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Electrospinning and electrospun based polyvinyl alcohol nanofibers utilized as filters and sensors in the real world

  • Kamran-ul-Haq Khan EMAIL logo , Suhaib Masroor and Ghaus Rizvi
Published/Copyright: June 27, 2023
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Journal of Polymer Engineering
From the journal Journal of Polymer Engineering Volume 43 Issue 7

Abstract

Electrospinning is a contemporary and effective technique for producing fine fibers with diameters as small as nanometers by using an electric field. These fibers have numerous industrial applications, including filtration, sensors, composite materials, and membranes. This study provides an overview of the electrospinning process and discusses a few applications of polyvinyl alcohol based electrospun nanofibers in the development of filters and sensors.

Keywords: electrospinning; filters; nanofibers; polyvinyl alcohol (PVA); sensors

1 Introduction

The production of nanofibers by electrospinning has received a lot of interest in recent years. Till today, it is the most effective technique for creating nanofibers with electrical charges. When an electric field is applied during the electro-hydrodynamic process of electrospinning, it causes a fluid in motion to stretch out and produce thin fibers [1,2]. This technique has the advantages of being quite easy, inexpensive, rapid, adaptable, and using a variety of materials. The method also allows for control of the diameter, microstructure, and fiber arrangement [3,4]. The evolution of electrospinning technology has been extensive, beginning with fundamental concepts and progressing significantly in the development of highly advanced products with diverse applications today. Polymer solution electrospinning and melt electrospinning are the two fundamental forms of electrospinning. Due to its capacity to create nanoscale fibers, solution electrospinning is more frequently used. The absence of comprehensive study on melt electrospinning theory and equipment contributes to a huge gap between the implementation of the two processes. Although solution-based electrospinning was used in most of the studies, the melt electrospinning process has its own advantages. There are various distinguishing characteristics [5], [6], [7], [8] between these two approaches, some of which are as follows:

  1. Cost effective: melt electrospinning is preferable to solution electrospinning in terms of cost savings and productivity gains, as there is no need of a compatible solvent for a particular polymer to be spun.

  2. Eco-friendly: the solvent gets evaporated before reaching the collector in solution electrospinning to obtain solid fibers. While, in case of melt electrospinning no such evaporation is needed, and the solidification of fibers occurs due to heat transfer. The later, makes the process environmental friendly.

  3. Smooth surface morphology: melt electrospinning produces highly homogeneous fibers with minimal fluctuations in fiber diameter (FD).

  4. Fiber diameter: compared to melts, electrospinning of polymer solutions often results in smaller-diameter fibers.

  5. Crystallinity: one of the most crucial elements affecting the mechanical characteristics of the fiber is its crystalline makeup. In general, the degree of crystallinity leads to a rise in the elastic modulus of the fibers, which produces improved mechanical qualities. In case of solution electrospinning, the solvent evaporation causes the aligned polymer chains to solidify, resulting in the creation of crystals. In contrast, melt-electrospun fibers are believed to have a very low degree of crystallinity and a less stable crystal structure due to the fast quenching generated by electro-hydrodynamically driven air movement near to the polymer-jet.

  6. Experimental setup/arrangements: in melt-electrospinning, the heating mechanism is a significant problem. Consideration should be given to problems like the interference between heating sources and high electric fields. This complicates the melt electrospinning experimental setup.

  7. Easy to model: solvent-free melt-electrospinning technology allows for the development of theoretical approaches to characterize electrospinning without the issues caused by solvent evaporation.

1.1 Historical background

William Gilbert conducted an earlier investigation in 1600 that gave rise to the idea of electrospinning [9]. John Cooley [10] and William Morton [11] separately submitted two patent applications on electrospinning in 1902, each of which included descriptions of a working prototype of the electrospinning apparatus. In the year 1914, John Zeleny focused on how to handle liquid droplets at the extreme ends of iron capillaries and attempted to develop a mathematical model of liquids subjected to electrostatic forces during this research [12]. Additionally, he published some recorded observations (utilizing photography) from some experiments he conducted in 1917 on the electric discharge from liquid surfaces [13]. However, Formhals’ work was considered as a pioneer not only in the electrospinning field, but also in the production of electrospun yarn, as evidenced by patents dating from 1934 to 1944 [14], [15], [16], [17], [18]. Formhals holds four patents for parallel fiber bundle production, while the other three are for electrospun twisted yarn production. Electrospinning was further theoretically corroborated by Sir Geoffrey Ingram Taylor during the period of 1964 and 1969. His work has aided in the advancement of electrospinning by simulating the hopper in which liquid drops were generated by an electric field [19], [20], [21]. In the 1990s, Reneker then employed high voltage which charged the polymer solution and created fibers with a diameter less than 5 μm [22], [23], [24], [25], [26]. The most frequent arrangement in laboratories is shown in Figure 1 [27] and forms the foundation for electrospinning till date. It has a reservoir for polymer dispersion with a pump, a high-voltage source, a nozzle, and a conductive collector. The polymer solution is collected on the surface of the collector screen based on the electrostatic field between the nozzle and collector.

Figure 1: Basic electrospinning apparatus [27]; reprinted with permission.
Figure 1:

Basic electrospinning apparatus [27]; reprinted with permission.

1.2 Process of electrospinning

Numerous hypothetical studies on electrospinning technique have been put forward by many researchers [28], [29], [30]. Towards the end of the 1500s, the work of Sir William Gilbert on magnetic and electrostatic emanation has proven to be quite enlightening. He also mentioned that when an electrostatic field is applied to a water drop, it adopts the shapes of a cone and a hopper, with a drop ejecting from the top of the hopper. This established the primary method of electro-spraying. One may consider electrospinning to be a type of electro-spraying. To increase the liquid electrostatic potential, a power source having a high voltage is connected to electrospinning raw material. Polymers that have high molecular degree are usually employed as raw substances primarily depending upon their interaction at molecular level. The electrostatic potential and surface charge on the fluid are directly related, therefore, by decreasing or increasing any one amongst them, a similar activity will occur for the other. Typically, the shape of the volume of fluid is derived from the surface tension. When the liquid is charged, the surface charge interacts with the surface tension in a way that is opposed, causing the liquid to shift shape and take on the Taylor cone shape [19]. Various parameters affect the electrospinning of fibers; this makes research and investigation in this area critical but attractive.

This paper is organized into four sections. Introduction, historical background, and basics of electrospinning are described in Section 1. Section 2 discusses some of the crucial parameters which affect the process of electrospinning. Section 3 describes the electrospinning ability of PVA to form nanofibers together with their applications in making filters and sensors. Finally, the paper is concluded in Section 4 including few future directions.

2 Essentials of electrospinning

The electrospinning process is impacted by a number of variables. These elements fall under the categories of solution parameters, electrospinning parameters, and environmental parameters. The characteristics of electrospun fibers, such as fiber shape, average fiber size, homogeneity, porosity, and mechanical qualities, rely on a wide range of these factors. Solution characteristics are influenced by the polymer concentration (polymer solubility in solvent), solution conductivity, and viscosity. Applied voltage, solution flow rate, collector substrate geometry, collector-to-needle distance and internal needle diameter are the most crucial electrospinning parameters. Temperature and relative humidity are among the environmental parameters. Many of these variables have sufficiently large ranges; altering them outside of an ideal range may cause outcomes to deviate either slightly or even dramatically. Because the variables are interconnected, what is permissible in one case may not apply in another because changing one parameter can affect the acceptable range of another. A brief overview of the electrospinning parameters is described in the following section.

2.1 Applied voltage

In electrospinning the applied (spinning) voltage plays a significant role in the final characterization of the fiber. Electrospinning charge transfer occurs as a polymer stream is pointed at the collector. This happens because a charged jet is perceived from the apex of the Taylor cone due to the spinning voltage. The polymer mass stream flow that exits from the needle tip has a direct influence on increasing or decreasing the spinning current. Spinning current can be decreased by decreasing the applied voltage. A beaded morphology occurs with the rise of spinning current resulting in a lowering of the surface area. The shape and structure of fibers can alter as a result of an increase or decrease in applied spinning voltage [31]. According to some earlier research, a rise in spinning voltage causes the fibers length to expand their diameter to contract [32], [33], [34].

2.2 Internal needle diameter

Several earlier researches on the relationship between internal needle diameter (IND) and FD have come to the conclusion that the average FD decreases as the IND decreases [35], [36], [37], [38]. Even when the statistical analysis indicates that there is no considerable association between these factors, one can still make predictions about it based on experimental evidence. The FD cannot be significantly modified by a smaller IND, but it can be changed by utilizing a needle with a bigger diameter [39].

2.3 Collector design

A variety of fiber patterns could be created by experimenting with different collector designs. Information about the morphology of electrospun fibers and the manner in which they are organized into structures with distinctive properties for particular applications are intensely influenced by the type of collectors [40], [41], [42], [43]. Different shapes of collector used in electrospinning are shown in Figure 2 [27]. Rotatory drum (collector) shown in Figure 1 is the most extensively used collector. Diameter of fiber is generally monitored with the help of this type of collector (by varying the speed of the drum) [44,45]. To produce uniaxial oriented fibers a rotating disk is employed. The main advantage of utilizing the disc collector as opposed to a drum-shaped collector design is that the rim of the disc is covered in massive deposition of aligned fibers [46], [47], [48], [49], [50]. The other type of collector employs more than two parallel electrodes to achieve perfect alignment on each electrode [51], [52], [53]. The design of collection drum or a disc, and speediness both have an impact on the fiber’s alignment [45,54,55]. Further, U-shaped collectors can also be employed to successfully fabricate well-aligned and very long fibers [56].

Figure 2: Different types of collectors are utilized in an electrospinning arrangement [27]; reprinted with permission.
Figure 2:

Different types of collectors are utilized in an electrospinning arrangement [27]; reprinted with permission.

2.4 Separation between tip of needle and collector

The distance between the nozzle and the collector is another factor that has an impact on the structure, morphology, and physicochemical characteristics of electrospun fibers. Based on the evaporation rate, inconsistency interval, and deposition time, it has a direct impact on the final fiber’s qualities. Different studies reveal that we can produce wet electrospun fiber with a beaded structure by shortening the distance between the collector and the nozzle. This also affects the ultimate fiber morphology. In some instances, flat shaped fiber has been observed as compared to circular shape fiber [32], [33], [34]. It is typically advised to keep a certain space between objects when creating smooth fibers free of pores and beads. Furthermore, the research demonstrates that a greater separation is necessary to obtain dried fiber from polymer solution [34].

2.5 Rate of dispersion

Polymer flow rate is another influential factor on the physical and chemical characteristics of fabricated fiber. Fiber morphology changes as a result of variations in polymer flow rate (from the syringe pump). The diameter of the fiber grows as the flow rate rises, and a beaded morphology is seen [32,57–59]. Due to the jet’s ability to polarize and elongate with enough time, a low flow rate is typically advised for creating thinner fibers.

3 Electrospinning of PVA

PVA has long been regarded as a significant synthetic thermoplastic commercial polymer that is relatively inexpensive, easily processable, optically transparent, and mechanically durable. Technological advancements in electrospinning as well as all varieties of electrospun nanofibers present new possibilities for the creation of novel nanostructured materials. By adopting a straightforward electrospinning technique, PVA fibers can be produced. For nearly two decades, researchers have been developing and analyzing PVA nanofibers and their blends using electrospinning to investigate the effect of the essentials discussed in Section 2 on the diameter and uniformity of the fabricated fibers. However, the effects of these factors are still being investigated for optimized values to obtain the finest fibers with uniform morphology. Several works have been published in this regard; for instance, nanofibers with uniform and bead-less structures were achieved with minimum fiber diameters in the range of 3–11 nm and 6–18 nm, respectively, before and after the crosslinking of PVA [60]. The study concludes that for a 50:50 ratio of chitosan (CS) to PVA, the optimum values of the electrospinning parameters were found to be 30 kV, 20 cm, and 1.48 mL/h, which produced the greatest amount of phenol adsorption. Moreover, a few more studies based on PVA and PVA blends nanofibers with ranges of diameters obtained together with the operating values of the electrospinning parameters are summarized in Table 1.

Table 1:

Diameter of PVA nanofiber along with essential parameters.

Electrospun material Voltage (kV) Solution concentration (wt %) Distance (cm) Flow rate (mL h−1) Fiber diameter (nm)
PVA [61] 5–15 6–8 8–15 0.1–0.3 87–246
PVA [62] 7 to 19 7, 9, 11, 13, 15 4–12 Not mentioned 50 to 250
PVA [37] 10 6 and 14 Not given Not given 230–465
PVA/nano-Au [63] 9 8 17 0.3 200 (average)
PVA/(polyethyleneimine) PEI [64] 18.6 12 (w/w = 3:1) 25 0.3 459.7 (average)
β-CS/PVA [65] 15 40:60 8 Exact value not mentioned 120–550
PVA with glyoxal and phosphoric [66] 19 10 8 Not given 280 (average)

The PVA fibers have shown superior physicochemical qualities and can be utilized in making filters and sensors, as well as in a variety of other applications. Although PVA produces excellent nanofibers when electrospun, its applications are constrained by its strong hydrophilicity, which causes it to disintegrate instantly when in contact with water. Therefore, to enhance their mechanical characteristics and water resistance, PVA fibers are subjected to either chemical or physical crosslinking modifications.

3.1 Application of PVA nanofibers in filtration

Electrospinning is an eminently efficient technique in the production of nanofibers from polymers that have a lot of potential to be used in the filtration field [67], [68], [69]. Air pollution is a complicated problem that has long affected both human health and the atmosphere. The most important and efficient way to enhance air quality is through air filtration. Due to their porous structure, high specific surface area, adjustable morphology, and multi-functional fiber surface, electrospun nanofiber membranes have a potential role in the field of air filtration [70,71]. Ahmad Kusumaatmaja and et al. have successfully fabricated a PVA nanofiber membrane that was used as a smoke filter. After qualitative examination and study (using three smoke sources namely, trash, cigarette smoke, and vehicle combustion smoke) of the shape of PVA membrane, it was concluded that the membrane was reasonably effective in the filtration process. The PVA membrane almost completely prevented the adhesion of all small smoke particles due to its porous and adsorbent qualities [72]. Recently, experiments were conducted by Ga Yeun Kim and his team for preparing composite nanofibers that can be used in the developments of efficient and effective air filters, utilizing the polyethylene terephthalate (PET) in the electrospinning of PVA. The produced nanofibers were stable enough to withstand the humid environment; this was achieved by crosslinking the PVA with Citric Acid (CA) as a crosslinking agent. It is anticipated that this composite PVA can be useful for developing a variety of applications in the field of air filters [73]. Ji Hyun and his co-workers were able to produce photo-catalytically degradable nano-filters (PVA/titanium dioxide (TiO2)). A schematic illustration of the photocatalytic decomposition of PVA/TiO2 nano-filters is shown in Figure 3. These filters, being eco-friendly, could be the solution to overcome the problems of disposing of existing filters, which were done in landfills or by burning them, both of which could be harmful to the environment [74]. Also, in another study done by Han Jung Kim and his colleagues regarding eco-friendly disposable filters, the filters were developed utilizing the electrospinning technique, composed of dual layer structure of PVA/(Polypropylene) PP based nonwoven fabric. This can be used in different applications for developing air filters, such as cabin filters, dust masks, and high efficiency particulate air (HEPA) filters [75]. Agne daneleviciute-vaisniene and his colleagues investigated the organic compounds that can be removed from gas (cigarette smoke) using a nonwoven PP material filter wrapped in electrospun PVA nanofiber membrane. The filter can also remove ethers, carbonyl compounds, and organic polar compounds from gas [76]. Li et al. had successfully electrospun PVA nanofibers with average diameters of about 100 nm coated on a nonwoven fabric to create a composite filter material. Their research demonstrated high effectiveness and low pressure drop for filtration of sodium chloride (NaCl) nano-sized particles, while depositing a nanofibers layer less than 3 μm. Fabricated nanofiber mats in a multi-layer configuration can produce greater filtering efficiencies with a high-quality factor and significantly lower mass in comparison to HEPA filters [77]. Furthermore, a few more studies involved in making efficient filters based on PVA electrospinning are described in Table 2. According to [78], the cellulose (cotton) nanocomposite fabrics (CNCFs) were found to have effective antibacterial action against both Gram-positive and Gram-negative microorganisms. A combination of nano-Ag and CNCFs with PVA nanofibers may be considered in the future for medical applications such as surgical aprons, wound cleaning and wound dressing materials, and so on, as PVA with silver nanoparticles is also used to address antibacterial activities (see Table 2).

Figure 3: PVA/TiO2 nanofiber photocatalytic degradation scheme [74]; reprinted with permission from American Chemical Society (https://pubs.acs.org/doi/10.1021/acsomega.9b03944), copyright (2020).
Figure 3:

PVA/TiO2 nanofiber photocatalytic degradation scheme [74]; reprinted with permission from American Chemical Society (https://pubs.acs.org/doi/10.1021/acsomega.9b03944), copyright (2020).

Table 2:

PVA-based electrospun filters.

Spinning solution Problem addressed Remarks
PVA/nano-Ag [79] The author examined:

  1. Effective air filtration of particles in range of nano size

  2. Air flow resistance to provide breath ability

  3. Antibacterial activity for microorganisms of aerosols size

 The suggested PVA/Ag electrospun nanofibers found to be the best feasible applicant for prospective replaceable filtering media that may be used in facemasks or into indoor air purification systems
PVA/(cellulose nanocrystals) CNCs [80] Air pollution is one of the factors which affect public health, particularly in the nations that are heavily industrialized. In this regard composite filter (PVA/CNCs) are created using electrospinning to capture particulate matter (PM) The developed filter is capable to work at low air resistance and have great potential for applications in indoor air filtration
PVA-(poly (acrylic acid) PAA [81] The author creates a nanofibrous composite membranes (PVA-PAA) using electrospinning for research on a combined antibacterial activity and air filtration The developed nanofibrous membranes have exceptional qualities like high filtration effectiveness, biological compatibility, antibacterial capabilities, and low airflow resistance, which may prove to be useful materials in the fighting against air pollution, for application in personal air filtration systems
PVA/CNCs [82] The author determines the optical conditions for producing PVA/CNCs filters employing response surface methodology (RSM) and assess the filtering effectiveness of electrospun filters (PVC/CNCs) based on the simultaneous influences of significant parameters A polynomial prediction model of second order was developed which provides more comprehensive and accurate results. With a pressure drop (34.9 Pa), a 94 % removal efficiency of created filter for PM was achieved. Furthermore, RSM reduces the number of trial runs and the associated cost

In addition to that, it was reported by Xi Lu and colleagues that cross-linked zein nanofibers have the potential to be used in air filtration. By electrospinning zein with polyvinyl alcohol and cross-linking with glutaraldehyde, the performance of zein nanofibers to withstand moisture and air filtration was increased. The enhanced nanofibers demonstrated superior mechanical characteristics and a filtering effectiveness of over 97 % for PM 0.3 μm and various pollution particle sizes [83]. For extremely effective air filtration, multifunctional filters based on zein and PVA nanofibers were reported by Li et al. The degree of alcoholysis and various PVA contents are significant variables determining filtration effectiveness. For the purpose of trapping particles and gas molecules smaller than the pore size of the nanofibers, denaturation of the zein protein can considerably improve the interactions between nanofabrics and contaminants. High removal effectiveness for particles with a wide size range of 0.1–10 μm was demonstrated by the zein/PVA nanofibers [84].

Moreover, Yankang Deng and his colleagues recently proposed an environmental friendly, highly breathable, and effective sodium sulphobutylether-cyclodextrin and PVA electrospun nanofiber membrane, which was made for the first time using green one-step electrospinning. The curved-ribbon nanofiber membrane with multi-hierarchical structure demonstrated superior filtration performance in comparison to conventional nanofiber membranes, with a tolerable pressure drop (57.5 Pa) and 99.12 % filtration efficiency for PM1.0 (see Figure 4). The core-filter layer of the commercial mask was replaced, and the completed mask’s filtration effectiveness for PM1.0–10 with little air resistance (60 Pa) was close to 100 %. A green technique was used during the fabrication process to minimize secondary environmental pollution. This method holds promise for replacing existing filters in the future in order to achieve sustainable development [85]. Based on PVA/sodium alginate/hydroxyapatite (T-PVA/SA/HAP) nanofibrous membranes, Yankang Deng created a high-performance, environmental friendly, and biosafe air filtration membrane. The developed materials have electrostatic adsorption for charged PM as well as sustainability. A high-performance protective mask was created using T-PVA, SA, and HAP nanofibrous membranes and morphology-modification engineering to increase the contact area between nanofibers and PM. The actual outcomes demonstrated that the built mask had adequate air permeability, the capacity to filter out significant atmospheric PM, the ability to remove more than 99 % of PM0.3–2.5, and the ability to produce a tolerable air pressure drop [86]. Through green preparation, Yankang Dengour and colleagues further produced a typical granular-convex structure on the surface of sodium phytate/polyvinyl alcohol (T-PANa/PVA) fiber that has been thermally crosslinked. This secondary structure effectively removed air contaminants through physical interception and polar adsorption. It showed exceptional air pollution removal (removing PM2.5 at a rate of more than 99.9 % while having a low air resistance of 36.5 Pa). The T-PANa/PVA fiber membrane also exhibits mechanical and water-resistant qualities. This research offers a useful method for creating hierarchical fiber membranes for high-performance air filtration, which is anticipated to replace conventional air filtration materials and accommodate sustainable development in the future [87].

Figure 4: Comparison of the filtration effectiveness and pressure drop of different nanofiber membranes [85]; reprinted with permission from Elsevier, copyright (2022).
Figure 4:

Comparison of the filtration effectiveness and pressure drop of different nanofiber membranes [85]; reprinted with permission from Elsevier, copyright (2022).

The thickness of the nanofiber filter is crucial for determining the effectiveness of material transport, although several earlier studies have shown that nanofiber characteristics can be adjusted by altering the electrospinning parameters. However, merely altering the electrospinning parameters is not likely to result in consistent nanofiber filter thickness. The current methods for regulating the deposition of nanofiber filters depend on a quick and ineffective method of adjusting the electrospinning time. Additionally, bending instability can cause non-uniform deposition, resulting in a locally thin nanofiber filter area with poor mechanical strength or filtration efficiency. To accomplish a uniform deposition, it is required to create an electrospinning system that can control the deposition of nanofibers. To create uniform-thickness nanofiber filters, an adaptive electrospinning technology based on reinforcement learning (E-RL) was recently introduced by Seok Hyeon Hwang et al. The E-RL detected the non-uniformity of the nanofiber filter thickness (real time) and manipulated the movable collector to alleviate it. This finding has great potential for improving the reliability of electrospinning and nanofiber filters used in research and industrial fields [88]. Moreover, A.M. Abd El-Aziz and et al. prepared composite nanofiber of PVA/HA (hydroxyapatite) using electrospinning and suggested that the composite has capability of removing heavy metals from wastewater [89].

3.2 Application of PVA nanofibers in sensors

Nanofibers made up of PVA are broadly used in making sensors [90,91]. Gas sensors are becoming increasingly significant for environmental monitoring, industrial manufacturing facilities, human health and safety, agriculture, and defense [92,93]. The gas sensor’s tiny size, low cost, low power consumption, and great sensitivity are its most advantageous traits [94]. Conducting polymers provide a number of advantages over metal oxides, including a quick response time, room-temperature operation, high sensitivity, and the ability to combine chemical and physical properties [95]. Conductivity is often slightly low in pure forms of conducting polymers; however, this property is easily enhanced through doping. Polyvinyl alcohol (PVA) is a well-known synthetic polymer hydrogel with a good charge storage capacity, high dielectric strength, and dopant-dependent electrical properties [96]. By using the specific dopants, PVA becomes conductive, as it is a poor conductor of electricity. PVA’s conductivity is primarily governed by the amorphous area features and results from a high rate of physical interaction between polymer chains via hydrogen bonding between the dopant and hydroxyl groups [97]. Numerous experiments, based on electrospinning, have been conducted to create ultrasensitive gas sensors capable of detecting vapors like NH3, H2S, and CO [98], [99], [100]. With the aid of electrospinning, Gomaa F. and his colleagues [101] successfully produced nanofibers for gas sensor applications using polyvinyl alcohol and pluronic solution with varying concentrations of titanium dioxide (TiO2) nanoparticles. The study revealed that the diameters of the nanofibers increased from 280 nm to 310 nm when TiO2 nanoparticles were added to the blended solution. Liquid petroleum gas (LPG), carbon dioxide (CO2), and oxygen (O2) were chosen to examine the gas sensor response of TiO2 nanofibers as a function of temperature (Figure 5). TiO2 nanofibers (0.01 %) were observed to achieve the highest response value (100 %) for LPG at 160 °C. These findings indicate that the fabricated nanofiber materials have promising gas-sensing properties, including lower operating temperatures and adequate gas responses.

Figure 5: Temperature-dependent response of TiO2-nanofiber gas sensors for (A) CO2, (B) O2, and (C) LPG gases. (PVAT1, TiO2 = 0.01 %, PVAT3, TiO2 = 0.03 %, and PVAT5, TiO2 = 0.05 %) [101]; reprinted with permission from Springer Nature.
Figure 5:

Temperature-dependent response of TiO2-nanofiber gas sensors for (A) CO2, (B) O2, and (C) LPG gases. (PVAT1, TiO2 = 0.01 %, PVAT3, TiO2 = 0.03 %, and PVAT5, TiO2 = 0.05 %) [101]; reprinted with permission from Springer Nature.

Furthermore, to preserve the environment and human health, NO2 gas monitoring is essential [102]. NO2 is a hazardous gas created when fossil fuels are burned and released as exhaust [103,104]. Over the past few decades, organic field effect transistors OFET sensors have emerged as a research hotspot due to their ease of setup, high sensitivity, low cost, and multi-functional integration [105], [106], [107], [108]. They are widely used in industries as gas sensors, pressure sensors, and other applications [109], [110], [111], [112]. However, the previously reported OFET-based gas sensors need to be properly modified or improved [113], [114], [115]. In this regard, Lu Wang and his team have developed an OFET-based, highly sensitive NO2 sensor with a stereoscopic structure. Copper phthalocyanine (CuPc) is employed as the sensitive substance, and it is evaporated on the stereoscopic electrospun PVA nanofibers. CuPc stereoscopic film sensors with PVA NFs have greater sensing performance than CuPc continuous film sensors. Figure 6 shows different response currents and recovery rates for CuPc continuous film OFET-based sensors and CuPc/PVA NFs stereoscopic OFET-based sensors. Strong response currents were present in the CuPc continuous films of OFET-based sensors (see Figure 6A), but recovery from baseline drifts was practically impossible. In contrast, quick response and recovery were achieved by the CuPc stereoscopic OFET-based sensors with 5.0 wt% PVA nanofibers (see Figure 6B). The stereoscopic structural sensor’s most significant impacts are its modest baseline drift, short average reaction time (less than 10 min), high average sensitivity (more than 800 % per ppm), and low detection limit (less than 1 ppm). Because of the improved detecting capabilities of the CuPc/PVA/NFs OFET-based sensor, other hazardous gas sensors can benefit from the design concept of this suggested stereoscopic sensor [116]. Lu Wang and his colleagues expanded on their previous work by evaporating CuPc on PVA parallel nanofiber arrays (PNAs) to build a three-dimensional (3D) CuPc OFET sensor. They used an electrospinning receiving board with a clined gap to create well-ordered PVA nanofibers. When compared to single-layered and disordered PVA nanofibers, CuPc/PVA/PNAs sensors reduce the lowest detection concentration by one-third. Furthermore, the CuPc/PVA PNAs sensors have response and recovery times of 0.02 min for 25 ppm NO2, which are 350 and 130 times faster than the CuPc sensors using disordered PVA nanofibers, respectively [117].

Figure 6: Real-time monitoring of the NO2 curves for (A) CuPc continuous films OFET-based sensors and (B) CuPc/PVA NFs stereoscopic OFET-based sensors [116]; reprinted with permission from American Chemical Society, copyright (2020).
Figure 6:

Real-time monitoring of the NO2 curves for (A) CuPc continuous films OFET-based sensors and (B) CuPc/PVA NFs stereoscopic OFET-based sensors [116]; reprinted with permission from American Chemical Society, copyright (2020).

Humidity sensors have evolved greatly in response to growing concerns about humidity monitoring and control in recent years. Among various polymers, PVA has proven to be a good, sensitive material for humidity sensors [118,119]. Barkauskas, nearly two and a half decades ago, created a composite by mechanically combining carbon black (CB) and PVA, and reported it as a possible humidity-sensitive material capable of sensing low humidity [120]. The electrospun based PVA nanofibers with regulated nano-size ranging from 1 nm to 100 nm were used to create a capacitive humidity sensor by Haroon-ur-Rashid and et al. It was determined that the instrument has a linear and repeatable response, is affordable, and is simple to make. Additionally, it appears from the results that PVA nanofibers have better sensing qualities for relative humidity [121]. Furthermore, a few of the notable research efforts involved in making humidity sensors based on PVA electrospinning are described in Table 3.

Table 3:

PVA-based electrospun sensors.

Spinning solution Problem addressed Remarks
PVA-(polyvinyl pyrrolidone) PVP- (polyethylene glycol) PEG [122] The author designs a composite nanofiber-based humidity sensors, made up of PVA, PVP, and PEG that are reinforced with titanium carbide (TiC) as filler The created humidity sensors in this work have a lot of promise for use in target-based environments
PVA [123] The author proposed a flexible photoluminescent-humidity sensitive material (nanofiber film) through electrospinning of PVA containing carbooxylated quantum dots QDs The synthesized material is anticipated to be used in the creation of flexible sensors (tactile) for human comfort as well as for robot perception and control
PVA/nano-ZnO [124] A PVA/nano-ZnO nanofiber film-coated optical fiber sensor (peanut-shaped) was proposed and created for use in sensing temperature and humidity The PVA/nano-ZnO composite film used in the suggested sensor had a better sensitivity than the film without ZnO

Moreover, Yen-Lung Chou and their colleagues designed an optical fiber sensor (U-Shaped) for temperature measurements. To reduce humidity sensitivity, electrospinning was used to coat PVA, on top of the sensor layer. Variations in temperature from 30 °C to 100 °C are measured by the sensor. The study’s goal was to utilize COMSOL to model the wavelength signals produced at various electrospinning durations and to examine the sensitivity variation of the sensor with varying sensor layer thicknesses resulting from those durations. The results showed that the sensor’s maximum wavelength sensitivity, transmission loss sensitivity, and linearity were all improved [125].

Paloma Vilchis-León and his co-workers reported nanomaterials that can be utilized in biomedical microelectromechanical systems as selective biosensors for diagnostic reasons. The study described a nanocomposite made up of PVA and multiwall carbon nanotubes (CNTs) doped with nitrogen, which changes the electrical properties and viscosity of the polymer to produce nanofibers via electrospinning. To illustrate how well the produced nanofibers, work for electrochemical analysis, the CNx mats were subjected to several aqueous solutions in a potentiostat. Cyclic voltammograms were used to detect the CNx-induced changes in the polymer’s electrical characteristics, and electrochemical investigation confirmed super-capacitor functionality [126]. For detecting biogenic amines, a work has been reported in which authors fabricate PVA nanofibers using electrospinning and depositing them on glass substrates along with Ag nanoparticles (NPs) and assess the adaptability of the technique. The benefits of this strategy can be summed up as a quick and affordable preparation process, the ability to quantify the entire amount of amines, and the minimal amount of equipment needed. The drawbacks include a lack of remarkable sensitivity and the need for food processing in order to remove the amines [127]. Additionally, a lot of research is being done on biosensors and their prospective applications. Table 4 provides a summary of a few PVA-based biosensors and their uses.

Table 4:

PVA-based Electrospun biosensors.

Material/blended/composite Linear range Application References
CS/PVA 2.7–3.8 mM Used for colorimetric glucose sensing with the advantage of naked eye color confirmation [128]
PVA/polyamidoamine (PAMAM)-montmorillonite (Mt) 0.005–0.25 mM The fabricated PVA/PAMAM-Mt electrospun nanofiber is a promising design for the immobilisation of biomolecules because glucose detection was successfully accomplished/reported in this work utilizing pyranose oxidase (PyOx) as a model enzyme [129]
PVA/PEI/(glucose oxidase) GOx/(gold nanoparticles) GNPs 10–200 μM Used in ultrasensitive electrochemical glucose biosensing (The developed biosensor successfully allowed for the detection of glucose by electrochemical impedance spectroscopy while maintaining enzyme activity) [130]
PVA-styrylpyridinium/GOx/hexokinase//GNPs 25–200 μM (for ATP)

0.01–3 mM (for glucose)

  1. Utilized to successfully detect adenosine triphosphate (ATP) via chronoamperometry

  2. In samples with known or extremely low (less than 10 micro M) ATP concentration, the biosensor can also be utilized to detect glucose

 [131]

Khatri and his group fabricated PVA nanofibers using electrospinning which were UV-responsive and could be utilized to record and erase quick response (QR) codes [132]. In numerous fields, including the treatment of cancer [133,134] and the monitoring of water quality [135], radical sensing is crucial. In this regard, an optical detecting mat for peroxide and the related radicals, Nader Shehata et al. introduced a new nanocomposite of ceria nanoparticles embedded in crosslinked PVA electrospun nanofibers. It was also revealed that the produced nanocomposite emits visible light when fluorescent under near-UV excitation. Through a fluorescence quenching mechanism, it was observed that the visible fluorescence intensity peak is diminished with increasing peroxide concentration. In conclusion, the research could be extremely beneficial for future applications in cancer detection and environmental monitoring [136].

4 Conclusion and future directions

One of the few technologies for producing fibers at the nanoscale is electrospinning. Important fundamental details of electrospinning and its processes are given in this review, along with a comprehensive historical work of the electrospinning techniques, including a detailed analysis of essential electrospinning parameters such as applied voltage, internal needle diameter, collector shape, flow rate, and distance between collecting screen and capillary. Further, the improved surface area-to-volume ratio of nanoscale fibers makes them an appealing material with two key uses: as a filtration medium and as sensing components. In this regard this review also briefly describes some important applications of PVA and PVA composites based electrospun nanofibers used as sensing material and filter media. Moreover, for future work, the following profound information is extracted from this review:

  1. Numerous applications in filters and sensors have been reviewed for electrospun-based PVA nanofibrous membranes. But problems with repeatability, reusability, and sustainability of the membranes are still continuing to limit their effectiveness. Since the ability of any membrane to be commercialized will depend on the aforementioned qualities, researchers are urged to carefully consider these problems in order to extend the membrane’s life and increase its effectiveness for industrial applications.

  2. The multi-hierarchical and hierarchical structure of electrospun-based PVA nanofibrous membranes exhibited a balance reversal between pressure decrease and filtering performance in comparison to the previously reported dense network structure of electrospun-based PVA nanofibrous membranes. This reveals that researchers should focus their efforts in the upcoming years on the development and modification of these structures.

  3. The fabrication of uniform-thickness membranes is crucial, which is usually monitored by the electrospinning time. A work is cited in this review that addresses the real-time monitoring of thickness in this regard; hence, more attention and consideration are required towards the modification in the electrospinning setup.

Corresponding author: Kamran-ul-Haq Khan, Department of Physics, University of Karachi, 75270 Karachi, Pakistan, E-mail:

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2023-02-17
Accepted: 2023-05-29
Published Online: 2023-06-27
Published in Print: 2023-08-28

© 2023 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Material Properties
  3. The degradation behaviors of optical cellulose triacetate films in alkali/acid solutions
  4. Exploration of dielectric spectra of variously synthesized epoxy/ZnO nanocomposites
  5. Preparation and Assembly
  6. Preparation and evaluation of polyvinyl alcohol hydrogels with zinc oxide nanoparticles as a drug controlled release agent for a hydrophilic drug
  7. PVA-borax/g-C3N4 nanocomposite hydrogel with excellent mechanical property and self-healing efficiency
  8. Fabrication and characterization of microencapsulated dimethyl adipate phase change material with melamine-formaldehyde shell for cold thermal energy storage in coating
  9. Preparation and performance of “three-layer sandwich” composite loose nanofiltration membrane based on mussel bionic technology
  10. Engineering and Processing
  11. Electrospinning and electrospun based polyvinyl alcohol nanofibers utilized as filters and sensors in the real world
  12. Synergistic effect of GMA and TMPTA as co-agent to adjust the branching structure of PLLA during UV-induced reactive extrusion
https://doi.org/10.1515/polyeng-2023-0044
Keywords for this article
electrospinning; filters; nanofibers; polyvinyl alcohol (PVA); sensors

Articles in the same Issue

  1. Frontmatter
  2. Material Properties
  3. The degradation behaviors of optical cellulose triacetate films in alkali/acid solutions
  4. Exploration of dielectric spectra of variously synthesized epoxy/ZnO nanocomposites
  5. Preparation and Assembly
  6. Preparation and evaluation of polyvinyl alcohol hydrogels with zinc oxide nanoparticles as a drug controlled release agent for a hydrophilic drug
  7. PVA-borax/g-C3N4 nanocomposite hydrogel with excellent mechanical property and self-healing efficiency
  8. Fabrication and characterization of microencapsulated dimethyl adipate phase change material with melamine-formaldehyde shell for cold thermal energy storage in coating
  9. Preparation and performance of “three-layer sandwich” composite loose nanofiltration membrane based on mussel bionic technology
  10. Engineering and Processing
  11. Electrospinning and electrospun based polyvinyl alcohol nanofibers utilized as filters and sensors in the real world
  12. Synergistic effect of GMA and TMPTA as co-agent to adjust the branching structure of PLLA during UV-induced reactive extrusion
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