly in agreement with the experimental result (0.33 cm).
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22 Figure 5. Snapshot of the jet configuration at the beginning of the bending section.
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24 Comparison between the predicted value and the experimental observation. Adapted
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Despite the blowspinning process is quite simple, it still involves
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many variables and factors, such as the concentration of an additive
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macromolecule, the solvent volatility, the air flow speed, the liquid supply
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speed, the diameter of the needle tip. These factors play a role in the
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definition of the spinning stability and of the fiber morphology.
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40 The additive amount of polymer in the spinning solution influences
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42 the spinnability of the solution itself. The overlap concentration (c*) in
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44 Equation 4 defines a critical point during the process: the polymer
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46 entanglement is significant enough to stabilize the polymer jet.29, 30 The
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48 value of c* guides the preparation of the precursor solution. The effect of
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52 verified by Srinivasan et al.31 When the polymer in the solution reaches the
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54 overlap concentration, a stable liquid jet forms. Figure 6 (a–c) show the
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56 microtopography of a blowspinning fiber with different polymer
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can be observed.31 Upon the increase in the polymer concentration, the bead
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9 10 c*. The overlap concentration approach requires the solvents to
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13 pivotal when using this method. In fact, c* is highly influenced by the
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15 polymer properties, such as its chain-end type and molecular weight. 32, 33
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17 Different polymer properties lead to a different interplay between the
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19 viscous forces, the inertio-capillary forces, and the polymer relaxation time,
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24  3/2 M W
c* 
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Figure 6. SEM images of the PMMA fibers for different concentration of PMMA in
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45 from ref 31. Copyright 2011 Elsevier.
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48 Due to influence factors are many and complicated, it is difficult to
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50 fully explain the whole process by a single theory. Therefore, some
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52 researchers analyze the impact of various factors on the blowspinning
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54 process based on experimental results.34-40 Based on the Box-Behnken
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56 Design, Lou et.al investigate the effects of the solution concentration
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58 airflow speed, syringe needle diameter, and solution injection speed on the
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fiber morphology and on the fiber diameter.39, The researcher obtained the
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empirical formula, which links these four factors to the evolution of the
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fiber diameter. The results show that the solution concentration has a
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decisive impact on the fiber formation. The mix-solvent experiment
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conducted by Zhang et al. demonstrates that any improvement in the
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14 volatility of the solvent helps in increasing the yield rate of spinning and
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16 optimizes the fiber morphology.40 Although these studies are only
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26 3. SPINNING EQUIPMENT
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29 The basic laboratory equipment for blowspinning consist of four
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31 major components(Figure 7a) 13, ie., (1) a high-speed gas flow supply, (2)
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33 solution supply, (3) collector, (4) a spinneret. For a high-speed gas flow
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35 supply, either gas cylinder or air compressors is often used. For solution
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37 supply, the injection pump is the most widely used(Figure 7b). Our group
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39 also recommend to use gas pressure to supply solution(Figure 7c). Both
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41 two methods are easy to operate, which are suitable for laboratory, but
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43 these two methods cannot transport solution continuously due to limit of
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45 solution loading. If continuous solution delivery is required, gear pumps
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47 and diaphragm pumps are generally used. For the collector, there are no
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49 more restrictions. A rotating drum should only need to be used when
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51 preparing nonwoven. In the spinneret, the polymer solution is surrounded
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53 by a high-speed air flow and thereby focus into a thin liquid jet. The
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55 spinneret directly affects the formation of fibers, which is core component
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57 of the equipment. According to the different requirements, specific
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modifications to spinneret have been done by researchers. 17, 41-48 In next
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paragraphs, these progresses are reviewed.
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34 Figure 7. (a) Schematic of the blowspinning system. Adapted with permission from
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36 ref 13. Copyright 2009 Wiley-VCH. Two methods for the solution supply: (b) syringe
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38 pump and (c) air pressure.
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41 3.1 Basic configuration of spinneret
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44 Gas/liquid coaxial is basic configuration of spinneret. As shown in
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46 Figure 8a, the spinneret consists of an internal and an external cavity.45 The
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48 polymer solution flows inside the internal cavity, whereas the high-speed
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50 airflow travels through the external one. Dispensing needle is usually used
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52 as internal cavity (Figure 8b). In order to achieve a good spinning stability,
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54 the needle tip should be positioned in the center of and sticks out the
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56 external cavity. Our group provided a simple configuration of spinneret
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58 (Figure 8c). The bent needle is directly placed in the front of the vent. When
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the next experiment is performed, the needle can be easily and quickly
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replaced. Besides, Tutak et al. creatively employed the existing hand-held
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airbrush to achieve the blowspinning process (Figure 8d).17 fibers can be
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directly sprayed in situ by using this device.47, 49 In addition to a single axial
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for liquid, multi-axial blowspinning enable the simultaneous spinning of
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14 different solution and are widely applied for the fabrication of composites
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16 core/shell nanofibers, 41 of hollow tubes.50
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41 Figure 8. (a) co-axial spinneret. Adapted with permission from ref 45. Copyright 2016
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American Chemical Society. (b) home-made co-axial spinneret. Adapted with
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44 permission from ref 46. Copyright 2017 Springer. (c) simple spinneret, and (d) airbrush.
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46 Adapted with permission from ref 17. Copyright 2013 Elsevier.
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49 3.2 Up-scaling
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52 Another important issue concerning process up-scaling. The capacity
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54 of high volume production is critically important in respect of practical
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56 application. Multi-spinneret can be useful for increasing the overall set-up
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58 output. Several research groups including our group have done some
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research on multi-spinneret. Alexander et al. first developed a multi-
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spinneret with 8 rows with 41 concentric annular nozzles. They claimed
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that nanofiber mats an area of the order of 0.1-1 m2 were formed in about
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10 s (Figure 9a–b).51 Our group has done a series of work for large-scale
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production. The “roll to roll” continuous spinning equipment has been
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14 designed by our groups (Figure 9c).52 With the help 3D printing technique,
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16 airways device was designed, which contain multiple gas outlets. The
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18 devices allow one to simultaneously spin 5–8 needles in series. On the basis
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20 of above, our group designed integrated multi-spinneret (Figure 9d).48
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22 Unlike the former, the integrated multi-spinneret have an integral liquid
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24 cavity, which can supply solution for multi-needle at the same time. In
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26 order to increase the output of hand-held devices, our group also designed
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28 a 4-needle hand-held spinneret (Figure 9e).53
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3 Figure 9. (a, b) Multi-nozzle blowspinning spinneret. Adapted with permission from
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5 ref 51. Copyright 2016 American Chemical Society. (c) New multi-nozzle
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7 blowspinning spinneret produced via 3D printing. Adapted with permission from ref
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52. Copyright 2017 Wiley-VCH. (d) Integrated multi-needle spinneret. Adapted with
10 permission from ref 48. Copyright 2020 Springer. (e) Four-needles hand-held
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12 blowspinning apparatus. Adapted with permission from ref 53. Copyright 2017
13
14 American Chemical Society.
15
16
17 In fact, most of researches for multi-spinneret of blowspinning are
18
19 look like in the experimental stage, which demonstrated the great potential
20
21 for integration and upscaling of blowspinng, but cannot meet actual
22
23 production demand due to deletion of stability and reliability. In order to
24
25 achieve large-scale production of blowspinning, there is still a long way to
26
27 go. Stability and reliability need more attention. Optimization based on
28
29 mature equipment is an effective way to make industrialization of new
30
31 technique. Improvement of melt-blown equipment is one of a correct
32
33 choice, but few studies show that the melt-blown spinneret can be adapted
34
35 to blowspinning. Zhuang et. al used a spinneret containing an air flue
36
37 （ similarly to the melt-blown technique ） to successfully prepare the
38
39
40 nanofibers.54 Unfortunately, the paper lacks details to reproduce the setup
41
42 and the results. Besides, the traditional multi-spinneret method is, in
43
44 principle, subject to problems related to nozzle clogging, which may limit
45
46 the continuity of the production process. Such clogging events can occur
47
48 because of the fineness of the needle and the turbulent airflow. In this
49
50 respect, other needleless configurations are deserved to be studied.
51
52
53
54
55
56 4. CHOICE OF SYSTEM AND PARAMETERS
57
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1
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3
4
In principle, the blowspinning technique exhibits a better
5
6
compatibility with the spinning solution, since it does not require a
7
8
conductive one. Almost all solvable polymers can be obtained via the
9
10
blowspinning, as long as the appropriate solution parameters (polymer,
11
12
solvent, concentration of the solution, solution viscosity, and surface
13
14 tension of the solution) and the preparation parameters (airflow speed,
15
16 solution supply speed, diameter of the needle tip, environmental
17
18 temperature, and relative humidity) are selected. The experience of the
19
20 researcher is critical to prepare the fiber. When selecting the system, the
21
22 first step is to select a suitable polymer based on the performance of the
23
24 fiber and the requirements of the spinning parameters. The polymer is
25
26 mainly used either as the main material or as a spinning additive. If the
27
28 polymer is used as the main material, its pure-phase has to be suitable for
29
30 spinning, and this depends on its physical, chemical, and
31
32 mechanical properties. If it is used as a spinning additive, the polymer
33
34 facilitates the spinning process in other materials and it sometimes needs
35
36 to be removed easily. For instance, a polymer may be added to improve the
37
38 spinnability of the precursor solution when preparing inorganic fibers.
39
40 Furthermore, it should be removed via pyrolysis.
41
42
43 The selection of a suitable system is a very complex process and there
44
45 is no way to summarize it into a simple theory. Therefore, in accordance
46
47 with the polymer function, the possible systems can be divided into four
48
49 categories: the single-phase polymer fiber, the blend polymer fiber, the
50
51 inorganic fiber, and the complex fiber. The proper selection of the solvent
52
53 is also a crucial step. The solvent must be, in fact, compatible with the
54
55 solute and with the polymer. In the blowspinning process, a volatile solvent
56
57 must be selected. If the solvent does not volatilize quickly enough, the fiber
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3
4
is difficult to dry, and it may dissolve again.40 Special attention must be
5
6
paid to the nontoxicity and to the environmental protection properties of
7
8
the solvent. In the medical field, the solvent must be harmless to human
9
10
body.55-57 For these reasons, the most common solvents are water, acetone,
11
12
and other similar solvents. Selecting a non-toxic and an environmental-
13
14 friendly solvent during the production process is crucial. Although the
15
16 airflow can dilute the concentration of the solvent in during the process an
17
18 excessive amount of solvent may lead to exceed the standard value of
19
20 volatile organic compounds (VOC) concentration and generate
21
22 environmental damages. The concentration of the solute in the solution
23
24 (and especially the concentration of the polymer) affects the fiber
25
26 morphology. According to the experimental findings, the fibers tend to
27
28 become more uniform and more cylindrical as the concentration of the
29
30 polymer in solution rises. Moreover, the diameter of the fiber increases.
31
32 For low polymer concentration, the fibers become thinner, but the bead
33
34 occurs. The viscosity and the surface tension of the solution may also affect
35
36 fiber morphology, despite it is really challenging to find a reference value
37
38 for these parameters. Viscosity and surface tension are affected by the
39
40 solution proportion and the temperature. For this reason, comparative
41
42 control tests can only be carried out by varying the solution proportion and
43
44 temperature.58
45
46
47 The spinning parameters must be adjusted according to the different
48
49 solution systems. The ultimate target of such parameter adjustment is to
50
51 obtain stable liquid jets and guarantee the solvent volatilization to form the
52
53 fiber. The match between the liquid supply speed and the airflow speed is
54
55 the precondition to form stable liquid jets. If the liquid injection is rapid,
56
57 the solution does not draft, and it continuously accumulates inside the
58
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4
needle holes. This generates an interruption in the formation of the liquid
5
6
cone. If the airflow speed increases further, the liquid supply speed is lower
7
8
than the jetting speed of the solution and the stable liquid cone cannot form.
9
10
By adjusting the liquid supply speed and the airflow speed and obtaining a
11
12
match, a stable liquid cone forms inside the needle. If then the airflow
13
14 speed remains constant and the liquid supply speed increases gradually, a
15
16 change in the fiber morphology may gradually occur under the form of
17
18 fiber entanglement and bead.34 The experimental results show that the
19
20 diameter of the needle affects the spinning stability. For this reason, the
21
22 type of needle has to be selected according to the solution viscosity: the
23
24 lower the solution viscosity is, the smaller is the diameter of the needle tip
25
26 to employ.51 The environmental temperature and humidity affect the
27
28 solvent volatilization properties, in particular in the case of water-soluble
29
30 polymer systems.59 However, since a rigorous control of such parameters
31
32 is costly, it is generally neglected.
33
34
35 To summarize, the stable production of blowspun fibers requires to
36
37 adjust the solution and spinning parameters according to the physical and
38
39 chemical nature of the target material. In the following sections, various
40
41 material systems are discussed and a series of parameters to optimize the
42
43 fiber production are proposed.
44
45
46 4.1 Single-phase polymers
47
48
49 A single-phase polymer material system is used to produce a fiber
50
51 from a target polymer material via blowspinning. Polymers can be directly
52
53 used without employing additional materials. In general, such polymers
54
55 have a rather high molecular weight, can only solve in specific solvents,
56
57 and present a high solubility. Several examples are provided in the Table
58
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1. These rather common polymers, such as Polyethylene oxide (PEO),
5
6
Polyvinyl alcohol (PVA), Polystyrene (PS), Nylon6, Polycaprolactone
7
8
(PCL), Poly(D,L-lactide) (PDLLA), Polylactic acid (PLA), Polymethyl
9
10
methacrylate (PMMA), Polyacrylonitrile (PAN), Poly(vinylidene fluoride)
11
12
(PVDF), can be directly used in spinning applications and generate fibers
13
14 a diameter of 0.1–2 μm. The options for the solvent are diverse, non-toxic
15
16 solvents and environmental friendly solvents are the ideal candidates for
17
18 blowspinning. However, they only suit the water-soluble polymer systems,
19
20 such as PEO and PVA, which are rarely used. Due to their good solubility
21
22 and volatility, organic solvents are widely used for the blowspinning. For
23
24 instance, PLA can be dissolved in chloroform, dichloromethane, and
25
26 dichloroethane. When compared with three solvent options,
27
28 PLA/dichloroethane does not produce consistent fibers due to its lower
29
30 Hansen solubility parameters and solvent evaporation rate. In order to
31
32 obtain solvents with more suitable characteristics, it is possible to dissolve
33
34 two or more solvents together to form a mixed solvent.
35
36
37
Table 1. Blowspinning single-phase polymers.
38 Polymer system Solvent solution Ref.
39 PEO water 51
40 dichloroethane 60
41 acetone/DMF 61
42
PVA water 51
43
44 PVP ethanol 40
45 PS DMF 17
46 Toluene 13
47 Nylon 6 formic acid 62
48 PCL chloroform 63, 64
50
51
chloroform/methanol 17
52 PDLLA acetone 64
53 chloroform 17
54 DMC 65
55 chloroform/acetone 66
56 PLA chloroform 67, 68
57
dichloromethane 68
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3 chloroform/acetone 69
4
5
PMMA chloroform 66
6 acetone 64
7 PAN DMAc 22
8 DMF 70, 71
9 PVDF acetone/DMF; 61
10
11
12
4.2 Blend polymers
13
14
15
A blend polymer fiber system refers to the formation of a
16
17
homogeneous-phase solution by using two or more polymers during the
18
19
blowspinning process. Generally, the principal-phase polymer cannot be
20
21
used directly in blowspinning but only upon the addition of spinning
22
23
additives, such as PLA, PVA, and Nylon6. The spinning additive must be
24
25 selected according to the characteristics of the principal-phase polymer and
26
27 must be compatible with it. Moreover, the solvent must be able to jointly
28
29 dissolve all the polymers present in the solution. Several examples are
30
31 listed in Table 2. For instance, Polyaniline (PAni), a conductive polymer,
32
33 can be used to manufacture fibers with a diameter in the 0.14–0.59 μm
34
35 range if PLA is present in the solution. Several studies demonstrated that
36
37 polymeric fibers derived from plant and animal proteins could be
38
39 successfully prepared via blowspinning. Such as cellulose, the soy protein
40
41 and the fibroin one exhibit a high biological activity and biocompatibility.
42
43 For this reason, they can be used to perform wound dressing or as drug
44
45 transportation devices. However, since these polymers have a low
46
47 molecular weight, they cannot directly be used for spinning. Upon the
48
49 adding of nylon, PET, and other spinning additives, fiber polymers with a
50
51 0.1–2 μm diameter based on such compounds can be obtained.
52
53
54 Table 2. Blowspinning blend polymers.
55 Polymer system Solvent Solution Ref.
56
57 PANi /PLA HFP 13
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1
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3 PEG/ PLA Chloroform/acetone 72
4
5 cellulose acetate/PAN DMF 73
6
7 chitosan/ PVA formic acid 74
8
9
PDLLA-COOH/PDLLA acetone 75
10 RSF/ PEG water 76
11
12 protein/PET dichloroacetic acid 73
13
14 FSP/nylon 6 formic acid 77
15
silk sericin /nylon 6 formic acid 77
16
17 soy protein/nylon-6 formic acid 78
18
19 sulfonate lignin alkali/nylon 6 formic acid 77
20
21 zein/nylon 6 formic acid 77
22 soy protein/nylon-6 formic acid 28
23
24
25 4.3 Inorganic systems
26
27
28 Inorganic fiber system consists in using a homogeneous phase
29
30 solution or a sol-gel together with a series of inorganic ingredients and
31
32 polymer spinning additives. The precursor fiber is initially obtained via
33
34 blowspinning and then, thermally treated to eliminate the organic materials.
35
36 Finally, the inorganic fiber material can be obtained. During the
37
38 preparation process of the precursor solution, a precursor with a relatively
39
40 high concentration of inorganic salts is generally preferred because it can
41
42 make resulting inorganic fibers have higher strength and yield after thermal
43
44
45
treatment. But it may cause instability during electrospinning because the
46
47
electrical conductivity of the precursor rises with the increase of inorganic
48
49
salt content.79 In comparison, blowspinning has better adaptability to
50
51
produce inorganic fibers. Table 3 shows that the most widely used
52
53
inorganic ingredients in a solution are generally metal salts, such as AlCl3-
54
55
6H2O and ZrOCl2. To achieve a high solubility of the salts in solution, the
56
57
solvent is usually water or ethanol. For this reason, water soluble or ethanol
58
59
soluble polymers are used as spinning additives. An A12O3 fiber can be
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obtained by using an AlCl3 6H2O/ PVA system. A ZrO2 fiber can be
5
6
obtained by using the ZrOCl2/ PVP system. Silver fibers can be instead
7
8
manufactured by employing an AgNO3/PVP solution system. For the
9
10
production of TiO2 fibers and mullite fibers a sol-gel system has to be
11
12
prepared. Inorganic precursors are the organic alkoxides, such as tetrabutyl
13
14 titanate and ethyl orthosilicate. Since they exhibit effective hydrolyzing
15
16 characteristics, the adding sequence of the precursors has to be deeply
17
18 investigated. For instance, when preparing TiO2 fiber precursor solution,
19
20 PVP should be dissolved into ethanol firstly, and then mixed with the stable
21
22 solution of tetrabutyl titanate in order to avoid the hydrolyzation of
23
24 tetrabutyl titanate. Additionally, attention needs to be paid to the expiration
25
26 date of the solutions prepared via the sol-gel method.
27
28
29
Table 3. Blowspinning blend polymers.
30 Material Precursor Solvent Solution Ref.
31
32 Al2O3 AlCl36H2O/ PVA water 80
33
34 ZrO2 ZrOCl2/ PVP ethanol/water 81
35
36 YSZ zirconium n-propoxide/yttrium nitrate/ diacetone/ ethanol 17
37 PVP
38
39 BaTiO3 Ba(Ac)2/ Ti(OBu)4/ PVP acetic acid/ ethanol 82
40
41 ZnO2 TTIP/Zn(OAc)2/PVC THF 83
42
TiO2 titanium isopropoxide/PVP acetic acid/ethanol 46
43
44 17
Ti(OBu)4/ PVP ethanol/acetic acid
45
46 Mullite TEOS/Si(OC2H5)4/,Al(NO3).9H2O/PCL DMF 84
47
48 MFe2O4 Fe-nitrate and (Cu, Co or Ni)-nitrate/ ethanol/DMF 50
49 PVP
50
51 CaCoO Ca(NO₃)₂ · 4H₂O, /(Co(NO₃)₂ · 6H₂O/ ethanol/methanol 85
52
53
54 PVP
55
Ag AgNO3/PVP ethanol/water 86
56
57
58 4.4 Complex-phase systems
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A complex-phase polymer system consists of the addition of a broad
5
6
variety of materials in the main-phase polymer solution. These additives
7
8
usually have demand structure or function. Upon the addition of liquid
9
10
crystals (LCs), the blowspinning fiber exhibits novel electro-optical and
11
12
photo-thermal characteristics.87 After adding Ni nanoparticles in a PVDF
13
14 fiber 88, the fiber shows magnetic properties and it can be used in the
15
16 production of magnetic sensors. Fibrous material compounds based on
17
18 graphene and nylon exhibit an outstanding absorption capacity and a high
19
20 water permeability.89 Upon the addition of ZnO-LiCl, the conductivity and
21
22 the moisture sensibility of PVDF fiber materials improve.90 For this reason,
23
24 these compounds are used in the production of PVDF-based moisture
25
26 sensors. Benefiting from high adaptability of blowspinning, a variety of
27
28 material can be mixed and spun into more functional fiber materials
29
30 through this technique.
31
32
33
34
35
36 5. FIBER STRUCTURE AND PROPERTY
37
38
39 The macro/micro morphology of the material is responsible for its
40
41 functional characteristics. In this respect the manufacturing technique play
42
43 a key role in the morphology of the nanofiber. As a new technology for
44
45 nanofiber manufacturing, blowspinning can make a variety of fiber
46
47 materials, such as hollow nanofiber, nanofiber coating,47 nanofiber
48
49 nonwoven and nanofiber sponge (Figure 10a-b).91,92 Considering the effect
50
51 of nanofiber-based structure on performance has been widely discussed. In
52
53 the following, only features of blowspun nanofibers are discussed to avoid
54
55 duplication. Table 4 lists comparative data between blowspun fibers and
56
57 electrospun fibers. The observations of the morphology of a
58
59
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Polycaprolactone (PCL) fiber produced via blowspinning show that the
5
6
maximum porosity of the blowspun fibers reaches 95% and that its average
7
8
pore size measures 8–17 μm.17 When the electrospinning technique is used,
9
10
the porosity and the average pore size of fiber are lower (67% and 3 μm,
11
12
respectively). The airflow more easily blows away the fibers, which make
13
14 larger pore size and porosity in blowspun fibers. However, electrospun
15
16 fibers stack closer due to electric attraction.
17
18
Table 4. Comparison between the electrospinning and the blowspinning
19
20 technique.
21
22 Fabrication Blowspinning Electrospinning
23
24 Dimensions 100–1000 nm 10–500 nm
25
26
Mean pore size 8–17μm 3 μm
27 Porosity Up to 99% 67%
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47 Figure 10. (a) Image of blowspun nanofiber nonwoven; Adapted with permission from
48 ref 91. Copyright 2019 Wiley-VCH. (b) Image of blowspun nanofiber sponge; Adapted
49
51
52
53 A bundle of fibers is showed in the scanning electron microscopy
54
55 image of a blowspun fiber (Figure 11a). These phenomena have been
56
57 observed by several research teams.17, 60, 93 In comparison, the electrospun
58
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1
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4
fiber shows a more uniform distribution (Figure 11b).17 Our group also
5
6
observe in the experiment that the fiber bundles are more likely to form at
7
8
large solution supply. This phenomenon can be reduced by decreasing the
9
10
solution supply and accelerating the solvent evaporation. Daristotle et al
11
12
speculated that the formation of a fiber bundle may be related to the
13
14 bending instability of the airflow turbulence around the liquid jets during
15
16 the spinning process.29 This results in the formation of multiple bundles of
17
18 liquid jets, which spray out of a single nozzle and easily cross, forming
19
20 bundles of fibers before solidifying.45 The fiber bundles have a greater
21
22 impact on mechanical properties. Under the same strain, the stress that the
23
24 electrospun fiber can stand is higher than that of the blowspun fibers
25
26 (Figure 11c). The modulus of the former is 6 times higher than that of the
27
28 latter (Figure 11d).17 Moreover, fiber bundles can cause uneven fiber
29
30 distribution and reduce specific surface area, which requires special
31
32 attention in manufacturing.
33
34
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26
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28
29
30
31
32
33
34 Figure 11. (a) SEM image of blowspun nanfibers. (inset: SEM image of a YSZ
35
36 nanofiber Adapted with permission from ref 93. Copyright 2018 Wiley-VCH.) (b) SEM
37
38
image of electrospinning fibers. (c)Representative stress-strain plots for tensile testing
39 of blowspinning and electrospinning of PCL nanofiber mats. (d) Tensile modulus of the
40
41 blowspun PCL nanofiber and the electrospun PCL nanofiber. (a-d)Adapted with
42
43 permission from ref 17. Copyright 2013 Elsevier.
44
45
46 Fibers sponge is formed by three-dimension stacking of loose blowspun
47
48 fibers, which is the research focus of our group (Figure12a).14 This porous
49
50 structure is similar to the cotton candy and has a lower density. The density
51
52 of fibers sponge prepared by our group is usually only 8.5-35mg/cm3.14
53
54 With the help of Atomic Layer Deposition (ALD) method, the obtained
55
56 hollow fibers sponge possess density as low as 0.68 mg/cm3, which is lower
57
58 than that of most reported ultra-low density material.94 In addition to low
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1
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4
density, the compression properties of the fibers sponge are also
5
6
noteworthy. Unlike the stable porous structure of traditional sponge, the
7
8
porous 3D structure of blowspun fiber sponge is dynamic. From the micro-
9
10
morphology, fibers are non-oriented and intertwined in the fiber sponge.14
11
12
During compression, the fiber generally has three deformation types:
13
14 bending, breakage and movement (Figure12b-c). For fibers with low
15
16 stiffness, such as plastic polymer fibers, the shape of single fiber cannot be
17
18 maintained and relative movement between fibers is dominant during
19
20 compression. As result, the shape of whole fiber sponge deforms in the
21
22 vertical direction of compression and the porosity decreases. For fibers
23
24 with high stiffness, such as ceramic fibers, carbon fibers, the single fiber
25
26 itself does not undergo plastic deformation when compressed and can
27
28 return to the original state when the pressure disappears. Therefore, the
29
30 fiber sponge demonstrates rebound properties. But the movement and
31
32 breakage of single fiber are often inevitable in actual compression of fiber
33
34 sponge, the structure of fiber sponge cannot be perfectly restored after
35
36 multiple compressions. As Figure12d shows, the compressive stress of
37
38 TiO2 sponge decrease after 100 cycles.14 Structural stability of fiber sponge
39
40 can be improved with increasing the density and cross-adhesion between
41
42 the fibers.14
43
44
45
46
47
48
49
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25
26
27 Figure 12. (a) SEM image of millimeter-sized TiO2 blowspun nanofiber sponge
28
29 Zoomed-in section of TiO2 sponge. (b) Schematic of three deformation types of fiber
30
31 sponge during compression. (c) Zoomed-in SEM images during the compression
32 process, showing the bending and springback of a hank of nanofibers and the movement
33
34 of neighboring nanofibers, and the fourth picture shows their breakage after some
35
36 cycles. (d)The image of compression process. Cyclic compressive stress-strain curves
37
38
of TiO2 sponge. Energy loss coefficient of sponge compressed for three cycles. (a-d)
39 Adapted with permission from ref 14. Copyright 2017 American Association for the
40
41 Advancement of Science.
42
43
44
45
46
47 6. APPLICATIONS OF BLOWSPUN FIBERS
48
49
50 The importance of nanofibers in various applications has been
51
52 intensively studied. Industrialized manufacturing technologies of
53
54 nanofiber have been put into use and still face problems such as difficult
55
56 manufacturing technique and high manufacturing cost, which objectively
57
58 inhibits the large-scale application of nanofibers. Several advantages of
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1
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4
blowspinning technique and blowspun fibers have also been described in
5
6
detail above. Whether blowspinning technique can solve the problems in
7
8
existing applications and advance the application of nanofibers, it should
9
10
be discussed further. Therefore, the purpose of this section is to
11
12
demonstrate value, trends and problems of blowspinning technique in
13
14 application from the perspective of identifying that which problems have
15
16 been resolved based on the application research of blowspinning in
17
18 electronics, medical, filtration and water treatment.
19
20
21 6.1 Electronics
22
23
24 With the rapid development of flexible electronic devices in recent
25
26 years, the demand for flexible transparent conductive materials is
27
28 increasingly urgent. This kind of materials need to be conductive,
29
30 transparent and flexible. The traditional transparent conductive material
31
32 (Indium Tin Oxides, ITO) is no longer applicable in the field of flexible
33
34 electronics due to its brittleness. Metallic nanofibers have been proven to
35
36 be able to properly combine these three characteristics and are regard as
37
38 the next generation of flexible conductive materials.95, 96 However, metallic
39
40 nanofiber as flexible transparent conductive materials face two key
41
42 problems: one problem is that the metallic nanofiber is limited by its wire-
43
44 wire junction, which results in a high interface resistance. The second
45
46 problem is that the actual use of metallic nanofiber faces complex process
47
48 steps such as manufacture, transfer and package, which cause the increase
49
50 of cost.97-99
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28
29 Figure 13. (a) Photograph of precursor PVP/AgNO3 fiber without calcination.
30
31 Freestanding and folded Ag blowspun nanofiber network is conductive. A SEM image
32
33 of Ag nanofiber network. Adapted with permission from ref 86. Copyright 2016
34
American Chemical Society. (b) Photograph of the roll to roll equipment. Roll of
35
36 transparent AgNF electrode material used to illuminate an LED. (c) An Ag nanofiber
37
38 electrochromic window. (b,c) Adapted with permission from ref.52 Copyright 2017
39
40 Wiley-VCH. (d) An Ag nanofiber transparent heating device. Adapted with permission
41 from ref 100. Copyright 2019 Wiley-VCH.
42
43
44 Blowspinng technique provide a new solution to these problems. Our
45
46 group made a silver nanofiber network by blowspinning with high
47
48
49 transparency (up to 97%) and a sheet resistance as low as 6 Ω. Observation
50
51 from its microstructure (Figure 13a), the cross-linked network forms by
52
53 blowspun nanofiber and avoid high interface resistance, so it has higher
54
55 conductivity. And ultra-fine fiber (diameter below 200nm) can make light
56
57 pass through the fiber network smoothly. The blowspun nanofiber network
58
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1
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4
can turn on a LED lamp after switching on the power supply. In first
5
6
generation technique, we rely on a high temperature treatment to reduce
7
8
the precursor fiber into a sliver fiber and this significantly affects the
9
10
continuity of the fiber preparation. In order to overcome this disadvantage,
11
12
a continuous preparation technique was developed with help of ultraviolet
13
14 reduction. The whole process is that spraying the precursor fiber onto PET
15
16 via blowspinning and then make UV-light reduction simultaneously. An
17
18 Ag nanofiber / PET composite transparent conducting film is obtained
19
20 (Figure 13b). Using these materials, an electrochromic smart window and
21
22 transparent heater device was fabricated (Figure 13c-d). The entire
23
24 fabrication process is continuous and meets actual demands of the
25
26 applications.
27
28
29 6.2 Medical applications
30
31
32 The advantages and feasibility of nanofibers in medical application
33
34 have been studied a lot and the related products gradually go to market.
35
36 Nanofibers have a multitude of possible applications in medical field and
37
38 mainly because its nanoscale is particularly relevant for biological
39
40 systems.1 As a new technique of nanofiber, blowspinning brings fresh
41
42 blood to nanofiber application in medical field. In the following, we
43
44 demonstrate some change in use of blowspinning in tissue engineering and
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46 wound healing.
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3 Figure 14. The statistic results of cell survival rate. SEM image of the blowspun
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5 nanofibers containing living cells. SEM image of the electrospun nanofibers containing
6
7 living cells. Adapted with permission from ref 101. Copyright 2012 RSC Publishing.
8
9
10 In the tissue engineering field, the scaffold is used to provide a carrier for
11
12 the growth of seed cells. Good biocompatibility of the scaffolds with the cells
13
14 is required, which is affected by two aspects.102, 103 On the one hand, cells are
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16 usually seeded into the scaffold in tissue engineering, which requires that the
17
18 processing technique does not affect the viability of cell. Therefore,
19
20 researchers demonstrate the effect of blowspinning technique on cell
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22 viability and compare with electrospinning technique. Cells are seeded into
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24 nanofiber scaffold by using both techniques. According to the statistical
25
26 result (Figure14), 48.2% of cells in blowspun nanofiber scaffold survived
27
28 and only 11.2% of cells in electrospun nanofiber scaffold survived due to the
29
30 use of the high voltage.101 In comparison with electrospinning, blowspinning
31
32 has less effect on cell viability.
33
34
35 Another aspect is that the scaffold is suitable for cell survival. Rafaella
36
37 et.al study the compatibility of cells with blowspun nanofibers scaffold from
38
39 the perspectives of adhesion, migration and immune prevention. 72 Figure15a
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41 shows that actin accumulates at the site of contact between cells and
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43 blowspun fibers, which indicate the tight interaction between cells and
44
45 blowspun fibers. Figure15b show that the position of cell changes over time
46
47 and indicate blowspun fibers serve as effective tools for supporting cell
48
49 motility. Examination of immune markers also demonstrate blowspun fibers
50
51 do not cause an immune response. Another conclusion made was that the
52
53 features of blowspun nanofibers are more conducive to cell growth. In cell
54
55 culture experiments, blowspun nanofiber scaffold shows more cell
56
57 proliferation when compared with electrospun nanofber scaffold
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(Figure15c).104 The main reason is that large pores and high porosity of
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6
blowspun fibers can help cells migrate to a suitable growth site in whole
7
8
scaffold.
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39 Figure 15. (a) Distribution of microfilaments in dendritic cells (DCs) seeded on
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41 blowspun fibers. Immature DCs were seeded on blowspun fibers for 24 h, fixed and
42
43 labelled with fluorescent phalloidin and Hoechst. Left panels: actin labelling; middle
44 panels: phase contrast images; right panels: actin/Hoechst merged images. Regardless
45
46 of the fiber chemical composition, actin filaments in DCs were very dense in
47
48 correspondence of the contact sites between cells and fibers (arrows). At these locations,
49
the actin cytoskeleton was re-organized as parallel tracks likely corresponding to
50
51 accumulation of actin filaments at opposite sites of cylindrical fibers (arrows in insets).
52
53 (b) Motility of immature DCs along blowspun fibers. (a,b)Adapted with permission
54
55 from ref 72. Copyright 2017 Elsevier. (c) The statistic results of amounts of cell in
56 different nonwovens. The images of fluorescently labelled cells on the surface of
57
58 blowspun nonwoven. The images of fluorescently labelled cells on the surface of
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35

1
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3 electrospun nonwoven. Cell membranes stained with PHK26 are visualized in red; cell
4
5 nucleus stained with Hoechst33342 are visualized in blue. Adapted with permission
6
7 from ref 104. Copyright 2016 Elsevier.
8
9
10 In wounds treatment, the high porosity and breathability of nanofibers
11
12 are key to promoting wound healing. In several studies, blowspun
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14 nanofibers show a good promotion effect on wound healing.57, 105-108 By
15
16 directly spraying a PLGA/PEG nanofiber onto the wound of a rat, the burst
17
18 pressure of the animal achieved 71.4 ± 11.3 mmHg. This value is 3 times
19
20
21 higher than that measured on the control materials. After 7 days from the
22
23 experiment, 90% of the rats treated with blowspinning survived, whereas
24
25 in the control group only the 60% survived (Figure 16a).107 This result
26
27 depends on the benefits generated by using blowspinning fibers with a
28
29 large pore diameter, which guarantee a prompt air-liquid exchange and
30
31 prevent the accumulation of bacteria. In addition, hemocytes are prevented
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33 to attach the blowspun fibers coating and both the hemolysis and the blood
34
35 coagulation could be efficiently controlled.108 These effects are confirmed
36
37 by animal experiments (Figure 16b).57 The test results show that the
38
39 blowspun nanofibers blocked the liver bleeding and the insurgence of an
40
41 air leakage from the lung surface upon segmentectomy. Overall, in addition
42
43 to the superior properties of blowspun nanofibers, the biggest advantage of
44
45 application of blowspinning in wound treatment is that nanofiber layer can
46
47 be directly sprayed on the wound surface. The whole process can be
48
49 convenient and no secondary injuries to the wound.
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18 Figure 16. (a) 7-d cecal anastomosis survival study (inset: image of the blowspinning
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20 PLGA/PEG fibers deposited onto the sutured anastomosis). Adapted with permission
21
from ref 107. Copyright 2015 Wiley-VCH. (b) Direct deposition of PLGA nanofiber
22
23 mats on a liver injury. Adapted with permission from ref 57. Copyright 2014
24
25 American Chemical Society.
26
27
28 It is clear that blowspinning technique offer great opportunities for
29
30 nanofiber application in medical field. However, it is equally clear that the
31
32 development of blowspinning technique on medical application is just
33
34 beginnings.
35
36
37 6.3 Filters
38
39
40 The conversion of fiber diameter from micrometer to nanometer can
41
42 make the air filter material achieve higher filtration efficiency.109-112 In this
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44 application, electrospinning technique is already used extensively. For
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46 example, Donaldson Inc use electrospun nanofiber coating to extend the
47
48 life of the crude filters and have achieved great success in market.113
49
50 Similarly, nanofiber coating can be prepared on screen window by
51
52 electrospinning to prevent haze from entering the room (Figure17a).114, 115
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54 Our group optimize the production process of screen window. Nanofiber
55
56 coating can be manually sprayed on the window screen by blowspinng
57
58 equipment (Figure 17b). Upon a long filtration time, the nanofibers that
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contain dust can be wiped out and substituted with new fibers.
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Blowspinning technique improves convenience of product application. 53
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30 Figure 17. (a) Photograph of a roll-to-roll process to transfer electrospun nanofiber film
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32 onto screen. Adapted with permission from ref 114. Copyright 2016 American
33 Chemical Society. (b) Scheme of spay nanofiber on window screen. Successful wiping
34
35 of nanofibers from the window screen with the help of tissue paper. Adapted with
36
37 permission from ref 53. Copyright 2017 American Chemical Society. (c) Filtration
38
39
performance of a YSZ nanofiber sponge at 750 °C. Cross section image of the sponge
40 after filtration. SEM image of a YSZ nanofiber sponge. Adapted with permission from
41
42 ref 93. Copyright 2018 Wiley-VCH.
43
44
45 Another application concept of electrospun nanofiber is air filter
46
47 nonwoven. However, there are technical bottlenecks in manufacturing
48
49 electrospun nanofiber nonwovens. In electrospinning process, the
50
51 conductivity of the substrate is continuously reduced, which makes it more
52
53 and more difficult for nanofibers to be deposited on the substrate. When
54
55 producing nonwoven with high density, the yield will be very low.
56
57 Blowspinning technique never has such problem, which
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attract the interest of many researchers.48, 116 Furthermore, our group
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6
provide a new application concept of nanofiber air filter: nanofiber sponge
7
8
filter. Such 3D structure fiber materials with high porosity exhibit a high
9
10
dust capacity.93 The PM efficiency of ceramic blowspun nanofiber sponge
11
12
reaches up to 98% at a temperature of 750 °C (Figure 17c). Figure 18d
13
14 shows that the phenomenon of deep filtration and explaining the reason for
15
16 high dust capacity.
17
18 Blowspinning technique is still in the learning stage in filtration field.
19
20 The focus of research is the optimization and supplementation of
21
22 electrospinning. The filtration field requires a large amount of materials, so
23
24 the actual application of blowspinning in the filtration field must first solve
25
26 mass production problem.
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28
29 6.4 Water treatment
30
31
32 Many studies focus on the application of blowspun nanofiber in water
33
34 treatment. Some of them focus on that blowspun nonwoven with high
35
36 porosity is suitable for microfiltration. For example, Zhuang et al show that
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38 PVDF blowspun nonwoven has low entry pressure and high pure water
39
40 flux during microfiltration.54 Another research idea is to treat pollutants in
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42 water by expanding the functionalization of blowspun fibers. Our group
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44 make carbon nanofiber sponges with the 98% porosity and can be used as
45
46 the oil-absorbing material. The adsorbing capacity of a sponge equals 48–
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48 184 times of its own weight, which is much higher than traditional
49
50 absorbent (Figure 18a).92 Based on this idea, our group mass produce
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52 polyimide dioxime nanofiber adsorbents with chelating sites and excellent
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54 hydrophilicity.117 This blow spun PIDO nanofabric shows great adsorption
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56 capacity for uranium, which can be used to extract uranium from natural
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58 seawater (Figure 18b). The main functional group responsible for the
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uranyl binding is cyclic “imidedioxime which indicate that the adsorbent
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6
can be regenerated and reused (Figure 18c). The actual elution process is
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fast, which verifies the feasibility in kinetics (Figure 18d). These results
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10
suggest that blowspinning has a broad prospect on water treatment.
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41 Figure 18. (a) Photographs of the adsorption process of chloroform by a carbon
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43 microfiber sponge. Sorption efficiency of carbon microfiber sponge for different
44
45 organic liquids. Adapted with permission from ref 92 Copyright 2018 Elsevier. (b) The
46
47
uranium adsorption efficiency in uranium aqueous solution (8 ppm) with different pH.
48 The survey XPS spectra of PIDO and uranium loaded PIDO (PIDO-U). (c) CP/MAS
49
50 13C NMR spectra of raw material PAN (1), blow spun PIDO nanofibers (2), PIDO
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52 nanofibers after base conditioning in 10 × 10−3 m NaOH solution at 60 °C for 30 min
53
54 (3) and 3 h (4), respectively. (d) The images showing PIDO NF adsorbents before
55
56 adsorption, after adsorption and after elution. The photo of extracted uranium in eluent
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1
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3 from the 5 L of uranium (8 ppm) spiked seawater. (b-d) Adapted with permission from
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5 ref 117. Copyright 2018 Wiley-VCH.
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8
9
10 7. CONCLUSIONS AND OUTLOOK
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This review summarized researches for blowspinning including basic
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16
principle, empirical research, equipment and application. The research
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18
progresses demonstrate the great potential for practical application of
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20
blowspinning. Although the characteristics of ultrafine fibers have been
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22
widely studied before, the research work for the characteristics of
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24
blowspun fibers must not be neglected. CFD simulation and high-speed
25
26
camera have been applied very successfully to demonstrate the impact of
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28
the molding process on fiber properties. In comparison with
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30
electrospinning, blowspun fibers exhibit unique characteristics in
31
32
morphology (for example, larger pore size, fiber bundles), property (for
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34
example, tensile strength). Our group not only pays attention to the
35
36
characteristics of a single fiber, but also focuses on the macroscopic
37
38
characteristics of fibrous body. It is universal to produce the three-
39
40 dimensional structure of the fiberous body by blowspinning technique.
41
42 Expanding the fiber material from one-dimensional flexibility to three-
43
44 dimensional flexibility through blowspinning technique will expand the
45
46 function and application of ultrafine fiber materials, which is the main
47
48 purpose of our research. Especially for ceramic nanofiber sponges, the
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50 fragile ceramic material was turned into a three-dimensional flexible
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52 ceramic nanofiber sponge with the help of blowspinning technique, which
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54 has high temperature resistance, ultra-low thermal conductivity and
55
56 tailorable. It will be in great demand in field of thermal insulation.
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Blowspun fibers can be sprayed to a designated area, which will bring
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6
fiber technique closer to customer. One of our work is successfully to
7
8
prevent the haze by spraying fibers directly on the screens, which is good
9
10
demonstration of this function. Another result shows blowspun fibers can
11
12
accelerate wound healing, which will make blowspinning of great value in
13
14 medical field. However, the technological application of blowspun fibers
15
16 depends on a sufficient amount of fibers, which is possible to be achieved
17
18 by stable and efficient spinning equipment. Moreover, our group and those
19
20 of our peers show that various types of spinning equipment (for example,
21
22 handheld devices and multi-needle devices) can produce fibers. The results
23
24 demonstrate that blowspinning technique is highly scalable, which make
25
26 us full of expectations for large-scale production of blowspun fibers. In
27
28 order to achieve large-scale production of blowspinning, there is still a long
29
30 way to go. Among them, the use of melt-blown spinneret to achieve
31
32 blowspinning is a potential solution. The improvement and optimization of
33
34 equipment based on traditional spinning technique will promote the
35
36 industrialization of blowspinning technique rapidly.
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38
39
40
41 AUTHOR INFORMATION
42
43
44
Corresponding Author
45 ⁎Email:
46 huiwu@tsinghua.edu.cn
47
48 Author Contributions
49
50
51
The manuscript was written through contributions of all authors. All
52 authors have given approval to the final version of the manuscript.
53
54 Notes
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56
57
The authors declare no competing financial interest.
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6 ACKNOWLEDGEMENTS
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8 This work was supported by the Basic Science Center Program of the
9
10
National Natural Science Foundation of China (NSFC) under Grant No.
11 51788104 and NSFC projects under Grant No. 51661135025., National
12 Basic Research of China under Grant No. 2015CB932500. The images of
13
14
spinning set-up were provided by Shenzhen WeDo New Materials Co.,
15 Ltd.
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