You are on page 1of 23

Journal of Polymer Research (2020) 27:205

https://doi.org/10.1007/s10965-020-02173-7

REVIEW PAPER

The main blow spun polymer systems: processing


conditions and applications
Fernanda Trindade Gonzalez Dias 1,2 & Silvana Pereira Rempel 1 & Lucas Dall Agnol 1 & Otávio Bianchi 1,3

Received: 2 March 2020 / Accepted: 30 June 2020


# The Polymer Society, Taipei 2020

Abstract
This review aims at providing an examination of the central polymeric systems that have been tested by the Solution Blow
Spinning Technique (SBS). The SBS is an on-demand micro/nanofibrous material forming technique that uses simple instru-
mentation, thus making its research substantial. Although other studies had already presented the SBS parameters and their
correlations with fiber morphology, it’s still unclear for polymeric researchers which systems have already been tested, therefore
some questions remain unanswered, such as: “which polymers have been used most in the art?”, “which solvents have promoted
the fiber formation?”, “which additives or particles were tested for composite polymer fibers?”, “for which applications have the
fibers been targeted?”, “what adaptations have been investigated to overcome the challenges of the process?”. Seventy-nine
articles related to polymeric fibers produced by SBS, reported from January 2010 to May 2019, were chosen among four
databases, using precise keywords. The principal findings of these articles were presented and reviewed, using additional
references as support. From this study, polymeric researchers will have access to the current SBS state-of-the-art, being able
to try new polymer-solvents combinations, as well as to solve the existing process inconveniences.

Keywords Solution blow spinning . Micro/nanofibers . Polymeric systems . Literature review

Introduction storage, among others [2–5]. The global market for these
micro/nanofibers reached a staggering US$384 million dollars
The micro/nanofibers represent a relevant class of materials in 2015, and it is projected to approach US$2 billion dollars by
with a vast possibility of applications due to their unique 2020 [6].
properties, such as the large specific surface area, selective A simplified Solution Blow Spinning (SBS) technique set-
permeability, surface adsorption properties, and tailorable sur- up consists of a syringe pump, a customized nozzle, a high-
face functionalization [1]. Besides, their easily controllable velocity gas source (typically air), and a collector [7]. A ho-
architecture (porosity, diameter, etc.) considerably improves mogeneous polymer solution in a volatile solvent is also nec-
the materials properties. Great examples of materials could be essary [8]. The nozzle generally consists of an inner nozzle,
medical consumables, high technology applications for the through which the polymer solution is pumped, and a concen-
aerospace industry, transistors, textiles, air and water filters, tric outer nozzle that supplies the pressurized gas. The pres-
sensors, wound dressings, drug delivery systems, energy surized gas produces a conduction force, and when it exceeds
the surface tension of the solution, the polymeric drop at the
tip of the nozzle is stretched into an ultrathin jet and solidified
* Otávio Bianchi into micro/nanofibers in a collector, as shown in Fig. 1 [2,
otavio.bianchi@gmail.com 9–12]. As this jet travels through the surrounding atmosphere,
the solvent evaporates, resulting in a nonwoven structure [9,
1
Materials Science Postgraduate Program, University of Caxias do Sul 13–15]. The nozzle geometry creates a region of low pressure
(UCS), Caxias do Sul, RS, Brazil
around the inner nozzle, which helps draw the polymer solu-
2
Postgraduate Program in Technology and Materials Engineering tion into a cone comparable to Taylor’s cone, formed by the
(PPG-TEM), Federal Institute of Rio Grande do Sul (IFRS),
Feliz, RS, Brazil
electrospinning process. The outer concentric nozzle makes
3
use of Bernoulli’s principle, in which changes in pressure
Department of Materials Engineering (DEMAT), Federal University
of Rio Grande do Sul (UFRGS), Porto Alegre, RS, Brazil
are converted into kinetic energy [13, 16–18]. The increasing
205 Page 2 of 23 J Polym Res (2020) 27:205

Fig. 1 Conventional apparatus


for the solution blow spinning
(SBS) system [9]. Reproduced
with permission from Ref. 9,
Medeiros ES, et al. (2009) J Appl
Polym Sci 113:2322–2330.
Copyright © 2009 by John Wiley
Sons, Inc.

velocity of the air leaving the outer nozzle (Fig. 2, P1) causes The differences in the driving force types between
an air pressure drop at the center of the jet (Fig. 2, Patm), thus electrospinning and blow spinning, bring several advantages
creating a driving force that is responsible for the acceleration to SBS, such as (i) a higher fiber production rate, since it is
of the polymer solution [9, 19]. The polymer solution and the possible to apply higher feed rates [21, 26, 27]; (ii) versatility
gas jet are brought together via independent delivery mecha- on choosing the solvent, as it is no longer conditioned by the
nisms. This approach helps avoid clogging, and the uncontrol- dielectric constant [8, 27–30]; (iii) the deposition of fibers
lable increase of the pressure, which are known to occur in directly onto a broad range of collectors and surfaces
other devices of nanofiber formation [20]. [31–33], including living organs in situ [25]; (iv) the feasibil-
Medeiros et al. [9] initially reported the solution blow spin- ity of producing multicomponent fibers, or fibers containing
ning technique (SBS) when obtaining polymeric fibers with a additives, particles, and/or fillers [20, 22, 34–36]; and (v) the
higher production rate compared to other spinning methods, simultaneous use of multiple nozzles [7, 8, 10, 12, 30, 37, 38]
such as electrospinning [3, 8]. Although electrospinning has or air-jet spinning devices [39].
been thoroughly researched, the low solution feeding rate per The different driving forces involved in the electrospinning
orifice of this technique limits its scale-up and, therefore, its and SBS processes result in chain orientation and crystallinity
industrial efficiency [21, 22]. While electrospun fibers are variations, which ultimately impact on both the degradation
generated ex-situ using specialized equipment, high voltages, rate and mechanical properties of the mats [40]. The locally-
and electrically conductive targets, blow spun fibers can be oriented fibers, using SBS, increase the mechanical strength of
produced on any surface in situ, using only a commercial the fibrous scaffold, in contrast with the randomly-oriented
airbrush and compressed gas [23, 24]. Certainly, an automated electrospun mats [19]. Specific bulk material properties and
SBS with a built nozzle coupled to a syringe pump would scaffold morphology, including Young’s modulus, network
ensure a better feed rate control and reproducibility, but the pore size, and porosity, were reported to be different between
advantage of a commercial airbrush is that the equipment is electrospun and airbrushed scaffolds [41]. One limitation of
cost-effective and readily available [25]. the SBS process, however, is the possibility of the formation

Fig. 2 A nozzle geometry used in


SBS [9]. Reproduced with
permission from Ref. 9, Medeiros
ES, et al. (2009) J Appl Polym Sci
113:2322–2330. Copyright ©
2009 by John Wiley Sons, Inc.
J Polym Res (2020) 27:205 Page 3 of 23 205

of bundled fibers due to the influence of a poorly controlled published from January 2000 to May 2019. The articles found
gas flow. These bundles may result in a non-homogeneous were analyzed, and those that were duplicated, or already re-
fiber distribution, thus yielding poor performances in several visions, or not polymeric systems, were excluded from the
fields [4]. results. Considering these criteria, a total of seventy-nine
In SBS, fiber morphologies and properties are controlled (79) relevant articles were found in the databases search,
by (i) solution variables (polymer concentration and molar which is presented in Table 1 and mandatorily cited in this
mass, viscosity, surface tension, solvent type, presence of an- review text. The variables analyzed in the eligible articles
other phase, particle or additives), (ii) processing parameters were: polymer, solvent system, particle/additive, solution con-
(solution feed-rate, gas pressure, nozzle-collector distance), centration, critical concentration, gas type/pressure,
(iii) system configuration (nozzle diameter, nozzle geometry, temperature/relative humidity, needle-collector distance, col-
polymer feed mode), and (iv) ambient parameters (tempera- lector type, feed rate, nozzle diameter, mean fiber diameter,
ture, humidity, atmospheric pressure) [11, 13, 16, 28, 32, and application. The other bibliographic references mentioned
42–44]. Controlling these parameters is the way of optimizing here were used as support for the discussion of the results.
the SBS process to obtain morphologically tailored micro/
nanofibers for any soluble polymeric system.
Since SBS is a much newer technique than electro-spin- Results and discussion
ning, there is still a considerable lack of knowledge in
predicting and controlling the fiber diameter through this pro- The systematic articles search identified a total of ninety-
cess, and the experimental results are partially contradictory seven (97) distinct articles. From those, eighteen (18) articles
[38]. A better understanding of fiber formation may optimize were discarded because they did not meet the eligibility
the spinning parameters for a more uniform fiber morphology, criteria, that is, either they were review articles or did not
thus creating tools to predict the optimal spinning conditions use polymeric systems. A total of seventy-nine (79) articles
[45, 46]. Some studies have already reported the general were included in this study that evaluated the reports from the
mechanisms responsible for fiber formation, as well as the last nineteen years. This shows how recent the SBS technique
effect of some processing parameters on fiber morphology is for the production of polymeric micro/nanofibers. Table 1
[47–49], but none of them have been concerned with exam- summarizes the central polymeric systems whose blow spin-
ining the central polymer systems already tested by SBS ning was reported in the period from January 2000 to
technique. May 2019, and their particular processing variables.
In this review, we systematically analyzed the critical spin- Regarding the polymers selected in the studies, we noticed
ning conditions of fiber-production for the principle blown the extensive choice for blown spun biodegradable polymers.
spun polymer systems reported in the literature, from From the 79 results, 22 used poly(lactic acid) (PLA) for blow
January 2010 to May 2019. Here, articles found in at least spinning [3, 5, 9, 11, 13, 15, 16, 19, 27, 28, 31, 33, 34, 44, 57,
four databases (Scopus, Web of Science, Science Direct, and 66–72]. Poly(ε-caprolactone) (PCL) was the second most
Google Scholar) using particular keywords, were analyzed chosen polymer, represented by twelve studies [25, 29, 31,
and described. The present report will guide new researches 32, 39, 41, 57–61, 87], followed by poly(L-lactic acid)
in optimizing the main operational parameters for each (PDLLA) (six studies) [25, 41, 62–64, 87].
polymer-solvent system to provide the most suitable fibers This search for biodegradable polymers is directly related
for the application of choice. to the intended application, with tissue engineering (bone tis-
sue, surgical implants, vascular prostheses, wound dressings,
etc.) being the dominant choice. Biodegradable polymers play
Review methodology an external matrix role in bioengineering, offering physical
support for cellular events, and enabling the replacement of
The publications were searched using the Scopus (https:// injured tissue by regenerated tissue. The property of fiber deg-
www.scopus.com), Web of Science (https://www. radation or consumption throughout the application also al-
webofknowledge.com), Science Direct (https://www. lows it to be used as a controlled release vehicle, whether of
sciencedirect.com), and Google Scholar (https://scholar. drugs, natural compounds, antimicrobials, or, pheromones for
google.com.br/) online databases. The keywords used were agriculture, etc.
([solution blow spinning or blow spinning or SBS or The use of non-biodegradable synthetic polymers in SBS
airbrush or air-jet spinning or air jet], and [polymer or poly] was also observed. Some of these were polystyrene (PS) (sev-
and [fiber or nanofiber or microfiber] and ([concentration or en studies) [9, 25, 30, 37, 58, 59, 74], poly(ethylene oxide)
viscosity or surface tension or viscoelasticity or molecular (PEO) (eight studies) [7, 20, 28, 46, 52, 57, 65, 87],
weight] or [pressure or distance or diameter or feed rate or polyamide-6 or nylon-6 (PA6) (five studies) [17, 39, 42, 47,
nozzle])). The search was limited to English language articles 56], poly(vinylidene fluoride) (PVDF) (five studies) [52,
Table 1 Processing conditions and applications of the blow-spun polymeric systems selected in the databases search
205

Polymer Solvent system Particle/Additive Solution concentration Critical Gas type/Pressure Temperature/ Needle-collector
concentration Relative distance
humidity
Page 4 of 23

EVA Chloroform [50]; xylene/chloroform Synthetic sex pheromones 0.5–15 wt.% 5 wt.% [51] Air (0.05–0.5 MPa) 45 °C 15–25 cm
(146 kg/mol) (96:4) [51] or (25 wt.% related to EVA) [51]
chloroform/dimethylcloride (5:5)
[52]
PAA DMF – 6–8 wt.% – Nitrogen (0.06–0.12 MPa) 60 °C 10–25 cm
(molar mass not
specified)
PAN DMAc [45] or DMF [53–55] TCF-H 5–20 wt.% – Air (0.05–0.30 MPa) – 45–80 cm
(70–120 kg/mol) (0.1–5 wt.%) [53]
PA6 (11,46 [42] Formic acid [47, 56] or formic – 5–22 wt.% – Air (0.08–0.5 MPa) 25 °C; 25–60 cm
kg/mol) acid/acetic acid (80:20)[23,39,42] 38–45% Rh
[17, 39, 42]
PCL DCM [31, 39, 57, 58] or HFP [59] or Zr-ACP 2–9 wt.% [25, 29, 31, – Air (0.03–0.45 MPa) [29, 25 °C; 10–70 cm
(50–90 kg/mol) chloroform [25, 29, 32, 41, 60, 61] (5–20 wt.%) [41] 32, 39, 41, 57, 58] or 31, 32, 39, 41, 57, 58, 60, 40% Rh [39]
or acetone [29] or chloroform 2–12% w/v [59–61] 61] or nitrogen
/methanol (85:15) [29] or acetic (0.01–0.24 MPa) [25, 59]
acid/ water (80:20) [29]
PDLLA Acetone [41, 62] or DMC [63] or nBG (5–10 wt.%) [63] or Zr-ACP 5–12 wt.% [25, 41, 62, 10% w/v [63] Air (0.1–0.3 MPa) or 25 °C [64] 15–30 cm
(25–200 kg/mol) chloroform/acetone (3:1 v/v) [64] or (5–20 wt.%) [41] 64] or 4–20% w/v nitrogen
chloroform/methanol (85:15 wt.%) [63] (241 kPa) [25]
[25]
pDTEc Dioxane – 15 wt.% – Nitrogen – 20 cm
(183 kg/mol) (241 kPa)
PEO DCM [57] or chloroform [28] or – 1–10 wt.% – Air (0.01–0.6 MPa) – 10–15 cm [28, 52,
(100–300 ethanol [7] or water [46] or 57] or 50 cm
[16,26,29,51,67] or acetone/chloroform (5:5) [52] or [46, 65] or
1000–2000 kg/mol water/ ethanol (2:1–1:2 v/v [65] or 1–1.8 [16,26]
[20, 46, 65]) 1:10 v/v [20])
PHBV (molar mass not HFIP Diclofenac sodium 8 wt.% – Air – 12 cm
specified) (5–20 wt.%) (0.4 MPa)
PLA TFE [9, 66] or Linalool (10–20 wt.%) [15]; BCNW 4–12% w/v [3, 9, 11, 69] 2.5% w/v [57] Air (0.2–0.6 MPa) or – 10–20 cm
(66–75 kg/mol) chloroform/acetone (3:1, v/v) [3, 5, 11, (5–30 wt.%); carvacrol (12 wt.%); or 4–10 wt.% [15, nitrogen (276 kPa [9])
19, 44, 66–68] or HFIP [15, 27] or TCH (2–20 wt.%) [27, 66]; gelatin 19, 27, 28, 44,
chloroform [28, 69] or DCM or (30 wt.%) [27]; PVP (0–20 wt.%) 66–68]
dichloroethane [69] [3, 11]; copaiba oil (20%, w/v) [3,
J Polym Res

11]; MWCNT
(0–3 wt.%) [5, 67]; progesterone
(0–8 wt.%) [68]; TiO2
(0–17 wt.%) [44]
PLA DMC [13, 16, 33] or HFP [13] or nHA 1–15% w/v [13, 16, 33, 4–7% w/v Air (0.2–10 MPa) [13, 16, 21–25 °C; 5–110 cm
(100–200 kg/mol) chloroform [13, 70] or DCM [31, (0.1–0.3 g) [34] or CNCs 70, 71] or 2–10 wt.% [16, 70] or 31, 33, 34, 70] or argon 35–55% Rh
34] or (0.1–3% w/v) [33] [31, 34, 72] 2.5 wt.% (0.2–0.25 MPa) [71, 72] [16, 31, 33,
(2020) 27:205

chloroform/ethanol (3:1 v/v) [71, 72] [31] 34]


PLLA Chloroform [40] or chloroform – 4–8 wt.% [21] or 4–7% – Air (0.05–1.5 MPa) 25 °C 20 cm
(100–200 kg/mol) /acetone (3:1 v/v) [21] w/v [40] 45–50% Rh
Table 1 (continued)
PLGA (molar mass not Acetone [23] or chloroform [73] – 6–10% w/v – CO2 [23] or air (207 kPa) – 10–23 cm
specified) [73]
J Polym Res

PMMA Chloroform [9] or acetone [41] Zr-ACP 10% w/v [9] – Nitrogen (276 kPa) [9] or – 20 cm
(120–500 kg/mol) (5–20 wt.%) [41] or 10 wt.% [41] air (0.2–0.27 MPa) [41]
PS DMF [25, 59]; DCM [37, 58]; toluene; MOF 8–30 wt.% [25, 30, 37, – Air (140 kPa) [74] or 25 °C [74] 10–35 cm
(80–350 kg/mol) orange oil [9, 74] or ethyl acetate (10–50 wt.%) [30] 74] or nitrogen
[30] 10–30% w/v [9, 59] (68–300 kPa) [9, 25, 30, 37,
58, 59]
PSF (molar mass not Chloroform /acetone TiO2 10% w/v – Air – 4–5 cm
(2020) 27:205

specified) (8:2 v/v) (0–10 wt.%) (0.4 MPa)


PU THF [64]; DMF [43, 76] or DMF/THF MWCNT 5–20 wt.% – Air (0.1–0.6 MPa) 20–65 °C [64, 15–50 cm
(107–150 kg/mol) (10:0–3:7) [1] (0.5–5 wt.%) [1] 76]
PVAc DCM [18, 31, 36] TiO2 [36] or HA [18] 1.7–6 wt.% – Air (275–420 kPa) 25 °C; 5–110 cm [18, 31,
(500 kg/mol) or ethyl acetate [7] (5–10 wt.% on solution basis) 40–45% Rh 36] or 1.8 m [7]
[18, 31, 36]
PVDF DMF [77, 78]; DMAC/acetone TiO2 10–30% w/v [78, 80] or – Air (0.1–0.7 MPa) 45 °C [79] 5–60 cm
(10–27 [70] or (8:2 v/v) [79] (0–10 wt.%) [80] or Ni-NPs (0.1 g) 11–22 wt.% [52, 77,
100–275 kg/mol or acetone/ DMF (9:1 v/v) [52, 80] [77] 79]
[52, 77, 78])
PVP Isopropyl alcohol/water (50:50 v/v%) – 2–10 wt.% – Air (68–275 kPa) – 1.8 m [7]
(360 [27] or 1300 [7] [26] or ethanol [7]
kg/mol)
SIS (molar mass not THF – 20% w/v – Air – –
specified) (0.34 MPa)
VDF-TeFE (molar Acetone [8] or MEK/DMF (1:2 v/v) – 3–11 wt.% – Air (0.35–0.4 MPa) – 30–40 cm
mass not specified) [12]
WPS (molar mass not Ethyl acetate – 4–14 wt.% – Nitrogen (0.29–0.68 MPa) 25 °C; 5–20 cm
specified) 40% Rh
Zein (molar mass not Acetic acid – 20–40 wt.% – Air (0.28–0.62 MPa) 21 °C 60 cm
specified)
PA6/PCL Formic acid/acetic acid 4:1 wt.% – 22 wt.% (PA6) and – Air 25 °C; 30 cm
11,46/80 kg/mol (PA6) and THF (PCL) 7 wt.% (PCL) (0.5 MPa) 38% Rh
(100:0–10:90 weight
ratios)
PCL/PS DCM – 7 wt.% – Nitrogen – 18 cm
(90/248 kg/mol) (1:1–1:4) (0.3 MPa)
PG/ HMWFG (10–20/ Acetic acid – 10–25% w/v – Air (0.27–0.48 MPa) – 50 cm
10–25% w/v) 20% (v/v)
PLA/Pani HFP – 10% w/v – Nitrogen (276 kPa) – 20 cm
(molar mass not (PLA/Pani
specified) 96:4 wt.%)
PLA/PEG Chloroform/acetone (3:1 v/v); 40% w/v terpinen-4-ol or 0.12% w/v 10% w/v PLA and – Air (2.4 and 344 kPa) 21 °C; 18–20 cm
(76–125/8 kg/mol) (99:1–80:20 wt.%) [85] chlorhexidine gluconate [86] 10–30% w/v PEG 35% Rh [85]
related to PLA [86]
or 12 wt.% [85]
PLA/PEO Chloroform – 6 wt.% – Air – 12 cm
(75/100 kg/mol) (0.4 MPa)
PLGA/PPy (molar Chloroform – 6% w/v (PLGA) and – Air – 17 cm
mass not specified) 3% w/v (PPy) (152 kPa)
Page 5 of 23 205

(90/10 wt.%)
Table 1 (continued)
205

PVAc/PVP (50/1300 Chlorobenzene/methanol for bi-lobal MWCNT 3:3 wt.% [35] – Air (0.14 MPa) for primary 20–25 °C 1–1.98 m
[20] 500/1300 [35] [35] and chlorobenzene/1-butanol 1.5 wt.% (1 wt.% related to polymers) or 1:1 wt.% (3 wt.%) jet and nitrogen 19–25% Rh
kg/mol) for IPN [35] or isopropanol/ethyl [20] [20] (0.14–0.2 MPa) for
acetate (1:1 wt.%) [20] secondary jet [20, 35]
PCL/PEO/ PDLLA Dichloromethane or – PCL (0.5–14% w/v); – CO2 (0.05–0.3 MPa) – 10–25 cm
Page 6 of 23

(80/600/50–80 kg/- chloroform/methanol (7:3 v/v) PDLLA (4–12%


mol) w/v); PEO (5–2%
w/v)

Polymer Collector type Feed rate Nozzle diameter Mean fiber diameter Applicattion Ref.

EVA Rotating 0.2–6 mL/min 0.2–0.5 mm (inner); 0.7 mm (outer); 2 mm 95–426 nm [51]; Biological [50] and [50–52]
(146 kg/mol) (270 rpm) [50]; cylindrical [52] or flat protrusion; concentric nozzle 2.19–3.41 μm [52] and [67,79]pheromone release [51]
[51] films [50]
PAA Rotating 0.8–3.2 mL/h 0.3–0.6 mm; 4.5 mm protrusion; concentric 178 nm Not specified [10]
(molar mass not (150 rpm) nozzles
specified)
PAN Flat (stainless) [45] 0.025–0.34 0.38–0.91 mm (inner); 1.25–2.5 mm (outer); 178 nm − 1.4 μm Colorimetric sensor [53]; [45, 53–55]
(70–120 kg/mol) mL/min −2–4 mm protrusion; concentric nozzle adsorbents for Cr(VI) [54] and
filtration [55]
PA6 (11,46 [42] Rotating 5–19 mL/h [47, 56] 0.25–1 mm 90–750 nm Air filtration [47, 56] and vascular [17, 39, 42,
kg/mol) (1000 rpm) [39] or flat (PP) [17, 56] tissue [17, 39, 42] 47, 56]
PCL Rotating (0–300–1000 [31, 39, 60]) or 10–800 μL/min 0.2–0.8 mm[15,30 39,41,59,60] concentric 100–1.38 μm or fibers not Tissue engineering, regenerative [25, 29, 31,
(50–90 kg/mol) flat [61] (aluminum foil[15,30,32,]; [57, 59, 61] or nozzle [57] or 1–2 mm protrusion, nozzle obtained [58] using medicine [25, 29, 31, 32, 39, 32, 39, 41,
PS discs [41]; glass or water bath 0.9–50 mL/h area (polymer): 0.2 mm2 acetone and acetic 41, 57, 59–61] and oil recover 57–61]
[31]) [25, 31, 32] nozzle area (air): 0.5/12.56 mm2 [32] acid/water) [29] [58]
PDLLA Rotating (600 [64] or 11,000 [65] rpm) 120 μL/min [63] or 0.2–0.3 mm [25, 41] or 1–2 mm protrusion, 99–412 nm Tissue engineering [25, 41,
(25–200 kg/mol) or flat (aluminum foil [25], PS discs 0.16–1.15 mL/- 0.5 (ratio in/out nozzle), (concentric 62–64]
[41], fiberglass or teflon mesh [62]) min [25, 62, 64] nozzle) [62–64]
pDTEc Flat (aluminum foil) 0.31 mL/min 0.2 mm 677 nm Biomedical [25]
(183 kg/mol)
PEO Rotating (1800 rpm [65]) or flat 6–120 μL/min 0.2–1.22 mm [7, 20, 28, 46, 52, 65]; 242–642 nm [7, 28, 52, 57] Tissue engineering [65], electric [7, 20, 28, 46,
(100–300 (copper [46] or glass plate covered concentric nozzle [28, 57]; 2–4 mm or 134 nm − 2.5 μm [20, and biomedical [52] 52, 57, 65]
[16,26,29,51,67] or with aluminum foil [52]) protruded [28, 46, 52] 46, 65]
1000–2000 kg/mol
[20, 46, 65])
PHBV (molar mass not – 7.2 μL/min 2 mm protrusion, concentric nozzles of 263–320 nm Drug release [2]
specified) 0.5 mm
PLA Rotating 0.66–120 μL/min 0.2–0.5 mm [3, 9, 11] or 2 mm protrusion, 34 nm–1.25 μm Wound dressing [3, 11, 66], drug [3, 5, 9, 11,
J Polym Res

(66–75 kg/mol) (180–800 rpm) or flat (glass plates concentric nozzles of 0.5 mm release [15, 27, 68] and sensors 15, 19, 27,
with indium oxide and tin) or biosensors [5, 67] 28, 44, 57,
66–69]
PLA Rotating (180–500 rpm) [13, 16, 31]) 0.02–15 mL/min 0.3 mm [71, 72]; 2 mm protrusion, 60 nm–0.97 μm Tissue engineering [31, 34, [13, 16, 31,
(100–200 kg/mol) or flat (PET films [34, 70], glass and concentric nozzles [13, 16, 33]; 70–72], membranes and 33, 34,
water bath [31]) 0.1–0.6 mm (needle) [70] or 250 μm [34] adsorbents [33] 70–72]
PLLA Rotating [21] (200 rpm) 10–45 mL/h – 35–678 nm Biomedical [21] and vascular [21, 40]
(2020) 27:205

(100–200 kg/mol) or flat [40] prostheses [40]


PLGA (molar mass not Flat (glass) [23] or cylinder wrapped 95 μL/min [73] 0.2 mm [23] or 0.9 mm [73] 377 nm Tissue engineering [23, 73]
specified) with aluminum foil) [73]
Table 1 (continued)
PMMA Rotating 20 μL/min [9] 0.2 mm protrusion [9]; 0.3 mm [41] 0.79–7.8 μm Bone tissue [41] [9, 41]
(120–500 kg/mol) (800 rpm) [9] or flat (PS) [41]
J Polym Res

PS Rotating (400–800 rpm [9, 74]) or flat 20–75 μL/min [9, 0.2–0.5 mm [25, 37, 58]; 0.2 mm protrusion 144 nm–5 μm Biomedical [25, 59]; oil recovery [9, 25, 30, 37,
(80–350 kg/mol) (aluminum foil [25, 30] or plastic 59] or [9, 74] or 0.84 mm (needle); 2.0 mm [37, 58]; active food packaging 58, 59, 74]
[37]) 7–120 mL/h (nozzle); 1 mm protrusion; concentric [74] and separation– catalysis
[25, 30, 74] nozzles [30] [30]
PSF (molar mass not Flat – 0.5 mm 50–200 nm Biomedical [75]
specified) (glass)
PU Rotating 20–25 μL/min [1] 2 mm protrusion; concentric nozzle (0.5 100–670 nm Biomedical [64] and reinforcing [1, 43, 64, 76]
(2020) 27:205

(107–150 kg/mol) (180–11,000 [6,65] rpm) or flat [43] or 1–50 mL/h ratio) [43, 64] or 0.7 mm [1] agent for composites [1]
[43, 64]
PVAc Rotating 0.8 [16] or 15 0.25–1.22 mm 117 nm–1.19 μm Biological [18, 31], filter and [7, 18, 31, 36]
(500 kg/mol) (500 rpm) [31] or flat [5,24,36] photocatalyst [36]
(Ti [18]; glass, water bath [31]) mL/min
PVDF Rotating 0.075–0.5 mL/min 0.2–0.7 mm; 2 mm protrusion 60–633 nm and film [80] Biological [52, 80], [52, 77–80]
(10–27 [70] or (400 rpm) [77]; cylindrical [52] or flat [52, 77] or formation electric/magnetic fibers [77]
100–275 kg/mol (porous [79], glass [80] 16 mL/h [79] and microfiltration membrane
[52, 77, 78]) [79]
PVP Rotating 0.06–0.8 mL/min 0.3–1.22 mm (inner diameter) [7] 186 nm–1.3 μm Not specified [7, 26]
(360 [27] or 1300 [7] (150–350 rpm) [26]
kg/mol)
SIS (molar mass not Flat 10 mL/h 1.02 mm 1.66 μm Elastic conductors [81]
specified) (metal mesh)
VDF-TeFE (molar Flat [8] 25 μL/min [8] or 0.35–0.6 mm (inner nozzle) and Microfibers (0.53–2.81 μm Biomedical [8, 12]
mass not specified) 50 mL/h [12] 0.53–0.9 mm (outer nozzle) [12]) and nanofibers
(170 nm) [8]
WPS (molar mass not – – 0.5 mm 329–536 nm Oil recovery and wastewater [82]
specified) treatment
Zein (molar mass not Static aluminum plate 0.02–0.1 mL/min 2 mm protrusion, concentric nozzles 174 nm–9.59 μm Not specified [83]
specified)
PA6/PCL Flat – 0.3 mm 275 nm–4.77 μm Tissue scaffolds [42]
11,46/80 kg/mol
PCL/PS Flat – 0.5 mm 1.05–1.51 μm Oil recover [58]
(90/248 kg/mol) (PP mat)
PG/ HMWFG (10–20/ Aluminum plate 0.04–0.06 mL/min 0.69–1.48 mm (inner); 1.07–3.11 mm 39–188 nm Not specified [84]
10–25% w/v) (outer); 2 mm protrusion, concentric
nozzles
PLA/Pani Rotating 20 μL/min 0.2 mm protrusion 140–590 nm Not specified [9]
(molar mass not (800 rpm)
specified)
PLA/PEG Rotating 7.2 [82] or 100 [81] 0.5–2 mm protrusion; 0.5 mm (inner) [85]; 100 nm–1.41 μm Drug release [86] and tissue [85, 86]
(76–125/8 kg/mol) (180 or μL/min concentric nozzle engineering [85]
600 rpm)
PLA/PEO Rotating 120 μL/min 2 mm protrusion, concentric nozzles, 0.5 mm 681 nm −0.85 μm Not specified [28]
(75/100 kg/mol) distance between nozzles
PLGA/PPy (molar Cylinder 159 μL/min 0.9 mm – Not specified [73]
mass not specified)
PVAc/PVP (50/1300 – 0.5 mL/min 0.83 mm [20] 248 nm (primary gas jet) to Not specified [20, 35]
[20] 500/1300 [35] 89 nm (secondary jet)
Page 7 of 23 205

kg/mol)
205 Page 8 of 23 J Polym Res (2020) 27:205

hydroxybutyrate-co-3- hydroxyvalerate); PLA: poly(lactic acid); PLGA: poly(lactic-co-glycolic acid); PLLA: poly(L-lactic acid); PMMA: poly(methyl methacrylate); PP: polypropylene; PPy: polypyr-
role; PS: polystyrene; PSF: Polysulfone; PU: polyurethane; PURAC: polylactic acid; PVA: poly(vinyl alcohol); PVAc: poly(vinyl acetate); PVDF: poly(vinylidene fluoride); PVP: poly(vinyl pyrrolidone);
gelatin; HPMC: hydroxypropyl methylcellulose; IPN: interpenetrateng networks; MEK: methylethylketone; MOF: metal-organic frameworks; MWCNT: multi-walled carbon nanotubes; nBG: nano-

SIS: poly(styreneblock-isoprene-block-styrene); TCF-H: tricyanofuran-hydrazone; TFE: 2,2,2-trifluoroethanol; TCH: tetracycline hydrochloride; THF: tetrahydrofuran; TiO2: titanium dioxide anatase;
bioactive glass; Ni-NPs: nickel nanoparticles; PAA: polyamic acid; PA-6: polyamide-6; PAN: polyacrylonitrile; PAni: polyaniline; PCL: poly(ε-caprolactone); PDLLA: poly(D,L-lactide); pDTEc:
poly(desaminotyrosyl-tyrosine ethyl ester carbonate); PEG: poly(ethylene glycol); PEO: poly(ethylene oxide); PET: polyethylene terephthalate; PG: type A pork skin gelatin; PHBV: poly(3-
BCNW: bacterial cellulose nanowhiskers; CA: cellulose acetate; CNCs: cellulose nanocrystals; DCM: dichloromethane; DMAC: N,N-dimethylacetamide; DMC: dimethyl carbonate; DMF: N,N-
dimethylformamide; EVA: Poly (ethylene-co-vinyl acetate); HA: hydroxyapatite; HFIP: hexafluoroisopropanol; HFP: 1,1,1,3,3,3-hexafluoro-2-propanol; HMWFG: high molecular weight fish skin
77–80], polyacrylonitrile (PAN) (four studies) [45, 53–55],
polyurethane (PU) (four studies) [1, 43, 64, 76], poly(vinyl
[87] acetate) (PVAc) (four studies) [7, 18, 31, 36], poly (ethylene-
co-vinyl acetate) (EVA) (three studies) [50–52], as well as a
mixture of two or more polymers [9, 20, 28, 35, 42, 58, 73,
84–87]. Other polymers were also solution blown spun, but in
smaller amounts [2, 7–10, 12, 21, 23, 25, 26, 40, 41, 73, 75,
81–83]. Besides tissue engineering, blown spun fibers have
also been applied as adsorbents, sensors, biosensors, filtering
Drug release

VDF-TeFE: tetrafluoroethylene copolymer with vinylidene fluoride; WPS: waste expanded polystyrene; Zr-ACP: zirconium-modified amorphous calcium phosphate
membranes, or air filtration devices.
Regarding the polymer solution parameters, it was ob-
served that: (i) polymer concentrations generally varied from
5 to 15% (up to 40%), (ii) the organic solvents dichlorometh-
ane (DCM), ethyl acetate, acetone, methanol, N,N-
or 101 nm–1 μm

dimethylformamide (DMF), and formic acid were the most


502 nm–1.59 μm

used ones, mainly due to the volatility of these compounds,


and (iii) solvent mixtures, such as formic acid/ acetic acid,
xylene/chloroform or chloroform/dimethylchloride, and chlo-
[20]
[35]

robenzene/methanol, also were used.


Concerning the SBS processing variables, it was observed
that the works that used water as a polymer-solvent required a
thermal blower attached to the process to help evaporation.
Most studies used air at room temperature as a gas flow, al-
though others nitrogen, argon, and carbon dioxide (CO2), with
outlet pressures ranging from 0.2 to 0.6 MPa. Most of the
feeding rates employed by the systems reported in Table 1
ranged from 10 to 30 μL/min [18, 31, 36]. Regarding the
micro/nanofibers collector type, the studies used rotary or
fixed flat surfaces, with average needle-collector distances of
10–30 cm, with the longest up to 1.8 m. Concerning the fiber’s
average diameter, a high variability of values was observed,

from nanometric fibers of 100–600 nm up to micrometric


0.025–2.5 mL/-

sizes of 5 μm. The priority that determines the average diam-


0.02–2 mL/min

min (shell)

eter of the produced fibers is the same as considering the effect


(core) and

of the presence, or absence, of beads on the scaffolds, i.e. the


fiber’s application. The discussion of the main findings re-
garding the blow spun polymer systems described in
Table 1, mainly concerning the solution parameters, process-
Flat (polymer mesh under vacuum)

ing variables, and applications of fibrous materials can be


found here.

Polymer solution

The ability of SBS to form stable and continuous jets of poly-


mer solutions is dictated by the polymer solution properties,
such as polymer concentration and molar mass, viscosity, and
surface tension [7, 9, 10, 12, 13, 16, 72]. Among these prop-
Table 1 (continued)

erties, polymer solution concentration was deemed as the most


(80/600/50–80 kg/-
PCL/PEO/ PDLLA

significant variable to control fiber diameter [1, 18, 21, 70,


72]. The formation of well-defined fibers is directly propor-
tional to the polymer concentration and occurs with increasing
mol)

solution concentration [17]. By changing polymer solution


concentration, it is possible to tailor the blown spun scaffold
J Polym Res (2020) 27:205 Page 9 of 23 205

Fig. 3 SEM micrographs of solution blown spun fibers of poly (vinyl 10,000x) (a), and 20%w/v (2,500x; inset 10,000x) (b) [88]. Adapted
alcohol) (PVA) (Mw 49,000 g.mol−1; degree of hydrolysis 98–99%) at with permission from Ref. 88, Santos AMC, et al. (2016) Mater Lett
different polymer concentrations in water: 12%w/v (2,500x; inset 176:122–126. Copyright © 2016 by Elsevier Inc.

topography, and therefore its surface properties [8, 34, 50]. surface tension and changes in the viscoelastic properties of
Low polymer concentrations produce highly fused morphol- the solutions [13, 16, 66].
ogies with a random microporous structure on the surface. As Solutions with a high polymer concentration exhibit a
the polymer concentration increases, a bead morphology is higher level of polymer chain entanglement and require a high
observed with a few distinct fibers. With further increases in driving force to overcome the upper surface tension and vis-
the polymer concentration, a particular fiber morphology cosity of the solution [16]. The chain entanglement is defined
without beads, is obtained (Fig. 3) [19, 30, 88]. At this con- by the critical overlapping concentration (c*), above which,
centration, fibrous scaffolds may exhibit highly localized satisfactory chain overlapping occurs [62, 82, 88]. Continuous
alignment or multiple fiber strands or bundles, which are very fibers are produced above the critical overlapping concentra-
difficult to achieve via electrospinning [8, 12, 19]. In general, tion (c > c*), while beaded structures and corpuscular mor-
lower polymer concentrations produce a narrower fiber diam- phologies are generated for solutions with c < c* [4, 13, 17,
eter distribution compared to higher polymer concentrations. 23, 31, 32, 51, 81, 88]. The parameter c*, and hence the chain
The higher standard deviation, associated with higher polymer entanglement, is favored by increasing the polymer concen-
concentration, may be directly related to the increase in tration as well as the polymer molar mass [43, 76, 84, 89]. The

Fig. 4 (a) Estimated concentration of semi-diluted overlap (c*) for molar mass of Mw = 2,276,000 g/mol [24]. Reproduced with permission
PMMA solution in hydrofluorocarbon as a function of molar mass from Ref. 24, Srinivasan S, et al. (2011) Polymer 52:3209–3218.
(Mw) (dotted line); (b) SEM image of the blow-spun fibers from the Copyright © 2011 by Elsevier Inc.
PMMA solution with concentration of c = 6 mg/ml (c/c * = 0.7) and
205 Page 10 of 23 J Polym Res (2020) 27:205

overlapping concentration (c*) is adequately estimated for the


semi-diluted environment in a system with interaction param-
eters favorable to solubilization by Eq. 1 [49]:

63=2 M w
c* ¼
3=2 ð1Þ
8N A R2

where: c* = critical concentration, Mw = mean molar mass,


NA = Avogadro’s Number, and 〈R2〉 = mean square distance
between terminals.
An approximation of the mean square distance between
terminals 〈R2〉 for the polymer-solvent system is necessary
to calculate the critical concentration required to form fibers:

hR2i ¼ α2C ∞ ð2M w =M 0 Þl2 ð2Þ

This value can be found at the Flory expansion factor


α, the characteristic ratio C∞, and the bond length l Fig. 5 Dependence of polymer solution viscosity (μ) and surface tension
which are used to represent deviations from the ideality (γ) on polymer concentration ratio (C/C*). Some images of fibers
obtained at various Ca numbers are also presented [7]. Reproduced with
of the polymer chain dimensions. The mean molar mass
permission from Ref. 7, Benavides RE, et al. (2012) ACS Macro Lett
(Mw) of the polymer of interest and Avogadro’s number 1:1032–1036. Copyright © 2012 by American Chemical Society
(NA) are also necessary. If the temperature is increased
for the same polymer, the polymeric coil expands, spinning process. Yu et al. [91] showed by extensional rheol-
thereby increasing the mean square distance between ogy measurements that the solution elasticity, or its extension-
terminals, due to the mobility of the chains. al viscosity, is not necessarily related to the polymer entangle-
At a constant solution concentration, an increased polymer ments in solution. According to them, uniform fibers can be
molar mass causes the system viscosity to grow and thus, there obtained by any suitably strong elastic solution’s response,
is an increase of the blow-spun fiber diameter [20, 88, 90]. even with dilute polymer solutions. Other authors have also
Different morphologies can be observed when a polymer so- stated the same [19, 27]. The presence of entanglements net-
lution is blow-spun at various molar masses (Mw), and in this work is a sufficient but not a necessary condition for the poly-
case, an estimated concentration can be set for the semi- mer solution to demonstrate strong elastic beahavior. The
diluted overlap (c*) as a function of Mw (dotted line in pseudo-elastic response can also be achieved at lower polymer
Fig. 4a). Circles represent the morphology observed when concentration if the relaxation time of the fluid is longer than
spinning neat PMMA in hydrofluorocarbon, at a specific con- the time of extensional deformation. This kind of elastic be-
centration and molar mass. For a moderate molar mass havior is typical of Boger fluids that show high elasticity at
(<106 g/mol), there is a transition from corpuscular morphol- concentrations well below c* [92]. The Rayleigh instability
ogies into fibers structures at c/c* ≈ 1, confirming the essential can be slowed down or suppressed by the viscoelastic behav-
role of chain overlap in the stabilization of fiber formation. At ior of the fluid jet [91]. For fluids that have relaxation time
a high molar mass (Mw = 2,276,000 g/mol), the extensional much greater than the instability growth time (i.e., large
viscosity of a diluted solution (c/c* < 1) is sufficiently large Deborah numbers, De > > 1), the formation of uniform fibers
to stabilize the formation of submicron fibers for long periods, is favored over the ‘beads-on-string’ morphology.
allowing the solvent to evaporate and the POSS/PMMA to Morphological transitions from smooth fiber, to non-uniform
solidify, as shown in Fig. 4b [24]. Hence, the fiber morphol- fiber, to ‘beads-on-string’, and finally to droplets are not only
ogy is systematically altered by increasing the polymeric con- observed by variations in polymer’s concentration but also as
centration in solution, and thus the molecular weight, but the a result of changes in solution elasticity [93].
specific morphological details, such as the presence and frac- Fibers with regular cross-sections can be obtained by the
tion of beads will depend on the molecular weight distribution balance between the viscosity and the shear forces imposed by
particularities [24]. Figure 4 shows that a dilute solution, but the compressed gas jet that drops out of the nozzle [19, 28, 31,
with a high molecular weight, is capable of producing fibers 35, 57]. As long as the viscosity increases, fiber elongation is
by blow-spinning. This means that it is not the overlapping hampered, and as a consequence, fibers with thicker diameters
concentration (c*) that governs fiber formation, but the in- are formed [3, 19, 46, 56, 57]. Large dispersion of the blow-
crease of the diluted solution’s elongated viscosity in high spun fiber sizes is also observed in situations of high solution
molecular weights which suppresses the jet break during the viscosity values [16, 33, 50, 83].
J Polym Res (2020) 27:205 Page 11 of 23 205

Fig. 6 Different rheological


regimes (shear rate 1 s−1, 25 °C)
for EVA solutions in
xylene:chloroform (96.4 wt%/
wt%), and schematic
morphologies of the polymer
chains: (1) diluted (0.5–5 wt%
EVA), (2) semi-diluted (5–
10 wt% EVA) and (3)
concentrated (15 wt% EVA) [51].
Adapted with permission from
Ref. 51, Rempel SP, et al. (2019)
J Appl Polym Sci 136 (24)47647
Copyright © 2019 by John Wiley
Sons, Inc.

The quality of the SBS micro/nanofibers can also be cannot be stretched by high-speed airflow, thereby preventing
assessed by the Capillary Number (Ca) (Eq. 3), which relates efficient solvent evaporation so leading to puddle formation.
to the dependence between polymer solution viscosity (μ) and Increased gas pressure may eventually cause fiber failure. The
surface tension (γ) [7]. For systems with a low Ca (in this puddles are likely to contain residual solvent. Puddles are
case, the surface tension dominating the process), the liquid macroscopic elements inside the scaffold that are easily visible
jet undergoes early break-up, due to Rayleigh instability, to the naked eye. While beads are formed at concentrations
which often leads to the production of beaded fibers. below the fiber-forming domain, puddles are produced at con-
Smooth fibers are produced at moderate values of Ca, centrations above the fiber-forming domain.
achieved by increasing the polymer solution viscosity or the Understanding the solution’s rheological behavior is essen-
velocity of the liquid jet. At very high values of Ca, the fibers tial to know the continuous flow of the fluid under external
show defects induced by the turbulent nature of the gas flow shear stress, as well as the degree of polymer chain entangle-
(Fig. 5). ment in the solution [26]. Four regimes describe chain overlap
and entanglements in a polymer solution: dilute, semidilute-
μV
Ca ¼ ð3Þ unentangled, semidilute-entangled, and concentrated [70, 84].
γ Figure 6 shows the rheological behavior of PLA solutions in
where μ, V, and γ are the viscosity, velocity of the liquid jet, dimethyl carbonate (DMC) at 25 °C [16, 94]. For this system,
and surface tension of the polymer solution, respectively. the onset of PLA chain entanglement occurred at a 7% w/v
The increase in fiber diameter also leads to an increase in concentration at the transition from the diluted to the semi-
average pore size and, therefore, an increase in air permeabil- diluted zone. The transition from the semi-diluted to the con-
ity. Thus, the mean pore size can be engineered by altering the centrated zone occurred at approximately 10% w/v of PLA in
polymer concentration which will enable the control of the DMC, representing the region of most significant polymeric
mat’s barrier properties [21, 43, 84]. Polymer concentration entanglement. In the concentrated zone, higher viscosities are
also affects the fiber adherence to the collector surface. Lower perceived for small increases in PLA concentration [16]. The
polymer concentrations produce fibers that do not stick well formation of bead fibers occurs when the polymer solution
due to their smaller diameters and quantity. These tinier fibers approaches the diluted solution circumstances [19].
tend to be blown off the collector before accumulating to form High viscoelasticity enables a polymer solution to be
a cohesive layer. Higher concentrations produce larger fibers stretched and drawn down in diameter as it travels to the
that attach to the collector and can be removed as a single collector [69]. Viscoelastic solutions produce fibers with a
sheet [30]. Sabbatier et al. [70] were the first to report the narrower diameter distribution and no beads [33]. If the ex-
formation of puddles in a fiber spinning process. Unlike bead tensional viscosity is not sufficiently raised along the jet
formation, these features occur due to instabilities at high length, the viscoelastic jet will split into single beads [19,
polymer solution concentrations. These viscous solutions 82, 95].
205 Page 12 of 23 J Polym Res (2020) 27:205

The solution’s elastic response can exceed the effects of proper solvent selection for the polymer dissolution is neces-
Rayleigh instability, allowing the formation of uniform diam- sary since solvent molecules interact differently with poly-
eter fibers [19]. However, extremely high viscoelastic solu- mers chains [34, 69]. Certain solvents can completely dissolve
tions can lead to fibers with varying diameters since two ad- a polymer while others only partially dissolve or swell it. To
jacent fibers may join to form a chord-type structure. After understand and predict the effect of polymer-solvent miscibil-
spinning, the aligned polymer chains tend to relax to recover ity on the morphology of blow-spun fibers, Oliveira et al. [69]
their original entangled and unaligned conformation, and this used the Hansen parameters. The Hansen parameters split the
effect is more pronounced for highly viscoelastic solutions. If total cohesive energy into three components, polar interac-
the timescale is favorable, the elastic recovery may counteract tions (δp), hydrogen bonding (δh), and van der Waals disper-
fiber-forming tendencies giving rise to fibers with a broad sion or interactions (δd). These parameters are based on the
range of diameters. Polymer chains with less mobility i. e., concept that “similar dissolves similar” and that materials with
at higher polymer concentrations or higher polymer molar equivalent values of δd, δp, and δh will be more miscible [69,
mass, should lead to larger fiber diameters. The mobility is 99]. Oliveira et al. [69] investigated the viscosity differences
scaled by the longest relaxation time (λ) (Eq. 4) of the poly- for polylactic acid (PLA) solutions prepared in chloroform,
mers in solution [20]. The longest Rouse relaxation time can and dichloroethane. Although chloroform and dichloroethane
also be determined by the dynamic modulus [96]. Using this present a very similar sum of all three Hansen’s parameters
correlation, one can attribute larger diameter fibers at higher (Table 2), significant differences in PLA solution viscosities
polymer molar mass to higher solution viscosities and longer were observed for these solvents. PLA solutions of 8 wt%
relaxation times [9, 30]. showed viscosities of approximately 107 mPa.s and 72 mPa.
s when prepared in chloroform and dichloroethane, respec-
6ηs ½ηM w
λ≈ ð4Þ tively. This was explained by an individual aspect of the
π2 RT Hansen’s parameters. Chloroform showed higher δh and δd
Where ηs is the solvent viscosity, [η] is the Mark–Houwink values, suggesting a higher degree of hydrogen bonding and
intrinsic viscosity (dependent on the particular polymer- dispersive or Van der Waals interactions with PLA, as com-
solvent system), R is the universal gas constant, and T is the pared to dichloroethane. The high viscosity of PLA/
temperature. dichloromethane solutions at low shear rates can be explained
The relationship between chain entanglement and diameter by the high solubility of the polymer since this solvent was the
distribution of fibers has been proposed for the electrospinning one that presented the closest Hansen’s parameters to the
process [97]. Such an approach is also applicable to SBS, due PLA. Thus, even if several solvents can solubilize PLA, they
to the similarity of the dynamics of liquid jet stretching, and is interact with the polymer in different ways, producing solu-
based on the concept of solution entanglement number (Ne)s. tions with unique properties capable of affecting the spinning
The parameter (Ne)s is defined as the ratio of the polymer process and, consequently, the fiber morphology [69].
molecular weight (Mw) to its solution entanglement molecular Another remarkable property of the solvent is its boiling
weight (Me)s (Eq. 5). Although the importance of entangle- point, which will directly influence its evaporation rate [23,
ment for the SBS process is recognized, it is not known pre- 73]. Most of the published work on solution blow spinning
cisely how many entanglements are required to affect/stabilize comprises the use of highly volatile organic solvents or sol-
fiber formation. Using the solution entanglement number vent mixtures [100]. Solvents with high boiling points pro-
(Ne)s, the required polymer concentration for fiber formation duce spun fibers with non-uniform morphologies because of
may be determined a priori, eliminating the trial-and-error improper volatilization [1, 29, 34]. At insufficient solvent
methodology typically employed to produce spun fibers. The evaporation, fiber welding occurs, and a wet, film-like mem-
entanglement number eventually determines whether a spray, a brane is observed [88, 101]. The welding process proceeds by
spindle-knotted fiber or a uniform fiber is obtained [38]. Thus, solvent-based re-dissolution, and subsequent solidification,
embryonic fiber formation is correctly predicted for a variety of and occurs when the fibers containing some un-evaporated
polymer/solvent systems at one entanglement per chain. For solvent come in contact with each other [82]. Polymer solu-
the electrospinning process, stable fiber formation occurred at tions produced from solvents with slow evaporation rates need
≥2.5 entanglements per chain.
Mw Table 2 Hansen’s
ðN e Þs ¼ ð5Þ parameters for PLA and System δp Δh δd
ðM e Þs
solvents in (J/cm3)1/2.
Poly(lactic acid) 9.9 6.0 18.6
Besides polymer structure and its molar mass, polymer- Chloroform 3.1 5.7 17.8
solvent interactions are also responsible for variations in the Dichloromethane 6.3 6.1 18.2
Dichloroethane 7.8 3.0 16.5
solution viscosity and surface tension [20, 33, 69, 83, 98]. The
J Polym Res (2020) 27:205 Page 13 of 23 205

a longer working distance to ensure that the fibers are suffi- in SBS [8, 16, 30, 69]. This process is sensitive to relative
ciently dry before they reach the collector. Miranda et al. [74] humidity higher than 30%. During fiber formation, solvents
observed that the mean diameters of blow-spun polystyrene with low vapor pressures generate inferior internal pressures
(PS) fibers were more dependent on the solvent evaporation and can diffuse through the clad structure without leaving any
rate than on the rheological behavior of the starting solutions. visible pores [69].
Spinning from low volatile solvents like water is challenging Besides affecting porosity, the solvent evaporation rate also
since the fibers do not get fully dry before reaching the col- impacts the crystal structure of the resultant polymer mat [17,
lector, causing the fibrillar morphology to be destroyed by the 69]. At higher solvent vapor concentrations in the surround-
coiling of the polymer molecules [88]. Difficulties in spinning ings, the polymer chains are likely to have more time to pack
high molecular weight PVA aqueous solutions have been into a thermodynamically stable form, inducing an increase in
overcome by introducing hot air at the point of fiber formation crystallinity. In contrast, a rapid solidification rate does not
to force solvent evaporation [88]. For thermoplastic polyure- provide enough time for the polymeric chains to organize
thane (TPU)-dimethylformamide (DMF) systems, the alterna- themselves into entirely regular structures. This condition
tive for increasing the evaporation rate of DMF (high boiling mainly influences the flexible polymers with a lower glass
point, 135 °C) and solving the residual solvent problem was transition temperature (Tg) since they have greater mobility at
the addition of small amounts of tetrahydrofuran (THF) (boil- their process temperatures and crystallize in a shorter time than
ing temperature of 65 °C). A series of DMF/THF solvent a rigid polymer with high Tg. For example, poly (lactic acid)
mixtures at the proportions of 7:3, 5:5, and 3:7 (w/w) were (PLA), poly(ethylene oxide) (PEO), and polycaprolactone
tested in the preparation of TPU solutions. The solvent mix- (PCL), have Tg values of 60, −11 and − 72 °C, respectively;
ture was shown to be an excellent option for obtaining more thus, the crystallization of PEO and PCL can be favored by the
homogeneous fibers. Interestingly, the higher the proportion chain elongation during fiber formation. Spun fibers of PEO
of THF in the DMF/THF mixture, the higher the TPU solu- and PCL showed a higher degree of crystallinity compared to
bility and the larger the diameter of the fibers [1]. PLA fibers, which was interpreted by the differences in glass
During spinning, the concentration and viscosity of the transition temperatures of these polymers [57].
solution filaments keep changing due to the gradual solvent Furthermore, the incorporation of any particle, biomole-
evaporation, which directly impacts the distribution of fibers cule, or agent, into the solution will influence the solubility
reaching the collector [55]. A conical dispersion of filaments parameters of the polymer, being fundamental to the investi-
is observed in the lower segment of the spray plume. The gation of the best polymer-solvent combination [51, 68]. The
radially symmetric spray pattern on the target shows two dis- presence of TiO2 in nanofibrous polysulfone/TiO 2 and
tinct fiber distribution zones: a dense zone with high fiber PVDF/TiO2 nanocomposites had a direct effect on the solvent
density and a dispersed zone with spatially distributed fibers. evaporation rate [75, 80]. An increase of polymer-particles
While the fibers are randomly oriented at the center of the interactions seemed to reduce the solvent-polymer and
dense zone, radially oriented elongated streaks of segregated solvent-particles interactions, leading to greater freedom for
fibers are observed emerging from the dense zone towards the solvent molecules, and favoring their evaporation.
dispersed zone. The radially outward gas flow, after impacting
the target, is responsible for the radially oriented elongated Spinning parameters
streaks of segregated fibers [82]. The evaporation rate of the
solvent depends directly on the polymer concentration since in While the solution properties dictate the microscopic features,
concentrated solutions, and therefore with less solvent, the such as beads or fiber formation, the operating parameters
segregation of polymer molecules is prevented, and entangle- govern the macroscopic characteristics (like film or fibrous
ment is favored [4, 19]. Due to the high surface area and the texture, crystalline structure, and physicochemical properties)
exposure to accelerated air flows, the solvent evaporation rates [12, 82].
in blow-spun fibers are usually higher.
It should also be taken into account that a suitable solvent Pressure and gas type
tends to further expand the polymeric coil due to the effect of
excluded volume [102]. A clad/core structure is formed during In solution blow-spinning, the driving forces involved are the
fibers formation due to the rapid solvent evaporation on the jet pressure and shear differences at the solution/gas interface
stream’s surface. During this short period, the diameter of the [90], the latter being responsible for the deformation of the
germinal fiber is still decreased. Furthermore, the evaporation polymeric solution from the internal nozzle to a conical shape
of the solvent entrapped at the inner region of the core gener- [9]. In this technique, the high-pressure gas must exceed the
ates a vapor pressure which is relieved by the formation of surface tension of the polymeric solution and, therefore,
small pores developed directly through the shell structure. stretch the solution into ultrafine fibers [8, 103, 104].
This means that the evaporation kinetics affects fiber porosity Simultaneously, due to the high speed and low pressure, the
205 Page 14 of 23 J Polym Res (2020) 27:205

air jet vaporizes the solvent of the produced nanofibers [9, 31]. the nozzle shapes the solution’s surface into a cone [17]. A
Different high-pressure gas sources can be used, including critical parameter in an airbrush spinning technique is the
pressurized air, hydrogen, nitrogen, argon, and carbon dioxide velocity at which the polymer jet reaches the collecting sur-
[1]. The “blowing medium” refers to any source of air or gas face. This process uses the energy stored in the high pressure
capable of stretching polymer solution, but most of the sys- compressed gas to elongate the polymer into thin fibers at very
tems described make use of compressed air or nitrogen [9, 30, high speeds [34]. When there is no gas flowing through the
57, 64]. In the case of fibers exposed to compressed air con- outer nozzle, a convex drop of the polymer solution is formed
taining moisture, their morphology will be as much influenced in the inner nozzle. While the gas flow is directed to the outer
the higher the affinity between the solvent and water. Behrens nozzle, a low-pressure region near the orifice of the inner
et al. [23] used CO2 in their experiments because of its capac- nozzle develops. The convex drop of the polymer solution
ity for in situ deposition, especially for avoiding the risk of air will be drawn into a cone shape in the same proportion as
embolism due to its solubility in blood. Khayet et al. [105] the gas flow increases through the outer nozzle (Fig. 7(A)).
studied the effects of the gas type (namely, air, oxygen, nitro- The photomicrographs demonstrate the solution jet flow from
gen, carbon dioxide, and argon) on the morphological proper- the cone to the collector. This is due to the combination of the
ties and performance of polyethersulfone (PES) spun fibers low-pressure zone and shear at the solution/gas interface, as
using atomic force microscopy (AFM) and solute transport shown in Fig. 7(B-D) [9].
analysis. The diameter, surface roughness, and porosity of The spinning pressure also interferes directly with the qual-
the polymer fibers were significantly affected by the type of ity of the microstructures formed during the process [8, 34]. In
gas used. The studied PES fibers could be divided into two a study using PLA in DMC, it was observed that pressures
groups: those prepared under gases with higher molecular below 30 psi did not provide an appropriate driving force to
mass and lower thermal conductivity (like carbon dioxide overcome the surface tension of the solution, and thus did not
and argon) and those prepared under the other gases (air, ox- form fibers. In contrast, for pressures greater than 90 psi, the
ygen and nitrogen) having lower molecular mass and higher fiber jets were delivered too fast to the collector, not giving
thermal conductivity. The PES fibers having the smallest di- sufficient time for adequate evaporation of the solvent [16].
ameters were those prepared using gases with high molecular This behavior was also observed by other authors [10, 16, 19,
mass. The fiber diameters increased following the order: Ar < 37, 45, 52, 78, 82, 107]. The low gas velocity does not form a
CO2 < N2 < O2 < air. The average surface roughness values suitable cone for fiber production, while the high gas velocity
decrease following the order: Ar > CO2 > N2 > air > O2. forms an unstable cone, in which the cone/fibers dry out in
Moreover, the pore sizes were found to be more significant
for the PES fibers prepared under Ar and CO2 compared to
those produced under N2, O2, and air. A plausible explanation
for these behaviors is based on the thermal conductivity of the
different gases used, which will directly influence the solvent
evaporation rate. The evaporation in high thermal conductiv-
ity media (i.e. air, O2 and N2) will be faster than in low thermal
conductivity media (i.e. Ar and CO2). When the thermal con-
ductivity of the gas media is high, more heat is supplied from
the gas media towards the external fiber surface and, conse-
quently, more evaporation of solvent takes place as its vapor
pressure is higher at higher temperature [106]. In addition to
the thermal conductivity of gases, other explanations should
not be discarded, like the gas/polymer interactions and the gas
solubility through the polymeric fiber. Unfortunately, because
the SBS technique is relatively recent, sufficient information
regarding the influence of the carrier gas type on fiber quality
is not yet reported in the literature [105].
During fiber formation in SBS, a jet of the polymer solution
is subject to aerodynamic drag. Throughout the air jet dis-
placement by the environment, the solvent evaporates, giving Fig. 7 Micrographs of blow-spun fibers taken by a high-speed camera.
rise to ultrafine semi-dry polymeric fibers that can be collected The low-pressure region at the end of the inner nozzle converted the
polymer solution into a cone (A). The dotted region in (A) was
on practically any substrate [17]. The conditions of fiber elon- magnified and shown in (B-D) [9]. Reproduced with permission from
gation and diameter distribution are consequences of the shear Ref. 9, Medeiros ES, et al. (2009) J Appl Polym Sci 113:2322–2330.
forces acting on the polymer solutions [2]. The gas that leaves Copyright © 2009 by John Wiley Sons, Inc.
J Polym Res (2020) 27:205 Page 15 of 23 205

random directions [59]. The increase of air velocity pro- Feed rate
motes an air pressure drop at the center of the jet,
creating a driving force responsible for the polymer so- By maintaining the polymeric solution jet at constant pressure,
lution acceleration [16]. Fiber diameters and fiber size the feed rate of the solution can be adjusted to control the
distributions decrease and become more uniform as the quality of the fibers being produced [18, 90]. The solution
gas pressure increases; however, the fibers may acquire can be fed into the system by gravity, as in commercial air-
a curled and/or twisted morphology at turbulent gas brushes, or through a syringe pump, in which flow control is
pressures [9, 10, 45, 56, 57, 59, 65, 104]. Inconsistent more accurate. A low feed rate does not release enough solu-
jets produce thicker fibers with a broader mean diameter tion to form continuous fibers and typically results in obstruc-
distribution, in addition to being superficially porous, tion at the needle tip. A high feed rate supplies too much of the
due to deficient solvent evaporation. Not only pressure polymer solution at the needle tip and results in the formation
interferes with the fiber diameter, but also the solvent of beads since the pressurized air cannot wholly remove the
type and the polymer solution concentration, as solvent [16, 43, 52, 107].
discussed before. When PLA was spun in chloroform Regarding the effect of feed rate on fiber morphology,
or HFP, an increase in pressure resulted in a decrease studies have shown that an increase in solution feed rate
in the fiber diameter. When DMC was tested as the causes an increase of fiber diameter and its distribution, main-
solvent, however, only the polymer concentration was ly because the fibers do not dry properly and begin to fuse on
shown to influence the fiber diameter, without any air the collector surface [10, 19, 65, 103, 104]. This effect may
pressure effect in this case [13]. become parabolic at lower concentrations [10, 30, 35]. At an
Studies report a parabolic dependence between fiber diam- optimal feed rate, a reduction in fiber diameter is expected
eter and pressure for low air pressures, and a linear relation- because when the feed rate is equivalent to the solution jet
ship for higher air pressures [19]. This condition occurs be- output rate, the conical shape at the nozzle remains stable,
cause the surrounding gas flow on the jet surface that leaves which is the opposite of the nozzle locking case (high feed
the nozzle does not allow the accumulation of solvent mole- rate) or jet instability (low feed rate) [19, 21, 65]. High feed
cules immediately above the jet surface, so causing a high rate rates can cause nozzle blockage due to the formation of a drop
of evaporation. This happens because the boundary lay- that accumulates and solidifies at the tip. Jet instability occurs
er on the evaporation surface decreases with the flow when the solution is drawn into the collector faster than the
velocity, reducing the diffusion of the solvent from the stag- feed rate. Higher feed rates would naturally increase fiber
nant layer [4, 43]. Thus, at high gas pressures, the solvent productivity, at least in cases where nozzle obstruction would
evaporation rate increases, which reduces the fiber diameter. occur. The optimal value of this parameter is considerably
The increasing gas pressure has a more noticeable effect on affected by the viscosity of the solution, which depends on
fiber morphology for more concentrated polymer solutions the molecular weight and the concentration of polymer [19].
(~10% wt.) [46]. The reduction in gas pressure increases the Medeiros et al. [9] tested a feed rate of 200 μl/min in a solution
fiber diameter and its distribution, negatively affecting the blow-spinning system, a rate well above the commonly
spinning process. At low pressures, there is not enough elon- adopted 20 μl/min, and found that it is possible to feed poly-
gation and, consequently, thicker fibers are formed and, when mer solutions at a higher rate, as long as a specific balance
the pressure is overly high, other effects occur such as jet between the feed rate and the gas pressure is respected.
instability caused by turbulence at the nozzle outlet [19]. Variations in any operational parameter affect the morphology
Rajgarhia et al. [35] proved that by adding a secondary gas and quality of spun fibers, regardless of the direct influence of
jet to the original turbulent gas jet, it is possible to obtain fibers the feed rate on their mean diameter. Besides fiber diameter,
with even smaller diameters. polymer chains orientation, porosity, and crystallinity are also
The results showed an almost 100% reduction in nanofiber affected by the feed rate [2, 8, 16, 84]. This parameter might
diameter of bilobal, and interpenetrating network type, nano- be the most important process variable of the fiber morpholo-
fibers by placing this secondary gas jet at the solution delivery gy homogeneity.
nozzle. The substantial reduction in fiber diameter occurred by
taking advantage of the synergy of stretching by the two gas SBS collector type
jets and the bending instability caused by the first gas jet. As in
electrospinning, there is a suitable balance between gas pres- The collector used to gather the spun fibers need not necessarily
sure and solution feed rate for successful solution blow-spin- be solid; it may be a liquid, in which the specific physicochem-
ning. Keeping the gas pressure constant and adjusting the ical reaction will occur. Abdal-Hay et al. [31] did not observe
solution feed rate, these two parameters equilibrate and coop- any differences in the average diameter of fibers collected in a
erate for the formation of uniform and bead-free fibers [9, 46, glass or a water bath. Both collector phases produced nanofi-
84]. bers with proper morphology. This significantly impacts the
205 Page 16 of 23 J Polym Res (2020) 27:205

Fig. 8 Effect of the distance between the spinning device and the collector on the morphology of PAA nanofibers [10]. Reproduced with permission
from Ref. 10, Li J, et al. (2017) Nanomaterials 7(11):395. Copyright © 2017 by Creative Commons
J Polym Res (2020) 27:205 Page 17 of 23 205

application potential of the technique. The authors also ana- distances, semi-solidified fibrous structures are agglomerated
lyzed the influence of drum velocity on the morphology of at the collector, and thick micro/nanofibers with many beads
PCL nanofibers through a rotary collector. Due to the high are produced [9]. Some changes in morphology, such as
production rate of the utilized technique, no significant effect beads, flat film-like fibers, agglomerations at fiber junction
was observed between PCL nanofibers obtained on the static points, and large interconnected fibers, are characteristic of
drum (speed = 0 rpm) and the rotating drum at 500 rpm [31]. the deposition of still wet fibers on the collector or substrate
Fiber diameter distribution is not affected by collector rotation. [18]. At longer distances, the solvent evaporates, and beaded-
Sometimes, the nature of the collector is more responsible free solid fibers are gathered in the collector. Figure 8 shows
for performing specific chemical/physical reactions in the fi- the polyamic acid (PAA) nanofibers (8 wt.%) produced from
bers than the rotation used. Although it does not cause signif- different spinning device-collector distances [10].
icant changes in the diameter of the fibers, the type of SBS
collector may influence the alignment of the micro/nanofibers Nozzle diameter and configuration
structure [67]. Generally, the use of a static collector provides
randomly and nonaligned deposited fibers [60]. Fiber align- The relation between nozzle diameter and fiber diameter is
ment can be achieved by the deposition of fibers onto a high- dependent on the polymer solution concentration which af-
speed rotating collector, although only partial alignment has fects the surface tension of the drop at the needle tip. Thus,
been reported so far for the SBS process [64, 67]. Fiber align- surface tension directly controls the drop size and the quantity
ment directly affects mechanical behavior in the perpendicular of solution that is instantly stretched [70]. Enlarging the noz-
direction of the aligned mats. Aligned mats are anisotropic, zle diameter reduces the friction force per unit volume be-
while nonaligned mats have isotropic behavior. The shape of tween the inner wall of the nozzle and the polymer solution,
the collector, such as opening radius and height, can affect the which provides multi-jet ejection because of the higher solu-
porosity of the 3D fibrous structures. For blown spun tion flow volume and the larger pendant droplet. As a conse-
polyethyleneoxide (PEO) scaffolds, their porosities when quence, the fiber becomes thinner with increasing the nozzle
shaped by a square collector, a hemispherical collector, and size. However, some studies have indicated that a needle with
a conical collector were 84.4%, 85%, and 86.9%, respectively a smaller diameter is the one that leads to fiber-free granules
[65]. and no clogging at the needle tip [49, 103]. Keeping the solu-
tion feed rate constant, the larger the nozzle diameter, the
Nozzle-collector x distance thicker the extrudate flow and the larger the mean diameter
of the fibers produced [10]. The best nozzle configuration is
The distance between the spinning device and the collector is one that reduces fluctuations and turbulence intensity, so
a processing variable that influences spinnability, but it has preventing instabilities in the fiber formation [45]. The dis-
little effect on fiber diameter and its distribution [9, 16, 78]. tance (d) the inner nozzle protrudes beyond the plane of the
The effective nozzle-to-collector distance range extends from outer nozzle had little effect on fiber diameter (Fig. 9).
the minimum distance required for the fibers to dry before However, processing was affected by d; when d was zero or
collection to a maximum distance that avoids the excessive greater than 3 mm, residue from the polymer solution formed
loss of the jettisoned fibers [10, 16]. The optimum working around the nozzle opening or on the inner nozzle itself [9].
distance will increase productivity and the formation of fibers Multi-orifice dies for solution blowing were designed
with the smallest mean diameter [10, 16, 43, 82]. For small to diminish the propensity for clogging [63, 79].

Fig. 9 Schematic representation


of the solution blow spinning
apparatus used fiber preparation
[19]. Reproduced with permission
from Ref. 19, Oliveira JE, et al.
(2011) J Appl Polym Sci
122:3396–3405.Copyright ©
2011 by John Wiley Sons, Inc.
205 Page 18 of 23 J Polym Res (2020) 27:205

Kolbasov et al. [89] blow-spun soy protein-poly(ethylene Other variables that affect the SBS process
oxide) nanofibrous nonwovens using industrial multi-
orifice concentric air nozzles (41 nozzles per row and 8 Spinning temperature
rows). Supplying air concentrically to the central soy pro-
tein jet ensured that the solvent evaporated uniformly, In the SBS process, the temperature will affect the volatiliza-
thereby eliminating the chances of uneven drying. tion speed of the organic solvent. When the temperature is
Zhuang et al. [79] used a 20-orifice die to produce low, the solvent volatilization is slow, and beaded micro/
polyvinylidene fluoride (PVDF) mats and observed that nanofibers are produced. However, if the temperature is too
the fibers were three-dimensional curly due to the effect high, the solvent volatilization becomes very fast, which dis-
of the turbulent flow in the gas flow field. This character- turbs solution spinning, and produces non-uniform fibers.
istic increased the porosity and enhanced the transport Moreover, fiber trickle would tangle in spinneret easily and
properties of the nanofibrous materials. Hofmann et al. plug it [76].
[38] presented a microfluidic nozzle device for the pro-
duction of perfluorinated copolymers and polycaprolactone
(PCL) ultrafine fibers. Relative environment humidity
In contrast to SBS with a concentric nozzle, the inner noz-
zle of the microfluidic device did not protrude beyond the The relative humidity of the surrounding environment can
outlet of the compressed air. Within the microfluidic nozzle, also affect the porosity and the fine topographic structure of
the air stream approached perpendicularly from the sides. the fibrous mats [13, 17, 18, 24]. Controlling the relative hu-
Uniform fibers with virtually endless length and narrow size midity of the environment is essential for the production of
distribution were produced in a continuous process while hav- bead-free smooth fibers [18]. The presence of micropores on
ing an accurate control over the fiber diam eter. the surface of the fibers has been related to high relative hu-
Hydrodynamics and mass balance quantitatively predicted midity (Rh > 30%) operations [13, 34, 82]. Analogous to the
the fiber diameter, which was only a function of feed rate electrospinning process, the pore formation in SBS is also
and air pressure, with a small correction accounting for any expected to arise from the complex polymer-solvent interac-
viscous dissipation during jet formation. Hell et al. [61] devel- tion with the moisture in the air. Fibrous mat thickness (fiber
oped a semi-automated SBS nozzle for the production of PCL mass) is another variable that affects the pore diameter of the
mats and compared the results to those found for airbrushing, final mat network. By increasing the mat thickness, and thus
using the same set of parameters. Although the fibers pro- the scaffold layers, fiber entanglement also increases, which in
duced by both methods exhibited equivalent diameters, the turn rapidly decreases the pore size [25, 39, 42, 64].
mats presented different microstructural characteristics.
Airbrushing seemed to generate more beads and fiber bundles
than the semi-automated process. This difference is neither Particle, additive or polymer phaseadditions
good nor bad, considering that there is a suitable morphology
for each application, but it will influence the scaffold’s The SBS process has been proven to be an efficient technique
properties. to produce hybrid fibers containing reinforcing and/or biolog-
The optimum spinning conditions are dependent on many ical agents. In this case, the viscosity and surface tension of the
parameters, whether related to the polymer solution or to the solutions increase with a higher solid content and a higher
operational variables. Through statistical and experimental nanofiller concentration, which will have an effect on the
analysis, it is possible to establish the optimal spinning con- morphology of the spun fibers [27, 67]. Depending on the
dition for a specific polymer system. For each polymer- type and intensity of the interactions between the solids/filler
solvent system, there will be ‘fiber spinnability limits’ capable and the polymer, the viscosity and surface tension of the so-
of maximizing fiber formation and producing materials with- lutions will change, resulting in polymer structural rearrange-
out any undesirable structural features [16, 82]. So, rather than ments, thus altering the spun fiber’s morphology [27, 68]. The
analyzing the effect of the isolated processing parameters, it is mean diameter of polyurethane (PU) nanofibers increased
imperative to evaluate their combined effect since interactions slightly when multi-walled carbon nanotubes (MWCNTs)
between experimental variables always exist [9, 13, 16, 26, were incorporated into the polymeric solution [1, 20].
70]. Once the processing window for the blow-spinning of a Considering scaffolds made from polymeric blends,
particular solution system is achieved, no significant changes transmission electron microscopy (TEM) provided evidence
in fiber formation or fiber diameter can be observed by vary- that fibers were comprised of core/sheath structures with one
ing the spinning parameters [26]. The reproducibility of the polymer in the core and the other in the sheath. Core/sheath
SBS method depends mostly on controlling the standard de- structures are formed due to differences in the surface tension,
viation of the fiber diameter [13, 16, 66]. and polymer-solvent, and polymer-polymer interactions [28].
J Polym Res (2020) 27:205 Page 19 of 23 205

Applications of SBS-spun fibers affects the mechanical properties is the presence of beads in
the polymer scaffold. Beads are generally considered as de-
Many applications can benefit from using the SBS process for merits in a spun fibrous material as they provide additional
preparing fibrous materials. This technique also allows tailor- stress points [42]. The presence of beads may create local
ing of the topography of the mat’s surface, further enhancing traction stress concentration and ultimately lead to early fail-
its applicability [75]. The mats can be built with as many ure [70]. The load distribution in a fiber is usually uniform if
layers as desired, achieving satisfactory structural integrity its diameter is uniform [1]. Overall, the number of polymer
[60]. Moreover, two air-jet spinning (AJS) devices can be beads within the scaffold structure should be minimized and
used simultaneously to produce dual-polymer hybrid fibrous not occupy a surface area of more than 3% of the fiber assem-
scaffolds deposited layer by layer with a variable pore struc- bly. Rempel et al. [51], however, reported a beneficial aspect
ture, and tunable mechanical properties [39]. Compared to of the presence of beads in ethylene-vinyl acetate (EVA) scaf-
electrospinning, airbrushed network scaffolds have greater folds, used as vehicles for the controlled release of phero-
pore size and higher porosity, which favors cell infiltration mones. According to the authors, the beads functioned as a
and justifies their use in biomaterials [12, 39, 41, 71, 85]. reservoir of actives agents, contributing to the incorporation
This specific microrelief in SBS nonwoven materials facili- and long release period of the active agent.
tates the migration and adhesion of cells into the bulk of the
mat and creates favorable conditions for the receipt of nutri-
ents and the removal of cell’s by-products [108]. SBS- Future perspectives
produced fibers can be used as cardiac engineered scaffolds
[64], controlled-release fiber systems of active agents [3, 85, The SBS process has great potential to be explored because of
86], and biomedical applications [73, 87], among others. its several advantages over other micro-nano fiber production
Researchers have discussed direct nanofiber deposition, using techniques. Compared to electrospinning, the SBS method
an airbrush technique, onto different targets and living organ- solves the drawback of fiber production under high electrical
isms for surgical hemostatics surgical sealants, or tissue conditions, allowing in situ targeting. The technique is adapt-
reconstruction/regeneration [29, 72, 87]. able for a range of solvents with limited toxicity, and different
SBS-spun materials can show magnetic properties when types of polymers, particles, fillers, and composite precursor
produced with nickel nanoparticles, so finding applications mixtures, hence expanding the manufacture of highly func-
as sensors and impurities removers from oil, water, and blood tional nonwoven micro and nano textiles [34–36]. Requiring
[77]. Polyacrylonitrile (PAN) blow spun nanofibers acted as a only a commercial airbrush, a concentrated polymeric solu-
proper support to immobilize tricyanofuran-hydrazone (TCF- tion, and a compressed gas source, the SBS can be used for the
H) multi-stimuli responsive molecular in the development of a deposition of fiber mats on non-conductive coverages, and in
solid-state colorimetric sensor [53]. Polyaniline (PANI)/poly- several applications on health care and agriculture [10].
acrylonitrile (PAN) core/shell composites nanofibers have po- Because they can be deposited on-demand, SBS can easily
tential applications in batteries, electromagnetic shielding, an- create conformal textiles, and materials with custom geome-
tistatic material, adsorption of heavy metal ions (like Cr(VI)), tries from a scalable self-contained process [49]. The simple
and other fields [54]. Polystyrene-based membranes prepared apparatus required for SBS will motivate researchers to inves-
through SBS have been used for oil adsorption in oil spills tigate unconventional applications for fibrous materials, such
cleanup and wastewater process [37, 58]. Metal-Organic as wearable electronics, energy storage batteries (ion separa-
Framework (MOF)-polymer fibers produced by SBS provide tor), biomaterials, virus barrier, and environmental monitoring
an exciting platform for applications in separation and cataly- sensors [112–115]. Direct deposition of cell-containing fibers
sis, as adsorbents, and as particulate filters [30]. Zirconia onto living targets enables the production of biological scaf-
(ZrO2) ceramic fibers, prepared by as-spun PVP/zirconium folds and biomimetic materials [116]. Moreover, the fibrous
oxychloride (ZrOCl3) composite precursor, have been applied materials developed by SBS are more commercially scalable,
as supports for catalysis, and filtration at high temperature which is crucial for their applicability. The portability of the
[109]. The SBS process has also been chosen as a route to technique also speeds production and reduces process ex-
industrialize other ceramic fiber mats, such as TiO2, SnO2, penses. Several researchers have improved SBS with multiple
SiO2, Al2O3, and Y-Ba-Cu-O (YBCO) [80, 103, 109–111]. nozzles and grids to increase the production scale, therefore
A compromise of properties limits the use of these mate- obtaining distinctive materials [89]. Since SBS is a newer and
rials. For example, a scaffold’s porosity may improve cell less reported technique, it is still necessary to establish a sub-
adhesion, but it may also interfere with its mechanical prop- stantiated relation between processing variables and fiber
erties [12]. The presence of a few PCL in PA6/PCL 90/10 morphology for the method to be controllable and reproduc-
composite scaffolds increased the porosity, the tensile ible. Most of the current applications of SBS fibrous materials
strength, and the elongation at break [42]. Another factor that are on the early proof-of-concept stage, and most
205 Page 20 of 23 J Polym Res (2020) 27:205

characterizations are still conducted only in vitro, which con- References


firms the urgency of further investigation.
This literature review had the purpose of enlightening the 1. Kuk E, Ha Y-M, Yu J, Im I-T, Kim Y, Jung YC (2016) Robust
and flexible polyurethane composite Nanofibers incorporating
academic community about the polymer systems already test-
multi-walled carbon nanotubes produced by solution blow spin-
ed by SBS, thus facilitating our choice for a more suitable ning. Macromol Mater Eng 301(4):364–370
system in a distinct application. It is now clearer which sys- 2. Souza MA, Sakamoto KY, Mattoso LHC (2014) Release of the
tems have been used most in the art and which challenges are Diclofenac sodium by Nanofibers of poly(3-hydroxybutyrate-co-
3-hydroxyvalerate) obtained from electrospinning and solution
most faced by scientists. From the studies reported in Table 1
blow spinning. J Nanomater 2014:129035
of this paper, researchers will be able to find new applications 3. Bonan RF, Bonan PR, Batista AU, Sampaio FC, Albuquerque AJ,
for the polymer systems which have already been tested. It Moraes MC, Mattoso LH, Glenn GM, Medeiros ES, Oliveira JE
will also be possible to optimize the reported limitations faced (2015) In vitro antimicrobial activity of solution blow spun
by other authors and having insights for new kinds of mate- poly(lactic acid)/polyvinylpyrrolidone nanofibers loaded with co-
paiba (Copaifera sp.) oil. Mater Sci Eng C Mater Biol Appl 48:
rials as well. 372–377
4. Tang D, Zhuang X, Zhang C, Cheng B, Li X (2015) Generation of
nanofibers via electrostatic-induction-assisted solution blow spin-
ning. J Appl Polym Sci 132(31):42326
5. Oliveira JE, Mattoso LH, Medeiros ES, Zucolotto V (2012)
Conclusion Poly(lactic acid)/carbon nanotube fibers as novel platforms for
glucose biosensors. Biosensors (Basel) 2(1):70–82
This review article aimed at analyzing the central polymeric 6. Ahmed J, Matharu RK, Shams T, Illangakoon UE, Edirisinghe M
systems that had been processed by the solution blow- (2018) A comparison of electric-field-driven and pressure-driven
Fiber generation methods for drug delivery. Macromol Mater Eng
spinning technique (SBS). A literature review was conducted
303(5):1700577
in four databases using specific keywords, which disclosed a 7. Benavides RE, Jana SC, Reneker DH (2012) Nanofibers from
total of seventy-nine relevant articles published in the last scalable gas jet process. ACS Macro Lett 1(8):1032–1036
nineteen years. The number of publications found already 8. Bolbasov EN, Anissimov YG, Pustovoytov AV, Khlusov IA,
denotes the early stage of the technique, which still has much Zaitsev AA, Zaitsev KV, Lapin IN, Tverdokhlebov SI (2014)
Ferroelectric polymer scaffolds based on a copolymer of tetraflu-
to be investigated. Even though other reviews have already oroethylene with vinylidene fluoride: fabrication and properties.
reported the fundamental principles of the technique, none of Mater Sci Eng C Mater Biol Appl 40:32–41
them summarized the central polymeric systems that have 9. Medeiros ES, Glenn GM, Klamczynski AP, Orts WJ, Mattoso
been studied, the adaptation strategies that have been tested, LHC (2009) Solution blow spinning: a new method to produce
micro- and nanofibers from polymer solutions. J Appl Polym Sci
and the application fields to which research has been pointing 113(4):2322–2330
out. This paper will help polymeric researchers who use SBS 10. Li J, Song G, Yu J, Wang Y, Zhu J, Hu Z (2017) Preparation of
to have an understanding of the current scenario and being solution blown Polyamic acid Nanofibers and their Imidization
able to explore new combinations of polymer-solvent systems into polyimide Nanofiber Mats. Nanomaterials (Basel) 7(11):395
11. Bonan RF, Bonan PRF, Batista AUD, Perez DEC, Castellano
not accessible to other spinning techniques. New fibrous ma- LRC, Oliveira JE, Medeiros ES (2017) Poly(lactic acid)/poly(vi-
terials may conveniently be produced and scalable from the nyl pyrrolidone) membranes produced by solution blow spinning:
knowledge compiled in this paper, given the potential of the structure, thermal, spectroscopic, and microbial barrier properties.
SBS. J Appl Polym Sci 134(19):44802
12. Bolbasov EN, Stankevich KS, Sudarev EA, Bouznik VM,
Kudryavtseva VL, Antonova LV, Matveeva VG, Anissimov
Acknowledgments The authors acknowledge financial support from the
YG, Tverdokhlebov SI (2016) The investigation of the production
Brazilian Agency Coordenação de Aperfeiçoamento de Pessoal de Nível
method influence on the structure and properties of the ferroelec-
Superior (CAPES) through the scholarships to Silvana Pereira Rempel
tric nonwoven materials based on vinylidene fluoride – tetraflu-
and Lucas Dall Agnol, and a post-doctoral fellowship to Fernanda Dias.
oroethylene copolymer. Mater Chem Phys 182:338–346
13. da Silva Parize DD, de Oliveira JE, Foschini MM, Marconcini JM,
Author’s contributions S.P.R. and O.B. had the idea to organize this Mattoso LHC (2016) Poly(lactic acid) fibers obtained by solution
review to support S.P.R.’s master’s dissertation. F.T.G.D. and L.D. de- blow spinning: effect of a greener solvent on the fiber diameter. J
signed the databases search for articles and built Table 1. S.P.R. was Appl Polym Sci 133(18):43379
responsible for obtaining the copyrights of the Figs. L.D. was responsible 14. RMDC F, Menezes RR, Oliveira JE, de Medeiros ES (2015)
for formatting the text and references. F.T.G.D. and O.B. made a critical Production of submicrometric fibers of mullite by solution blow
correction of the document. All authors read and approved the final spinning (SBS). Mater Lett 149:47–49
manuscript. 15. Souza MA, Oliveira JE, Medeiros ES, Glenn GM, Mattoso LH
(2015) Controlled release of linalool using Nanofibrous mem-
Compliance with ethical standards branes of poly(lactic acid) obtained by electrospinning and solu-
tion blow spinning: a comparative study. J Nanosci Nanotechnol
Conflict of interest The authors declare that they have no conflict of 15(8):5628–5636
interest regarding the publication of this article. 16. da Silva Parize DD, Foschini MM, de Oliveira JE, Klamczynski
AP, Glenn GM, Marconcini JM, Mattoso LHC (2016) Solution
J Polym Res (2020) 27:205 Page 21 of 23 205

blow spinning: parameters optimization and effects on the proper- nanocrystals from Eucalyptus Kraft pulp. Carbohydr Polym 174:
ties of nanofibers from poly(lactic acid)/dimethyl carbonate solu- 923–932
tions. J Mater Sci 51(9):4627–4638 34. Abdal-hay A, Sheikh FA, Lim JK (2013) Air jet spinning of hy-
17. Abdal-Hay A, Oh YS, Yousef A, Pant HR, Vanegas P, Lim JK droxyapatite/poly(lactic acid) hybrid nanocomposite membrane
(2014) In vitro deposition of Ca-P nanoparticles on air jet spinning mats for bone tissue engineering. Colloids Surf B Biointerfaces
nylon 6 Nanofibers scaffold for bone tissue engineering. Appl Surf 102:635–643
Sci 307:69–76 35. Rajgarhia S, Jana SC (2017) Influence of secondary stretching on
18. Abdal-Hay A, Hamdy AS, Khalil KA, Lim JH (2015) A novel diameter and morphology of bicomponent polymer nanofibers
simple one-step air jet spinning approach for deposition of poly(- produced by gas jet fiber process. Polymer 123:219–231
vinyl acetate)/hydroxyapatite composite nanofibers on Ti im- 36. Abdal-hay A, Makhlouf AS, Khalil KA (2015) Novel, facile,
plants. Mater Sci Eng C Mater Biol Appl 49:681–690 single-step technique of polymer/TiO(2) Nanofiber composites
19. Oliveira JE, Moraes EA, Costa RGF, Afonso AS, Mattoso LHC, membrane for Photodegradation of methylene blue. ACS Appl
Orts WJ, Medeiros ES (2011) Nano and submicrometric fibers of Mater Interfaces 7(24):13329–13341
poly(D,L-lactide) obtained by solution blow spinning: Process 37. Zhang X, Lv J, Yin X, Li Z, Lin Q, Zhu L (2018) Nanofibrous
and solution variables. J Appl Polym Sci 122(5):3396–3405 polystyrene membranes prepared through solution blow spinning
20. Shang JH, Benavides RE, Jana SC (2014) Effects of polymer with an airbrush and the facile application in oil recovery. Appl
viscosity and Nanofillers on morphology of Nanofibers obtained Phys A Mater Sci Process 124(5):362
by a gas jet method. Int Polym Process 29(1):103–111 38. Hofmann E, Kruger K, Haynl C, Scheibel T, Trebbin M, Forster S
21. Wojasiński M, Pilarek M, Ciach T (2014) Comparative studies of (2018) Microfluidic nozzle device for ultrafine fiber solution blow
electrospinning and solution blow spinning processes for the pro- spinning with precise diameter control. Lab Chip 18(15):2225–
duction of Nanofibrous poly(L-lactic acid) materials for biomedi- 2234
cal engineering. Pol J Chem Technol 16(2):43–50 39. Abdal-hay A, Memic A, Hussein KH, Oh YS, Fouad M, Al-Jassir
22. Magaz A, Roberts AD, Faraji S, Nascimento TRL, Medeiros ES, FF, Woo H-M, Morsi Y, Mo X, Ivanovski S (2017) Rapid fabri-
Zhang W, Greenhalgh RD, Mautner A, Li X, Blaker JJ (2018) cation of highly porous and biocompatible composite textile tubu-
Porous, aligned, and biomimetic fibers of regenerated silk fibroin lar scaffold for vascular tissue engineering. Eur Polym J 96:27–43
produced by solution blow spinning. Biomacromolecules 19(12): 40. Francois S, Sarra-Bournet C, Jaffre A, Chakfe N, Durand B,
4542–4553 Laroche G (2010) Characterization of an air-spun poly(L-lactic
23. Behrens AM, Casey BJ, Sikorski MJ, Wu KL, Tutak W, Sandler acid) nanofiber mesh. J Biomed Mater Res B Appl Biomater
AD, Kofinas P (2014) In situ deposition of PLGA Nanofibers via 93(2):531–543
solution blow spinning. ACS Macro Lett 3(3):249–254 41. Hoffman K, Skrtic D, Sun J, Tutak W (2015) Airbrushed com-
24. Srinivasan S, Chhatre SS, Mabry JM, Cohen RE, McKinley GH posite polymer Zr-ACP nanofiber scaffolds with improved cell
(2011) Solution spraying of poly(methyl methacrylate) blends to penetration for bone tissue regeneration. Tissue Eng Part C
fabricate microtextured, superoleophobic surfaces. Polymer Methods 21(3):284–291
52(14):3209–3218 42. Abdal-Hay A, Abdelrazek Khalil K, Al-Jassir FF, Gamal-Eldeen
25. Tutak W, Sarkar S, Lin-Gibson S, Farooque TM, Jyotsnendu G, AM (2017) Biocompatibility properties of polyamide 6/PCL
Wang D, Kohn J, Bolikal D, Simon Jr CG (2013) The support of blends composite textile scaffold using EA.hy926 human endo-
bone marrow stromal cell differentiation by airbrushed nanofiber thelial cells. Biomed Mater 12(3):035002
scaffolds. Biomaterials 34(10):2389–2398 43. Polat Y, Pampal ES, Stojanovska E, Simsek R, Hassanin A, Kilic
26. Cena CR, Silva MJ, Malmonge LF, Malmonge JA (2018) A, Demir A, Yilmaz S (2016) Solution blowing of thermoplastic
Poly(vinyl pyrrolidone) sub-microfibers produced by solution polyurethane nanofibers: a facile method to produce flexible po-
blow spinning. J Polym Res 25(11):238 rous materials. J Appl Polym Sci 133(9):43025
27. Martinez-Sanz M, Bilbao-Sainz C, Du WX, Chiou BS, Williams 44. Costa RGF, Brichi GS, Ribeiro C, Mattoso LHC (2016)
TG, Wood DF, Imam SH, Orts WJ, Lopez-Rubio A, Lagaron JM Nanocomposite fibers of poly(lactic acid)/titanium dioxide pre-
(2015) Antimicrobial poly(lactic acid)-based Nanofibres devel- pared by solution blow spinning. Polym Bull 73(11):2973–2985
oped by solution blow spinning. J Nanosci Nanotechnol 15(1): 45. Lou H, Han W, Wang X (2014) Numerical study on the solution
616–627 blowing annular jet and its correlation with Fiber morphology. Ind
28. Oliveira JE, Moraes EA, Marconcini JM, LHC M, Glenn GM, Eng Chem Res 53(7):2830–2838
Medeiros ES (2013) Properties of poly(lactic acid) and poly(eth- 46. Lou H, Li W, Li C, Wang X (2013) Systematic investigation on
ylene oxide) solvent polymer mixtures and nanofibers made by parameters of solution blown micro/nanofibers using response
solution blow spinning. J Appl Polym Sci 129(6):3672–3681 surface methodology based on box-Behnken design. J Appl
29. Bedeloğlu AC, Bhullar SK, Borazan I, Cin ZI, Demir A (2017) Polym Sci 130(2):1383–1391
Manufacturing and morphology of poly(−caprolactone) based 47. Sinha-Ray S, Sinha-Ray S, Yarin AL, Pourdeyhimi B (2015)
microfibre webs for biomedical applications through airbrush Theoretical and experimental investigation of physical mecha-
technique. Indian J Fibre Text Res 42(1):38–42 nisms responsible for polymer nanofiber formation in solution
30. Deneff JI, Walton KS (2019) Production of metal-organic frame- blowing. Polymer 56:452–463
work-bearing polystyrene fibers by solution blow spinning. Chem 48. Stojanovska E, Canbay E, Pampal ES, Calisir MD, Agma O, Polat
Eng Sci 203:220–227 Y, Simsek R, Gundogdu NAS, Akgul Y, Kilic A (2016) A review
31. Abdal-Hay A, Barakat NM, Lim JK (2012) Novel technique for on non-electro nanofibre spinning techniques. RSC Adv 6(87):
polymeric Nanofibers preparation: air jet spinning. Sci Adv Mater 83783–83801
4(12):1268–1275 49. Daristotle JL, Behrens AM, Sandler AD, Kofinas P (2016) A
32. Tutak W, Gelven G, Markle C, Palmer X-L (2015) Rapid polymer review of the fundamental principles and applications of solution
fiber airbrushing: impact of a device design on the fiber fabrication blow spinning. ACS Appl Mater Interfaces 8(51):34951–34963
and matrix quality. J Appl Polym Sci 132(47):42813 50. Teno J, González-Gaitano G, González-Benito J (2017) Poly (eth-
33. DDDS P, Oliveira JE, Williams T, Wood D, Avena-Bustillos RJ, ylene-co-vinyl acetate) films prepared by solution blow spinning:
Klamczynski AP, Glenn GM, Marconcini JM, LHC M (2017) surface characterization and its relation with E. coli adhesion.
Solution blow spun nanocomposites of poly(lactic acid)/cellulose Polym Test 60:140–148
205 Page 22 of 23 J Polym Res (2020) 27:205

51. Rempel SP, Engler LG, Soares MRF, Catafesta J, Moura S, fibrous membranes prepared by solution blow spinning. J
Bianchi O (2019) Nano/microfibers of EVA copolymer obtained Nanosci Nanotechnol 12(3):2733–2741
by solution blow spinning: processing, solution properties, and 68. Oliveira JE, Medeiros ES, Cardozo L, Voll F, Madureira EH,
pheromone release application. J Appl Polym Sci 136(24):47647 Mattoso LH, Assis OB (2013) Development of poly(lactic acid)
52. González Benito FJ, Teno Díaz J, Torres DD, M. (2017) Solution nanostructured membranes for the controlled delivery of proges-
blow spinning and obtaining submicrometric fibers of different terone to livestock animals. Mater Sci Eng C Mater Biol Appl
polymers. Int J Nanoparticles Nanotech 3(1):007 33(2):844–849
53. Khattab TA, Rehan M, Aly SA, Hamouda T, Haggag KM, 69. Oliveira J, Brichi GS, Marconcini JM, Mattoso LHC, Glenn GM,
Klapötke TM (2017) Fabrication of PAN-TCF-hydrazone nano- Medeiros ES (2014) Effect of solvent on the physical and mor-
fibers by solution blowing spinning technique: naked-eye colori- phological properties of poly(lactic acid) Nanofibers obtained by
metric sensor. J Environ Chem Eng 5(3):2515–2523 solution blow spinning. J Eng Fiber Fabr 9(4):117–125
54. Ren J, Huang X, Wang N, Lu K, Zhang X, Li W, Liu D (2016) 70. Sabbatier G, Abadie P, Dieval F, Durand B, Laroche G (2014)
Preparation of polyaniline-coated polyacrylonitrile fiber mats and Evaluation of an air spinning process to produce tailored biosyn-
their application to Cr(VI) removal. Synth Met 222:255–266 thetic nanofibre scaffolds. Mater Sci Eng C Mater Biol Appl 35:
55. Zhuang X, Jia K, Cheng B, Guan K, Kang W, Ren Y (2013) 347–353
Preparation of Polyacrylonitrile Nanofibers by solution blowing 71. Granados-Hernandez MV, Serrano-Bello J, Montesinos JJ,
process. J Eng Fiber Fabr. https://doi.org/10.1177/ Alvarez-Gayosso C, Medina-Velazquez LA, Alvarez-Fregoso O,
155892501300800111 Alvarez-Perez MA (2018) In vitro and in vivo biological charac-
56. Shi L, Zhuang X, Tao X, Cheng B, Kang W (2013) Solution terization of poly(lactic acid) fiber scaffolds synthesized by air jet
blowing nylon 6 nanofiber mats for air filtration. Fibers Polym spinning. J Biomed Mater Res B Appl Biomater 106(6):2435–
14(9):1485–1490 2446
57. Oliveira JE, Mattoso LHC, Orts WJ, Medeiros ES (2013) 72. Suarez-Franco JL, Vazquez-Vazquez FC, Pozos-Guillen A,
Structural and morphological characterization of micro and Montesinos JJ, Alvarez-Fregoso O, Alvarez-Perez MA (2018)
Nanofibers produced by electrospinning and solution blow spin- Influence of diameter of fiber membrane scaffolds on the biocom-
ning: a comparative study. Adv Mater Sc Eng 2013:409572 patibility of hPDL mesenchymal stromal cells. Dent Mater J
58. Lv J, Yin X, Li R, Chen J, Lin Q, Zhu L (2019) Superhydrophobic 37(3):465–473
PCL/PS composite nanofibrous membranes prepared through so- 73. Cerna Nahuis LE, Alvim Valente C, de Freitas OD, de Souza
lution blow spinning with an airbrush for oil adsorption. Polym Basso NR, Antonio Malmonge J (2019) Preparation and charac-
Eng Sci 59(S1):E171–E181 terization of polymeric microfibers of PLGA and PLGA/PPy
59. Chen C, Townsend AD, Sell SA, Martin RS (2017) Microchip- composite fabricated by solution blow spinning. Macromol
based 3D-cell culture using polymer Nanofibers generated by so- Symp 383(1):1800030
lution blow spinning. Anal Methods 9(22):3274–3283 74. Miranda KWE, Mattoso LHC, Bresolin JD, Hubinger SZ,
60. Simbara MMO, Santos Jr AR, Andrade AJP, Malmonge SM Medeiros ES, de Oliveira JE (2019) Polystyrene bioactive nano-
(2019) Comparative study of aligned and nonaligned fibers using orange oil as an ecofriendly solvent. J Appl Polym Sci
poly(epsilon-caprolactone) fibrous scaffolds prepared by solution 136(15):47337
blow spinning. J Biomed Mater Res B Appl Biomater 107(5): 75. Teno J, González-Gaitano G, González-Benito J (2017)
1462–1470 Nanofibrous polysulfone/TiO2 nanocomposites: surface proper-
61. Hell AF, Simbara MMO, Rodrigues P, Kakazu DA, Malmonge ties and their relation with E. coliadhesion. J Polym Sci B Polym
SM (2018) Production of fibrous polymer scaffolds for tissue en- Phys 55(21):1575–1584
gineering using an automated solution blow spinning system. Res 76. Guan KT, Zhuang XP, Yan GL, Cheng BW (2011) Fabrication
Biomed Eng 34(3):273–278 and properties of polyurethane Nanofibers nonwoven by solution
62. Behrens AM, Kim J, Hotaling N, Seppala JE, Kofinas P, Tutak W blowing. Adv Mater Res 332-334:1339–1342
(2016) Rapid fabrication of poly(DL-lactide) nanofiber scaffolds 77. Dias YJ, Gimenes TC, Torres SAPV, Malmonge JA, Gualdi AJ,
with tunable degradation for tissue engineering applications by de Paula FR (2017) PVDF/Ni fibers synthesis by solution blow
air-brushing. Biomed Mater 11(3):035001 spinning technique. J Mater Sci Mater Eletron 29(1):514–518
63. Medeiros ELG, Braz AL, Porto IJ, Menner A, Bismarck A, 78. Dias GC, Cellet TSP, Santos MC, Sanches AO, Malmonge LF
Boccaccini AR, Lepry WC, Nazhat SN, Medeiros ES, Blaker JJ (2019) PVDF nanofibers obtained by solution blow spinning with
(2016) Porous bioactive Nanofibers via cryogenic solution blow use of a commercial airbrush. J Polym Res 26(4):87
spinning and their formation into 3D macroporous scaffolds. ACS 79. Zhuang X, Shi L, Jia K, Cheng B, Kang W (2013) Solution blown
Biomater Sci Eng 2(9):1442–1449 nanofibrous membrane for microfiltration. J Memb Sci 429:66–70
64. Tomecka E, Wojasinski M, Jastrzebska E, Chudy M, Ciach T, 80. González-Benito J, Teno J, González-Gaitano G, Xu S, Chiang
Brzozka Z (2017) Poly(l-lactic acid) and polyurethane nanofibers MY (2017) PVDF/TiO2 nanocomposites prepared by solution
fabricated by solution blow spinning as potential substrates for blow spinning: surface properties and their relation with S.
cardiac cell culture. Mater Sci Eng C Mater Biol Appl 75:305–316 Mutans adhesion. Polym Test 58:21–30
65. Liang F, Fang F, Zeng J, Wang Z, Ou W, Chen X, Wu P, Wang H, 81. Vural M, Behrens AM, Ayyub OB, Ayoub JJ, Kofinas P (2015)
Zhang L (2017) Fabrication of three-dimensional micro-nanofiber Sprayable elastic conductors based on block copolymer silver
structures by a novel solution blow spinning device. AIP Adv nanoparticle composites. ACS Nano 9(1):336–344
7(2):025002 82. Sow PK, Ishita SR (2018) Sustainable approach to recycle waste
66. Bilbao-Sainz C, Chiou B-S, Valenzuela-Medina D, Du W-X, polystyrene to high-value submicron fibers using solution blow
Gregorski KS, Williams TG, Wood DF, Glenn GM, Orts WJ spinning and application towards oil-water separation. J Environ
(2014) Solution blow spun poly(lactic acid)/hydroxypropyl meth- Chem Eng. https://doi.org/10.1016/j.jece.2018.11.031
ylcellulose nanofibers with antimicrobial properties. Eur Polym J 83. Liu F, Avena-Bustillos RJ, Woods R, Chiou BS, Williams TG,
54:1–10 Wood DF, Bilbao-Sainz C, Yokoyama W, Glenn GM, McHugh
67. Oliveira JE, Zucolotto V, Mattoso LH, Medeiros ES (2012) Multi- TH, Zhong F (2016) Preparation of Zein fibers using solution
walled carbon nanotubes and poly(lactic acid) nanocomposite blow spinning method. J Food Sci 81(12):N3015–N3025
J Polym Res (2020) 27:205 Page 23 of 23 205

84. Liu F, Avena-Bustillos RJ, Bilbao-Sainz C, Woods R, Chiou BS, 102. Graessley W (1980) Polymer chain dimensions and the depen-
Wood D, Williams T, Yokoyama W, Glenn GM, McHugh TH, dence of viscoelastic properties on concentration, molecular
Zhong F (2017) Solution blow spinning of food-grade gelatin weight and solvent power. Polymer 21(3):258–262
Nanofibers. J Food Sci 82(6):1402–1411 103. Cheng B, Tao X, Shi L, Yan G, Zhuang X (2014) Fabrication of
85. Paschoalin RT, Traldi B, Aydin G, Oliveira JE, Rutten S, Mattoso ZrO2 ceramic fiber mats by solution blowing process. Ceram Int
LHC, Zenke M, Sechi A (2017) Solution blow spinning fibres: 40(9):15013–15018
new immunologically inert substrates for the analysis of cell ad- 104. Zhuang X, Yang X, Shi L, Cheng B, Guan K, Kang W (2012)
hesion and motility. Acta Biomater 51:161–174 Solution blowing of submicron-scale cellulose fibers. Carbohydr
86. Nepomuceno NC, Barbosa MA, Bonan RF, Oliveira JE, Sampaio Polym 90(2):982–987
FC, Medeiros ES (2018) Antimicrobial activity of PLA/PEG 105. Khayet M, García-Payo MC, Qusay FA, Khulbe KC, Feng CY,
nanofibers containing terpinen-4-ol against Aggregatibacter Matsuura T (2008) Effects of gas gap type on structural morphol-
actinomycetemcomitans. J Appl Polym Sci 135(6):45782 ogy and performance of hollow fibers. J Memb Sci J 311(1–2):
87. Singh R, Ahmed F, Polley P, Giri J (2018) Fabrication and char- 259–269
acterization of Core-Shell Nanofibers using a next-generation air- 106. Vasireddi R, Kruse J, Vakili M, Kulkarni S, Keller TF, Monteiro
brush for biomedical applications. ACS Appl Mater Interfaces DC, Trebbin M (2019) Solution blow spinning of polymer/
10(49):41924–41934 nanocomposite micro−/nanofibers with tunable diameters and
88. Santos AMC, Medeiros ELG, Blaker JJ, Medeiros ES (2016) morphologies using a gas dynamic virtual nozzle. Sci Rep 9:
Aqueous solution blow spinning of poly(vinyl alcohol) micro- 14297
and nanofibers. Mater Lett 176:122–126
107. Zhang L, Kopperstad P, West M, Hedin N, Fong H (2009)
89. Kolbasov A, Sinha-Ray S, Joijode A, Hassan MA, Brown D,
Generation of polymer ultrafine fibers through solution (air-)
Maze B, Pourdeyhimi B, Yarin AL (2015) Industrial-scale solu-
blowing. J Appl Polym Sci 114(6):3479–3486
tion blowing of soy protein Nanofibers. Ind Eng Chem Res 55(1):
323–333 108. Zhang Y, Ouyang H, Lim CT, Ramakrishna S, Huang ZM (2005)
90. Abdal-hay A, Hamdy AS, Lim JH (2014) Facile preparation of Electrospinning of gelatin fibers and gelatin/PCL composite fi-
titanium dioxide micro/nanofibers and tubular structures by air jet brous scaffolds. J Biomed Mater Res B Appl Biomater 72(1):
spinning. Ceram Int 40(10):15403–15409 156–165
91. Yu JH, Fridrikh SV, Rutledge GC (2006) The role of elasticity in 109. Rotta M, Zadorosny L, Carvalho CL, Malmonge JA, Malmonge
the formation of electrospun fibers. Polymer 47(13):4789–4797 LF, Zadorosny R (2016) YBCO ceramic nanofibers obtained by
92. Boger DV (1977) A highly elastic constant-viscosity fluid. J Non- the new technique of solution blow spinning. Ceram Int 42(14):
newton Fluid Mech 3:87–91 16230–16234
93. Fang Y, Dulaney AD, Gadley J, Maia JM, Ellison CJ (2015) 110. Costa DL, Leite RS, Neves GA, LNDL S, Medeiros ES, Menezes
Manipulating characteristic timescales and fiber morphology in RR (2016) Synthesis of TiO2 and ZnO nano and submicrometric
simultaneous centrifugal spinning and photopolymerization. fibers by solution blow spinning. Mater Lett 183:109–113
Polymer 73:42–51 111. Santos AMC, Mota MF, Leite RS, Neves GA, Medeiros ES,
94. Lopes AR (2016) Caracterização de soluções poliméricas para Menezes RR (2018) Solution blow spun titania nanofibers from
aplicação em revestimentos para a conservação de produtos solutions of high inorganic/organic precursor ratio. Ceram Int
alimentares. Master's thesis, Universidade D Coimbra 44(2):1681–1689
95. Regev O, Vandebril S, Zussman E, Clasen C (2010) The role of 112. Barhoum A, Pal K, Rahier H, Uludag H, Kim IS, Bechelany M
interfacial viscoelasticity in the stabilization of an electrospun jet. (2019) Nanofibers as new-generation materials: from spinning and
Polymer 51(12):2611–2620 nano-spinning fabrication techniques to emerging applications.
96. Roland CM, Archer LA, Mott PH, Sanchez-Reyes J (2004) Appl Mater Today 17:1–35
Determining rouse relaxation times from the dynamic modulus 113. Pampal ES, Stojanovska E, Simon B, Kilic A (2015) A review of
of entangled polymers. J Rheol 48(2):395–403 nanofibrous structures in lithium ion batteries. J Power Sources
97. Shenoy SL, Bates WD, Frisch HL, Wnek GE (2005) Role of chain 300:199–215
entanglements on fiber formation during electrospinning of poly- 114. Tutak W, Kaufman G, Gelven G, Markle C, Maczka C (2016)
mer solutions: good solvent, non-specific polymer–polymer inter- Uniform, fast, high concentration delivery of bone marrow stromal
action limit. Polymer 46(10):3372–3384 cells and gingival fibroblasts by gas-brushing. Biomed Phys Eng
98. Rajendran M, Bhattacharya AK (2004) Production of rare-earth Express 2(3):035007
orthoferrite ceramic fibres by aqueous sol-gel blow spinning pro- 115. Molnár K, Mészáros L (2020) Editorial corner – a personal view:
cess. J Eur Ceram Soc 24(1):111–117 the role of electrospun nanofibers in the fight against the COVID-
99. Hildebrand JH, Scott RL (1964) The solubility of 19. Express Polym Lett 14(7):605
nonelectrolytes3d edn. Dover Publications, New York 116. Pehlivaner Kara MO, Ekenseair AK (2016) In situ spray deposi-
100. Cena CR, Torsoni GB, Zadorosny L, Malmonge LF, Carvalho tion of cell-loaded, thermally and chemically gelling hydrogel
CL, Malmonge JA (2017) BSCCO superconductor micro/ coatings for tissue regeneration. J Biomed Mater Res A 104(10):
nanofibers produced by solution blow-spinning technique. 2383–2393
Ceram Int 43(10):7663–7667
101. Cena CR, Behera AK, Behera B (2016) Structural, dielectric, and
electrical properties of lithium niobate microfibers. J Adv Ceram Publisher’s note Springer Nature remains neutral with regard to jurisdic-
5(1):84–92 tional claims in published maps and institutional affiliations.

You might also like