- Nano Express
- Open Access
Fabrication of Continuous Microfibers Containing Magnetic Nanoparticles by a Facile Magneto-Mechanical Drawing
- Jin-Tao Li†1,
- Xian-Sheng Jia†1,
- Gui-Feng Yu†1,
- Xu Yan1, 2,
- Xiao-Xiao He1,
- Miao Yu1, 3,
- Mao-Gang Gong1,
- Xin Ning2, 4 and
- Yun-Ze Long1, 2Email author
© The Author(s). 2016
- Received: 30 June 2016
- Accepted: 20 September 2016
- Published: 23 September 2016
A facile method termed magneto-mechanical drawing is used to produce polymer composite microfibers. Compared with electrospinning and other fiber spinning methods, magneto-mechanical drawing uses magnetic force generated by a permanent magnet to draw droplets of polymer/magnetic nanoparticle suspensions, leading to fabrication of composite microfibers. In addition, because of the rotating collector, it is easy to control the fiber assembly such as fibrous array in parallel or crossed fibrous structure. The general applicability of this method has also been proved by spinning different polymers and magnetic nanoparticles. The resultant fibers exhibit good superparamagnetic behavior at room temperature and ultrahigh stretchability (~443.8 %). The results indicate that magneto-mechanical drawing is a promising technique to fabricate magnetic and stretchable microfibers and devices.
- Magnetic force
- Mechanical force
- Polymeric composites
Micro-/nanofibers have exhibited a lot of outstanding performance due to a very high specific surface-to-mass ratio and attracted much attention of various applications in the past two decades, such as filtration [1–3], biomedical science [4, 5], high-performance textile [6, 7], and catalysis . By now, different methods have been developed to generate micro-/nanofibers, such as melt-blowing [9, 10], electrospinning [11–13], and jet spinning [14, 15]. Melt-blowing is capable of producing high yield microfibers with an average diameter within several microns. Electrospinning is one of the most versatile and efficient methods and has been explored extensively recently in the laboratory and applied to industry . The electrospinning process can be simply summarized as the high voltage applies to the polymer solution, causing the solution electrification and leading to the fabrication of fibers. The fibers were stretched in the air with the solvent evaporated and finally collected on the collection device in the form of non-woven . Each of these methods has their advantages; however, each of them has some deficiencies. For instance, the distribution of melt-blown fiber diameters is uneven . The electric force generated by high voltage is needed to the formation of Taylor cone in electrospinning. The high voltage ranging from several kilovolts to tens of kilovolts may bring potential danger if improperly operated .
For the aim of increasing production, optimizing spinning process, and getting better micro-/nanofibers, the magnetic field has already been introduced into the spinning. For example, Wu et al. controlled stability of the electrospun fiber by applying a magnetic field in the electrospinning process . Yang et al. also obtained aligned fibrous arrays and multilayer grids by appending the magnetic field generated by two parallel-positioned permanent magnets above the collection device . Similar to Yang et al., Liu et al. introduced two bar magnets to the conventional configuration at the collector region, and electrospinning of aligned straight and wave polymeric nanofibers was achievable . In these approaches, the magnetic field affects the movements of charged jet to get fibers with different arrangements and to control instability in electrospinning. However, the high voltage was still applied while the magnetic field just played an auxiliary role.
In this study, we use a facile method termed magneto-mechanical drawing to prepare microfibers. In this method, we regard the magnetic field as the main part of the spinning. Spinning solution droplet doped with magnetic nanoparticles was stretched under the magnetic force generated by a revolving permanent magnet to form a bridge and finally translated into continuous fibers. Magneto-mechanical drawing possesses lots of advantages compared with other common spinning methods. The equipment of magneto-mechanical drawing is low cost, safe, simple, and convenient without high voltage or high temperature. The resultant continuous fibers are aligned in regular order and can be easily transferred onto other substrates, like glass, silicon wafer, and plastic sheet. The resultant fibers that contain magnetic nanoparticles show excellent superparamagnetic behavior and ultrahigh stretchability and may have potential application in magnetic sensor or targeted drug delivery.
Poly(vinylidene fluoride) (PVDF; M w ~ 550,000) and polymethyl methacrylate (PMMA; M w ~ 350,000) were purchased from Aladdin and Sigma-Aldrich, respectively. Solvents we used include N, N-dimethylformamide (DMF; HCON(CH3)2) and acetone (CH3COCH3). Three kinds of magnetic nanoparticles (γ-Fe2O3, Fe3O4, and NiO) with average diameters of 20 nm were supplied by Aladdin.
Preparation of Magneto-Mechanical Drawing Solution
Different concentrations of PVDF spinning solutions, their viscosity for spinning, and their spinning results
PVDF concentration (wt.%)
Result of spinning
Difficult to get fibers
Suitable for spinning, good fibers
Difficult to spin
Magneto-Mechanical Drawing Set-up
Magneto-mechanical drawing set-up requires no high voltage or other harsh terms, it is simpler, easier to assemble, and safer compared with common spinning methods like electrospinning, melt-blowing. It mainly consists of three parts, including feeding device (a syringe pump (Longer Pump LSPO1-1A) and a syringe for solution), collection device (a stage (r = 4.5 cm) on which equipped with a permanent magnet (1 cm × 1 cm × 2.2 cm) and several pillars (h = 2.5 cm)) and a rotary motor. The rotary motor is connected to the stage and used to control the rotating speed of the stage. The magnet and pillars are vertically glued onto the stage. The pinhead is placed perpendicular to the direction of the pillar. The distance between them can adjust to several millimeters.
Magneto-Mechanical Drawing Process
The resultant composite fibers were characterized by a scanning electron microscope (SEM; JEOL, JSM-7500F), a transmission electron microscope (TEM; JEOL, JEM-2100F), and a Fourier transform infrared (FTIR) spectrometer (Thermo Scientific Nicolet iN10). The average diameter of the fibers was measured by using a SEM image analysis software (Smile View). The viscosities of different spinning solutions were measured by a rheometer (Physica MCR 301). The magnetic properties of the fibers were measured using a vibrating sample magnetometer (VSM) of physical properties measurement system (PPMS) of quantum design) by sweeping the external field from −25,000 to 25,000 Oe at 300 K. The stress-strain characteristic curve of fiber bundle (fiber number ~100, average fiber bundle diameter ~10 μm) was obtained by a dynamic mechanical analyzer (Q-800, TA Scientific).
Morphology and Structure of PVDF/γ-Fe2O3 Fibers
Infrared Spectroscopy of PVDF Powder and PVDF/γ-Fe2O3 Fibers
FTIR peak assignments for the PVDF/γ-Fe2O3 fibers
Wave numbers (cm−1)
Functional groups and crystallites
β-crystal of PVDF
The Relation Between Rotating Speed and Fiber Diameter
Preparation of Well-organized Fibers
Magneto-Mechanical Drawing Other Composite Fibers
Mechanical Property of PVDF/γ-Fe2O3 Fibers
Magnetic Property of the Fibers
In this study, a facile magneto-mechanical drawing method has been used to prepare magnetic composite microfibers. This method utilizes magnetic force generated by a revolving permanent magnet to draw polymer/magnetic nanoparticle solutions, which is simple, energy-saving, and safe. PVDF/γ-Fe2O3 fibers with parallel and crossed structures were successfully prepared by this method. SEM and TEM images indicate that the average fiber diameter is 8.4 μm and magnetic γ-Fe2O3 nanoparticles are distributed in the PVDF matrix. In addition, the fiber diameter decreases gradually by increasing rotating speed of collecting stage. Different polymers and magnetic nanoparticles have also been applied in this work successfully to prove the general applicability of the method. Particularly, the resultant fibers show excellent superparamagnetic behavior and ultra-high stretchability (~440 %), indicating potential applications in functional fibers, stretchable devices/sensors, and magnetic drug delivery.
This work was supported by the National Natural Science Foundation of China (51373082, 51673103, and 11304173), the Taishan Scholars Programme of Shandong Province, China (ts20120528), and the Postdoctoral Scientific Research Foundation of Qingdao.
YZL developed the concept and designed the experiments. JTL, XSJ, and XXH performed the experiments. YZL, JTL, and GFY contributed to data analysis. All authors wrote and revised the paper. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Zhou Z, Lin W, Wu XF (2015) Electrospinning ultrathin continuous cellulose acetate fibers for high-flux water filtration. Colloids Surf A 494:21–29Google Scholar
- Wang Q, Bai Y, Xie J, Jiang Q, Qiu Y (2016) Synthesis and filtration properties of polyimide nanofiber membrane/carbon woven fabric sandwiched hot gas filters for removal of PM 2.5 particles. Powder Technol 292:54–63View ArticleGoogle Scholar
- Anka FH, Balkus KJ Jr (2013) Novel nanofiltration hollow fiber membrane produced via electrospinning. Ind Eng Chem Res 52:3473–3480View ArticleGoogle Scholar
- Jalaja K, Anil Kumar PR, Dey T, Kundu SC, James NR (2014) Modified dextran cross-linked electrospun gelatin nanofibres for biomedical applications. Carbohydr Polym 114:467–475View ArticleGoogle Scholar
- Hild N, Schneider OD, Mohn D, Luechinger NA, Koehler FM, Hofmann S, Vetsch JR, Thimm BW, Müller R, Stark WJ (2011) Two-layer membranes of calcium phosphate/collagen/PLGA nanofibres: in vitro biomineralisation and osteogenic differentiation of human mesenchymal stem cells. Nanoscale 3:401–409View ArticleGoogle Scholar
- Brozena AH, Oldham CJ, Parsons GN (2016) Atomic layer deposition on polymer fibers and fabrics for multifunctional and electronic textiles. J Vac Sci Technol A 34:010801View ArticleGoogle Scholar
- Gorji M, Jeddi AAA, Gharehaghaji AA (2012) Fabrication and characterization of polyurethane electrospun nanofiber membranes for protective clothing applications. J Appl Polym Sci 125:4135–4141View ArticleGoogle Scholar
- Bueres RF, Asedegbega-nieto E, Díaz E, Ordóñez S, Díez FV (2008) Preparation of carbon nanofibres supported palladium catalysts for hydrodechlorination reactions. Catal Commun 9:2080–2084View ArticleGoogle Scholar
- Tan DH, Zhou C, Ellison CJ, Kumar S, Macosko CW, Bates FS (2010) Meltblown fibers: influence of viscosity and elasticity on diameter distribution. J Non-Newtonian Fluid Mech 165:892–900View ArticleGoogle Scholar
- Ellison CJ, Phatak A, Giles DW, Macosko CW, Bates FS (2007) Melt blown nanofibers: fiber diameter distributions and onset of fiber breakup. Polymer 48:3306–3316View ArticleGoogle Scholar
- Greiner A, Wendorff JH (2007) Electrospinning: a fascinating method for the preparation of ultrathin fibers. Angew Chem Int Ed 46:5670View ArticleGoogle Scholar
- Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S (2003) A review on polymer nanofibers by electrospinning and their applications in nanocomposites. Compos Sci Technol 63:2223–2253View ArticleGoogle Scholar
- Reneker DH, Chun I (1996) Nanometre diameter fibres of polymer, produced by electrospinning. Nanotechnology 7:216–223View ArticleGoogle Scholar
- Borkar S, Gu B, Dirmyer M, Delicado R, Sen A, Jackon BR, Badding JV (2006) Polytetrafluoroethylene nano/microfibers by jet blowing. Polymer 47:8337–8343View ArticleGoogle Scholar
- Badrossamay MR, Mcllwee HA, Goss JA, Parker KK (2010) Nanofiber assembly by rotary jet-spinning. Nano Lett 10:2257–2261View ArticleGoogle Scholar
- Zhou FL, Gong RH (2008) Manufacturing technologies of polymeric nanofibres and nanofibre yarns. Polym Int 57:837–845View ArticleGoogle Scholar
- Frenot A, Chronakis IS (2003) Polymer nanofibers assembled by electrospinning. Colloid Interface Sci 8:64–75View ArticleGoogle Scholar
- Li D, Xia Y (2004) Electrospinning of nanofibers: reinventing the wheel? Adv Mater 16:1151–1170View ArticleGoogle Scholar
- Wu Y, Yu JY, He JH, Wan YQ (2007) Controlling stability of the electrospun fiber by magnetic field. Chaos, Solitons Fractals 32:5–7View ArticleGoogle Scholar
- Yang D, Lu B, Zhao Y, Jiang X (2007) Fabrication of aligned fibrous arrays by magnetic electrospinning. Adv Mater 19:3702–3706View ArticleGoogle Scholar
- Liu Y, Zhang X, Xia YN, Yang H (2010) Magnetic-field-assisted electrospinning of aligned straight and wavy polymeric nanofibers. Adv Mater 22:2454–2457View ArticleGoogle Scholar
- EI Mohajir BE, Heymans N (2001) Changes in structural and mechanical behaviour of PVDF with processing and thermomechanical treatments. 1. Change in structure. Polymer 42:5661–5667View ArticleGoogle Scholar
- Yu LY, Xu ZL, Shen HM, Yang H (2009) Preparation and characterization of PVDF–SiO2 composite hollow fiber UF membrane by sol–gel method. J Membr Sci 337:257–265View ArticleGoogle Scholar
- Saikia D, Kumar A (2004) Ionic conduction in P(VDF-HFP)/PVDF-(PC + DEC)–LiClO4 polymer gel electrolytes. Electrochim Acta 49:2581–2589View ArticleGoogle Scholar
- Luo H, Huang Y, Wang D (2013) The crystallization and crystal transition of PVDF in PAN nano-tube. Polymer 54:4710–4718View ArticleGoogle Scholar
- Agyemang FO, Sheikh FA, Appiah-Ntiamoah R, Chandradass J, Kim H (2015) Synthesis and characterization of poly(vinylidene fluoride)-calcium phosphate composite for potential tissue engineering applications. Ceram Int 41:7066–7072View ArticleGoogle Scholar
- Salimi A, Yousefi AA (2003) Analysis method: FTIR studies of β-phase crystal formation in stretched PVDF films. Polym Test 22:699–704View ArticleGoogle Scholar
- Tang B, Wang G, Zhuo L, Ge J, Cui L (2006) Facile route to α-FeOOH and α-Fe2O3 nanorods and magnetic property of α-Fe2O3 nanorods. Inorg Chem 45:5196–5200View ArticleGoogle Scholar
- Zhu Y, Zhao W, Chen H, Shi J (2007) A simple one-pot self-assembly route to nanoporous and monodispersed Fe3O4 particles with oriented attachment structure and magnetic property. J Phys Chem C 111:5281–5285View ArticleGoogle Scholar