Fabrication of ultrafine fibrous polytetrafluoroethylene porous
membranes by electrospinning
Jie Xionga)
Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education,
Zhejiang Sci-Tech University, Hangzhou 310018, China
Pengfei Huo
Department of Materials Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
Frank K. Ko
Advanced Fibrous Materials, University of British Columbia, Vancouver, BC, V6T 1Z4, Canada
(Received 19 February 2009; accepted 17 June 2009)
Poly(vinyl alcohol) (PVA) and poly(tetrafluoroethylene) (PTFE) emulsion were blended
with different mass concentrations and the blended spinning solutions were electrospun
into composite nanofibers. The influence of the blend ratio of PVA to PTFE and
electrospinning technical parameters on the morphology and diameter of the composite
nanofibers were investigated. According to the result of thermogravimetric analyzer
analysis, the composite membrane was sintered at 390 C. The membranes were then
characterized by differential scanning calorimetry, attenuated total reflection-Fourier
transform infrared (ATR-FTIR), and scanning electron microscopy, respectively. The
mechanical properties of the membranes before and after sintering were analyzed through
tensile testing. The results show that the PTFE porous membranes could be electrospun
effectively, thus demonstrating their potential application as filter media.
I. INTRODUCTION Poly(tetrafluoroethylene) (PTFE) is a fluorocarbon
Electrospinning differs from conventional fiber spinning polymer produced by tetrafluoroethylene polymeriza-
in that it makes use of the action of a high-voltage electrical tion. The strong bonds exist between fluorine and carbon
field on polymer solution with an objective to form nano/ atoms and the specific molecular structure give PTFE a
submicrofibers. In the past decade, electrospinning has good combination of chemical, physical, electric, anti-
gained increasing interest in the field of nanotechnology. friction, and other properties that are hard to find in any
Many polymers have been electrospun into nano/sub- other material. PTFE can be used in a wide temperature
microfibers successfully. Electrospun nano/submicrofiber range with excellent thermal and chemical resistance as
assemblies with porous structure can be applied to many well as good antifriction, electrical insulation, and me-
applications, such as tissue engineering scaffolds,1–3 drug chanical properties.20,21 Therefore, PTFE is widely used
delivery,4 enzyme immobilization,5 battery membrane,6 as high-temperature filter material. However, PTFE has
and filtration membrane.7 an unusually high melt viscosity, which makes it difficult
For example, the use of nanofibrous porous membrane to process using traditional processing technologies.22–25
in filtration has many advantages. These nanofibrous For this reason, the processing of PTFE, which is similar
filters are characterized by a high surface-area-to-vol- to powder metallurgy, has a complex manufacturing proc-
ume ratio, high porosity, pore sizes ranging from tens of ess and excessive influence factors. Nowadays, the fabri-
nanometer to several micrometers characterized by cation of PTFE porous membranes is usually by uniaxial
interconnected open pore structure, light weight, and and biaxial stretching.26–29 Many lubricating additives
ease of functionalization. Nanofibrous porous membrane would have to be used in the production process, causing
has been applied successfully in high-efficiency air fil- considerable environmental pollution.
ters,8–10 and they are being produced commercially.11 In this study, we demonstrate an alternate processing
Preliminary research on coalescent filter12–16 and high- route to fabricate PTFE porous membrane. We specifically
flux ultrafiltration membrane17–19 have also been suc- use poly(vinyal alcohol) (PVA) and PTFE emulsion to pro-
cessfully demonstrated in recent years. duce nano/submicrofibrous PTFE porous membranes that
have high-temperature resistance and corrosion resistance
a)
Address all correspondence to this author.
characteristics through electrospinning and sintering. This
e-mail:
[email protected] porous membrane has the potential to be used widely as
DOI: 10.1557/JMR.2009.0347 a candidate material for high-temperature filters.
J. Mater. Res., Vol. 24, No. 9, Sep 2009 © 2009 Materials Research Society 2755
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
II. EXPERIMENTAL on the result of thermogravimetric analyzer (TGA; PYRIS
A. Materials 1, Perkin Elmer, Fremont, CA), the sintering temperature
was defined. Then, a differential scanning calorimeter
PTFE emulsion (SFN-1) was purchased from Chen- (DSC; Pyris Diamond, Perkin Elmer), attenuated total
guang Research Institute of Chemical Industry (Zigong, reflection-Fourier transform infrared spectroscopy (ATR-
Sichuan). PVA powder (2488) was purchased from FTIR; Nicolet5700, USA), and SEM were used to analyze
Shanghai Goldentree Resin Powder Co., Ltd. (Jinshan, the composition and structure of the membrane.
Shanghai). These materials were used as-received with- The mechanical properties of membrane before and
out further purification. after sintering were determined using an Instron (5543)
tensile tester (Norwood, MA) at ambient temperature.
B. Preparation The specimens were cut into 25 mm (length) 5 mm
The PVA solution was prepared by dissolving PVA (width) test strips.
powder in deionized water at 90 C under constant stir-
ring for at least 6 h. When the solution was cooled down III. RESULTS AND DISCUSSION
to room temperature, the PTFE emulsion was added to A. Effects of different PVA/PTFE ratios on
PVA solution with constant stirring for 3 h to form hybrid(composite) fiber morphology
spinning solutions of different proportions and different
concentrations. The PVA/PTFE solution, with the mass ratios of
Figure 1 shows a schematic diagram of the electrospin- 10:90, 20:80, 30:70, 40:60, and 50:50, was electrospun
ning process. It consists of a syringe feeder system, a metal- at a concentration of 26 wt% using a constant spinning
lic ground fiber collector, and a high-voltage power supply. distance of 15 cm, at a voltage of 11 kV and a flow rate
A high electric field is generated between the polymer fluid of 0.01 mL/min. Morphological change of the electro-
contained in a glass syringe and the fiber collector. At a spun nanofibers are shown in Fig. 2.
sufficiently high level of electric field the polymer solution Because of its insolubility in common solvents, pure
jet travels through the air. As the solvent evaporates, the PTFE could not be readily electrospun into nanofibers.
solid polymer fibers are collected on the electrically To obtain pure PTFE porous membranes, a sacrificial
grounded target. In this study, spinning experiments were matrix polymer and post-treatment were introduced into
carried out with applied voltage of 7–15 kV, at a spinning the processing of PTFE nanofibers electrospinning.
distance of 15 cm and fluid flow rate of 0.01 mL/min. PVA, a water-soluble polymer, has good fiberizability
The electrospun nanofibrous porous membrane was and it can be electrospun into nanofibers easily. It was
then sintered in a muffle furnace less than 390 C for demonstrated that the spinnability of the chitosan, hy-
3 min to obtain the PTFE porous membrane. droxyapatite, and zinc oxide, which cannot be electro-
spun readily by themselves, could be achieved by
C. Characterization blending with PVA.30–32 In this experiment, we demon-
strated that the polymer blends transformed progressive-
The morphology of the gold-sputtered electrospun nano- ly from a beadlike structure to a fibrous structure as the
fibrous porous membrane was examined using scanning content of the PVA in the system increases. As shown in
electron microscopy (SEM; JSM-5610LV, JEOL, Tokyo, Fig. 2, when the mass ratio of the PVA/PTFE was 10:90,
Japan). The SEM images of the membrane were analyzed only beadlike structure could be obtained. As the content
using the Image-Pro Plus image analysis program. Based of the PVA increases, a mixture of fibers and beadlike
structure began to appear. When the PVA/PTFE mass
ratio reaches 30:70, fibers of about 300 nm in diameter
were formed, but the fibers were not uniform exhibiting
large nodules along the fiber. As the PVA/PTFE mass
ratio increases further, the fiber diameters were in-
creased with uniform fiber surface. To obtain porous
membranes with higher PTFE content, the content of
PVA must be kept to a minimum while assuring fiber
formation. In this study, a PVA/PTFE mass ratio of
30:70 was selected for further experiments.
B. Effects of electrospinning parameters on
composite fiber morphology
The electrospinning parameters have a strong influence
FIG. 1. Schematic diagram of the electrospinning apparatus. on fiber morphology. The concentration of the polymer
2756 J. Mater. Res., Vol. 24, No. 9, Sep 2009
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
FIG. 2. SEM images of the composite fibers with different mass ratios of PVA to PTFE: (a) 10:90, (b) 20:80, (c) 30:70, (d) 40:60, and (e) 50:50.
solution and the spinning voltage were found to be espe- beadlike structures. Further increase in the concentration
cially significant. In this study, the effects of concentra- of solution resulted in the formation of continuous
tion and spinning voltage on fiber morphology for PVA/ uniform nanofibers with large diameter. The changes of
PTFE with a blend ratio of 30:70 were observed. diameter with polymer concentration are shown in
Fig. 4. It is of interest to note that there is no obvious
change of diameter of fibers for those obtained from a
1. Effect of polymer concentration
solution with concentrations of 22 to 26 wt%. This can
The PVA/PTFE solution, with the mass ratio of 30:70, be attributed to the presence of surfactant in the PTFE
was electrospun at a concentration of 18, 20, 22, 24, 26, emulsion. The existence of surfactant in the solution
and 28 wt%, at a constant spinning distance of 15 cm, a tends to increase the solution conductivity and decrease
voltage of 11 kV, and a flow rate of 0.01 mL/min. The the surface tension, thus facilitating the formation of
morphological changes of the electrospun fibers are finer fibers.37 Since surfactant is a part of the PTFE
shown in Fig. 3. emulsion, the surfactant content changes with solution
It can be seen that the viscosity of the solution and the concentration. At lower concentration, there was little
spinnability increased with the increase of concentration surfactant presence thus polymer solution is the main
of the solution, which is consistent with other published influencing factor on fiber diameter. When the polymer
results.33–36 When the concentration of the polymer concentration is between 22 and 26 wt%, the influence of
solution is lower than 22 wt%, the fibers tend to form surfactant begins to become effective, and thus reducing
J. Mater. Res., Vol. 24, No. 9, Sep 2009 2757
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
FIG. 3. SEM images of the composite fibers with different concentrations: (a) 18 wt%, (b) 20 wt%, (c) 22 wt%, (d) 24 wt%, (e) 26 wt%, and (f) 28 wt%.
the concentration of spinning solution is kept constant,
we concentrated our observation on the effect of voltage
on fiber diameter.
For our experiment a PVA/PTFE solution, with mass
ratio of 30:70, was prepared for electrospinning at a
concentration of 26 wt%, at voltage levels of 7, 9, 11,
13, and 15 kV. The spinning distance was 15 cm with a
constant flow rate of 0.01 mL/min.
Figure 5 shows the relationship between mean fiber
diameters and spinning voltages. When the spinning
voltages are within the range of 711 kV, the diameter
decreased from 550 to 420 nm. This phenomenon relates
to the fact that increasing the voltage tends to increase
the electrostatic stress and thus a higher degree of draw-
ing on the polymer jet during spinning. At higher
FIG. 4. Changes in electrospun composite fibers diameters with solu-
spinning voltages from 11 to 15 kV, fewer changes in
tion concentrations. fiber diameter were found.
the influence of polymer concentration. As a result, the C. Determination of sinter temperature
diameter of fiber only increases slightly in this concen-
tration range. At higher concentration, the effect of sur- To obtain pure PTFE porous membrane, proper heat
factant tends to be stable, whereas polymer concentration treatment should be applied. The TGA curve obtained by
remains as the main influencing factor on fiber diameter, thermogravimetric analyzer for the heat-treatment proc-
with fiber diameter increasing rapidly as polymer con- ess is shown in Fig. 6.
centration increases. It can be seen that there are two weight-loss steps in
the TGA curve. The first weight loss of about 30 wt%, is
located at 300–400 C, which corresponds to traces of
2. Effect of voltage PVA in the composite membrane.38 The second weight
Considering the fact that voltage is the most influen- loss begins at 600 C. This can be attributed to decom-
tial parameter in the electrospinning of PVA/PTFE once position of PTFE. In the range of 400–600 C, there is
2758 J. Mater. Res., Vol. 24, No. 9, Sep 2009
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
FIG. 5. Changes in electrospun composite fiber diameters with voltages.
FIG. 7. DSC curves of porous membrane (a) before and (b) after sintering.
FIG. 6. TGA curve of composite fibrous porous membrane.
no weight change. This means that PTFE is preserved FIG. 8. ATR-FTIR spectra of porous membrane (a) before and
well and PVA decomposed completely. From the analy- (b) after sintering.
sis of the TGA curve, we concluded that 300–400 C is a
proper sintering temperature range. In this study, a sin- stretching of O–H bonds, whereas the absorption at 2911
tering temperature of 390 C was chosen. cm 1 is due to C–H stretching. The absorption corre-
sponding to the CH2 appears at about 1442 cm 1, and
D. Structural analysis of porous membrane the absorption at 1098 cm 1 attributes to the C–O
stretching. These are characteristic infrared absorption
To further confirm the chemical composition of the peaks of PVA in the composite nanofibrous porous
electrospun fibers, the DSC curves of porous membrane membrane.39 It is evident that all the absorption peaks
before and after sintering were examined, as shown in associated with PVA bonds disappear after sintering, and
Fig. 7. There is an endothermic peak that begins at only the strong absorption of the C–F bond at 1203 and
180 C at the DSC curve before sintering. After the 1147 cm 1 remain.40
sintering process the peak almost disappeared. The result
confirms that PVA has been decomposed completely;
only the pure PTFE porous membrane is left. E. Morphology of PTFE porous membrane
The ATR-FTIR spectra provide additional confirma- As shown in Fig. 9, the SEM images of porous PTFE
tion of this result. Figure 8 shows the ATR-FTIR spectra membrane reveal many differences between the mem-
of porous membrane before and after sintering. The branes before and after sintering. Before sintering, the
strong absorption at 3334 cm 1 is associated with the membrane is formed by randomly oriented nanofibers
J. Mater. Res., Vol. 24, No. 9, Sep 2009 2759
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
FIG. 10. Stress–strain curves of porous membrane (a) before and
(b) after sintering.
were no fibers sliding during the tensile testing thus
resulting at high strength and Young’s modulus for the
sintered PTFE membranes.
IV. CONCLUSION
A novel method for the production of PTFE porous
FIG. 9. SEM images of porous membrane (a) before and (b) after membrane through PVA-assisted PTFE emulsion elec-
sintering. trospinning was demonstrated. The PVA and PTFE
emulsion were blended in water with different mass ra-
tios to form spinning solutions. As the content of the
with well-defined fiber morphology. After sintering, the PVA increases, the spinnability of solution was found to
PVA fibers were decomposed and the remaining PTFE improve. When the mass ratio of PVA to PTFE reaches a
fibers were fused on the points of fiber crossovers to ratio of 30:70, uniform fibers with low PVA content was
form an interconnected fibrous network. obtained. When other electrospinning parameters are
kept constant, the diameter of fiber was found to in-
F. Mechanical properties of the porous membrane crease with increasing concentration of the spinning so-
lution, whereas the diameter of the fibers tends to
The tensile stress–strain curves of the porous mem- decrease with increasing voltage. After sintering, com-
brane before and after sintering are shown in Fig. 10. It plete decomposition of PVA was confirmed through the
can be seen that the mechanical properties of porous analysis of DSC and ATR-FTIR spectra. On sintering,
membrane improved significantly after sintering. The the PTFE particles were fused to form an interconnected
strength of the sintered fiber network increases from 4 to porous network of fibers in the micro- and nanoscale
10 MPa while the modulus increases from 22 to 260 MPa. with substantial improvement of mechanical properties.
Failure strain increases from 63–69%. This can be ex- This study demonstrates the feasibility of the formation
plained in terms of the structural and compositional of high-temperature PTFE nanofiber-based filter by the
changes due to sintering. Before sintering, the membrane electrospinning process.
was formed by multiple layers of randomly oriented com-
posite nanofibers of PTFE particles in a PVA matrix.
During the tensile testing process, the fibers are free to ACKNOWLEDGMENTS
slide along the direction of applied load, until the break- This work was supported by a Pre-973 Program
age of the fibers. Moreover, the PTFE particles were (2008CB617506), a Program for Changjiang Scholars
separated in the fibers. The PVA between PTFE particles and Innovative Research Team in University (IRT 0654),
became a weak link in the fibers when the fibers were and Open Fund of Key Laboratory of Advanced Textile
pulled. After sintering, the PVA matrix was decomposed Materials and Manufacturing Technology, Ministry of
and the molten PTFE particles were bonded together41 to Education (2006003). We thank Dr. Ni Li for her experi-
form an integrated fibrous network. As a result, there mental assistance with electrospinning.
2760 J. Mater. Res., Vol. 24, No. 9, Sep 2009
J. Xiong et al.: Fabrication of ultrafine fibrous polytetrafluoroethylene porous membranes by electrospinning
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