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Abstract

To meet today’s technological demands, nanofibrous materials (especially nanocomposite nanofibers) have been noticed more competent of sustaining anticorrosion, structural integrity, and radiation protection, as compared to traditional polymers or nanocomposites. Along these lines, this innovative review article strategically highlights the scientific merit of multifunctional polymer nanofibers and polymer nanocomposite nanofibers for radiation shielding purposes. Accordingly, distinct sections of this manuscript systematically address fundamentals, corrosion protection, and nuclear/electromagnetic shielding capabilities of nanofibrous materials. In this regard, design, fabrication, physical features, and performance aspects of electrospun nanocomposite nanofibers (reinforced with nanocarbons and inorganic nanoparticles) have been argued. Notably, microstructural continuity, electrical/electrochemical characteristics, percolation features, robustness, barrier effects, and self healing properties of nanocomposite nanofibers revealed technical worth for high end anticorrosion applications. Additionally, electron conductivity, dielectric/magnetic permittivity, mechanical/heat stability, and interfacial compatibility of nanocomposite nanofibers depicted next level radiation shielding competence. Consequently, radiation shielding nanofibrous materials with notable mechanical and corrosion protection characteristics attained utmost importance for futuristic real-world industries (aeronautical engineering, defense, electronics, energy devices). Despite the research progress so far, future industrial deployments of radiation shielding multifunctional nanocomposite nanofibers strongly rely on using sustainable green materials, optimized manufacturing methods/parameters, material reproducibility, degradation/biodegradation, and final life cycle assessments.

Keywords

Nanofibers polymers nanocomposites corrosion resistance self healing percolation nuclear shielding electromagnetic interference

Introduction

Nanofibers are unique one dimensional nanostructures derived from variety of materials, including polymers, carbonaceous, inorganic, or hybrid nanomaterials.¹ Particularly, scientific investigations have expanded the field of polymeric nanofibers by synthesizing diversities of thermoplastics, thermosets, elastomers, blends, and copolymers derived nanostructures.^2,3,4 In addition, multifunctional nanocomposite nanofibers have been designed using a number of inorganic and nanocarbon reinforcements to attain high end electrical, thermal, mechanical, dielectric, permissibility, barrier, tribological, and similar physical characteristics.^5,6 For industrial scale deployments of multifunctional nanofibers in devices and engineering structures, corrosion resistance characteristics have been essentially focused by the field researcher to date.^7,8,9 In due course, polymeric and nanocomposite nanofibers depicted superior surface area, optimal porosities, and surface functionalities to enhance the barrier properties against corrosion causing molecules.^10,11 Particularly, electrical conductivity, electrochemical, and percolation properties seemed to be crucial in enhancing the corrosion aspects of nanofibers.¹² Wide ranging applications of polymeric nanocomposite nanofibers with carbon/inorganic nanofillers may include electronics, optoelectronics, energy devices, antimicrobials, wound healers, and tissue engineering.^13,14,15,16

Another industrially viable research zone discovered for nanofibers and hybrid nanofibers includes radiation shielding performance.^17,18,19,20 Since, electromagnetic and nuclear radiations appeared as a major ecological pollution harming electronic device performance as well as living environments, so multifunctional nanofibers seemed to be promising to prevent these hazards.²¹ Hereagain, high performance nanofibers have been designed using inorganic and carbon nanoparticles.²² Accordingly, radiation shielding competences of nanofibers evidently rely upon structural, electronic, electrical, magnetic, and interfacial attributes.^23,24 Despite the significance of radiation shielding hybrid nanofibers in electronics, energy systems, defense, and aeronautic fields, a number of research challenges (process optimization, scalability, sustainability, biodegradability) have been encountered hindering their industrial scale implementations satisfying future green ecosystem.^25,26

Looking at the scientific state of nanofibers and hybrid nanofibers, present state-of-the-art review is designed (for the first time in the literature so far) aiming their corrosion and radiation defense characteristics, at one place. In this concern, designs, fabrication, microstructures, physical, and applied properties have been stressed for multifunctional nanocomposite nanofibers with inorganic and carbon nonreinforcements. Thus, this specific review aims to highlight the current state of multifunctional polymer nanocomposite nanofibers. To the best of knowledge, such specific review on nanocomposite nanofibers is not seen in literature before. The factual motivation behind this review is to report a ground-breaking and all inclusive article on the thriving physical and applied aspects of nanocomposite nanofibers as a future guide for field researchers. Surprisingly, only a few recent review articles dedicated to biological applications (tissue engineering, drug delivery) of nanocomposite nanofibers have been noted so far,^27,28 and no comprehensive review seen regarding wide ranging engineering applications of these materials for space, defence, corrosion protection, and radiation shielding industries. Although, recent research articles have been published on these high tech aspects of multifunctional nanocomposite nanofibers (as discussed in following sections of this manuscript); however, existing literature is not in a compiled and updated form. Subsequently, executing real world future and industrial level progressions in the field of nanocomposite nanofibers, are not possible for the concerned scientists/researchers before getting prior knowledge of the most recent literature in a well assembled form. As per our analysis, this comprehensive review will be certainly beneficial to further advance these next generation green multifunctional nanocomposite nanofibers for future sustainable high tech industries.

Polymer nanofibers and nanocomposite nanofibers

Recently, instead of using conventional polymers as films or coatings for high end applications, increasing scientific trends have been observed for employing nanostructured forms of polymers, like nanofibers or nanofoam architectures.²⁹ As compared to traditional polymers, polymeric nanofibers (submicronic fibers) have superior surface-to-volume ratio, higher aspect ratio, ease of surface functionalizations, and benefits of inducing nanoscale interactions in pristine polymers.³⁰ Additionally, conversion of polymers to nanoscale structures may positively affect the mechanical robustness, flexibility, electrical conductivity, optical features, wettability, heat stability, biocompatibility, and countless other physical aspects.³¹ Furthermore, the polymeric nanofibers also have ease of integration for technical systems or large sale industrial designs and engineering possibilities, relative to neat polymers. Along the same lines, polymeric nanocomposite nanofibers have been investigated for valuable structure-property-performance characteristics, as compared with the conventional polymeric nanocomposites; therefore technically preferred by the current field researchers.³²

Hence, polymer nanofibers and derived nanocomposite nanofibers have technically transformed the industrial scope of composites or nanocomposite materials.³³ Nanofibers of different shapes and textures (e.g., solid, hollow, flattened/ribbon like, wrinkled, core shell, etc.) have been reported hitherto from a variety of source polymeric matrices.³⁴ Generally, solid polymeric nanofibers with smooth surfaces have been considered efficient for deployments in high tech arenas.^35,36 Accordingly, thermoplastics, thermosets, conductive polymers, their copolymers, and blends have been used to fabricate pristine nanofibers or nanocomposite nanofibers.^37,38 In this regard, various synthesis techniques (like templating,³⁹ spinning,⁴⁰ solution or melt blowing,⁴¹ drawing,⁴² phase separation,⁴³ sol gel,⁴⁴ solution/chemical⁴⁵) have been practiced so far. Figure 1 displays some of the momentous nanofiber synthesis strategies. It has been observed that choice of fabrication strategy and optimization of processing conditions basically control the final structure and characteristics of the desired nanofibers or hybrid nanofibers.⁴⁸ As per scientific reports, spinning techniques have depicted remarkable success for designing high performance polymeric or nanocomposite nanofibers owing to easily controllable parameters and melt/solution precursors.^49,50,51 Nanofibers can be pristine unfilled polymeric nanofibers and secondly, nanoreinforced polymeric nanocomposite nanofibers. In the case of nanoscale polymer nanofibers, surface interactions and nanofiber-nanofiber interactions have been experiential leading to nanofibrous alignment, orientation, or crosslinking. In the case of nanocomposite nanofibers, matrix-nanofiller interactions have been observed as physical links (e.g., hydrogen bonding, crosslinking) or covalent interactions depending upon the functionalities of polymer and nanoparticles. Consequently, notable structural attributes of these one dimensional nanostructures may include superior surface/volume ratio, surface porosity, surface texture/evenness, microstructural contour, and the like.⁵² Moreover, physical properties, such as flexibility, electrical conductivity, dielectric feature, mechanical stability, heat resistance, thermal conductivity, and biological aspects have been focused for further technical considerations.^53,54,55

Figure 1.

Manufacturing procedures for nanofibers: (A) electrospinning; (B) phase inversion; (C) fiber drawing.⁴⁶ Reproduced with permission from Taylor and Francis; (D) melt blowing.⁴⁷ Reproduced with permission from Elsevier.

Herein, electrospinning method seemed to be the most dominating and successful fabrication route till now for high performance nanofibers.⁵⁶ This procedure employs a set up based on syringe (with needle), collector, and high voltage source.⁵⁷ Subsequently, solution/melt precursor evicted from the syringe needle forms nanofibers under electrostatic force effects, which are collected on the collector.⁵⁸ This method may generate nanofibers with diameters of few nm up to 100 nm.⁵⁹ Here, the resulting nanofiber texture and properties rely upon the specific electrospinning parameters.⁶⁰ A myriad of functional areas of electrospun nanofibers and hybrid nanofibers have been discovered to date, including aeronautics,^61,62 electronics and energy devices,^63,64 membranes,^65,66 textiles,⁶⁷ and medical zoned.⁶⁸ Figure 2 displays a multitude of applied field noticed so far for multifunctional nanocomposite nanofibers.

Figure 2.

Applications of polymer nanofibers and multifunctional nanocomposite nanofibers in industrial sectors.

Corrosion protection aspects of nanocomposite nanofibers

Recent research seems trending towards using carbonaceous or inorganic nanomaterials for effective protection of industrially viable metals, ceramics, etc., from harmful corrosion effects.⁶⁹ Accordingly, carbon nanomaterials, like carbon nanotube, graphene, fullerene, nanodiamonds, etc., and inorganic nanomaterials, such as metal, metal oxide, MOF, and MXene type nanoparticles have been used for corrosion protection.⁷⁰ Notably, corrosion prevention of metals by nanomaterials usually involves barrier effects and percolation phenomenon to prevent invasion of corrosion molecules through the desired surfaces.⁷¹

With advancements in the arenas of corrosion defense nanomaterials, one dimensional nanostructures, like nanofibers, revealed distinct performance advantages.⁷² In particular, superior surface area, nanostructural compatibility, structural robustness, and barrier attributes have been noticed for polymeric and hybrid nanofibers in erosion related environmental applications.^73,74 For efficient corrosion fortification of industrial structures, polymers as well as nanocomposite nanofibers have been extensively investigated for unique self healing effects.⁷⁵ Self healing phenomenon usually involves autonomous damage recovery under environmental influences, like shock, pressure, heat, light, etc.⁷⁶ In accordance, self healing nanofibers have been discovered more efficient towards corrosive damage repairs than traditional nanocomposite materials.⁷⁷ To enlighten self healing of macromolecules and hybrids, Figure 3(A) demonstrates probable self healing mechanisms, involving interdiffusion, phase separation, and shape recovery effects.⁷⁸ Moreover, Figure 3(B) presents roles of physical interactions and encapsulation/release of self healing agents in maintaining structural integrity of self healing nanostructures against corrosion occurrences. Subsequently, self healing nanofibers have been developed using a number of thermoplastics and thermosetting polymers for corrosion resistance deployments.^79,80

Figure 3.

Representation of probable self healing mechanisms including: (A) interdiffusion, phase separation, and shape memory characters; (B) van der Waals interactions and encapsulation/release of self healing agent.⁷⁸ Reproduced with permission from Nature.

According to today’s technological demands, self healing nanofibers and nanocomposite nanofibers appeared as the most valuable anticorrosion nanomaterials.^81,82 For example, An et. al.⁸³ formed self healing core shell nanofibers of poly (dimethyl siloxane) and polyacrylonitrile by coaxial electrospinning method (Figure 4(A)). This technique involves using two syringes simultaneously during electrospinning to generate core shell nanofiber nanostructures, which are collected on a collecting drum. Figure 4(B) and (C) illustrate scanning electron microscopy micrographs of core shell poly (dimethyl siloxane)/polyacrylonitrile blend nanofibers, before and after corrosion, respectively. After corrosion process, nanofiber surfaces showed small openings releasing poly (dimethyl siloxane) core resin. Moreover, Figure 4(D) displays electrochemical test set up and process used for analyzing self healing based anticorrosion performance of pristine poly (dimethylsiloxane) and core shell poly (dimethyl siloxane)/polyacrylonitrile blend nanofibers. According to outcomes, poly (dimethylsiloxane)/polyacrylonitrile blend nanofiberous coatings had better corrosion resistance, than that of the pristine poly (dimethylsiloxane) nanofibers. This effect can be attributed to the efficiency of coaxial electrospinning method and intrinsic healing properties of precisely designed core shell nanofibers.

Figure 4.

(A) (left) Coaxial electrospinning set up and (right) process for the formation of core shell nanofibers by two syringes simultaneously in coaxial electrospinning, where insets shows resulting sample and corresponding microstructure; (B and C) scanning electron microscopy micrographs of hybrid nanofiber samples after corrosion tests, at 0 and 5 min, respectively, where yellow circles show resin release points on nanofibers; (D) a snapshot of neat poly (dimethylsiloxane) and resin cure polyacrylonitrile nanofiberous coatings on steel substrate (before and after corrosion tests).⁸³ PDMS: poly (dimethylsiloxane); RC-PAN: resin cure polyacrylonitrile. Reproduced with permission from RSC.

Among hybrid nanofibers, inorganic nanofillers have been reinforced in matrices to form polymer/inorganic or metal nanoparticle based anticorrosion self healing nanofibers.⁸⁴ Initially, Nishimura et al.⁸⁵ studied anticorrosion performance of polyurethane coated aluminum nanoparticle hybrids. In accordance, Figure 5(A) shows the formation of polyurethane coating on aluminum nanoparticle surface. Figure 5(B) displays scanning electron microscopy micrographs of 3 and 10% coated aluminum nanoparticles, after corrosion tests of 0 and 7 days. The corrosion effect was observed by 20% reduction in the diameter of 10 wt% coated aluminum nanoparticle sample (after 7 days). On the other hand, in the case of 3 wt% coated aluminum nanoparticle sample, no reduction in diameter was observed. Consequently, Figure 5(C) demonstrates the effects of 1–10% coating contents on alumina nanoparticle sizes during corrosion test of 14 days. As per outcomes, increasing coating contents and time duration enhanced or retained the normalized surface areas of the nanocomposites. This trend reveals that higher polymer coating contents was almost 100% efficient to prevent the corrosion effects on aluminum nanoparticle surfaces.

Figure 5.

(A) Schematic for the formation of polyurethane coating on aluminum nanoparticles; (B) scanning electron microscopy images of 3 and 10 wt% polymer coated aluminum nanoparticles during corrosion test (0 and 7 days); (C) effect of 1–10% coating contents on the sizes of alumina nanoparticles during wet/dry corrosion test of up to 14 days (NaCl).⁸⁵ Reproduced with permission from MDPI; (D) neat epoxy, epoxy/graphene oxide, and epoxy/polyaniline/graphene oxide nanocomposite nanofibrous coatings after salt spray test of 450 h; (E) Bode-phase plots for the epoxy/polyaniline/graphene oxide nanofiber coating with defects and corrosion effects.⁸⁶ Reproduced with permission from Elsevier.

Recently, Xu et al.⁸⁷ designed core shell polyamide/silica nanofibers as anticorrosion coating for carbon steel substrate. It was observed that adding 1 wt% silica nanoparticles efficiently enhanced the tensile strength abrasion resistance self-healing efficiency by 15%, 33%, and 99%., respectively, relative to neat epoxy coatings. The notable performance was credited to matrix-nanoparticle synergies and self healing capabilities of core shell polyamide/silica nanofibers. A few similar studies can also be seen for self healing anticorrosion polyamide/silica nanocomposite nanofibers, in the literature to date.⁸⁸

Self healing anticorrosion polymer/graphene nanofibrous coatings have also been reported.⁸⁹ Dutta et al.⁹⁰ investigated anticorrosion performance of the epoxy/graphene nanomaterials using diffusion model studies. As per investigations, 1 wt% graphene loading in epoxy coating reduced the diffusion coefficient by a factor of 2.2, compared with that of the neat epoxy coating. It was suggested that dispersion of graphene in epoxy matrix efficiently developed interconnecting percolation network for better electron transfer and barrier effects for the prevention of corrosion processes. Hayatgheib et al.⁸⁶ studied the anticorrosion performance of neat epoxy, epoxy/graphene oxide, and epoxy/polyaniline/graphene oxide nanocomposite nanofibrous coatings on steel substrate. For this purpose, salt spray tests were performed by making 2 mm scars on metal surfaces, coating with desired nanomaterials, and performing salt spray test of 450 h. Figure 5(D) displays photographs of neat epoxy, epoxy/graphene oxide, and epoxy/polyaniline/graphene oxide nanocomposite nanofiber coated surfaces after. As per results, the epoxy/polyaniline/graphene oxide nanofiber coated surface showed lesser damaged area with blisters and delamination, relative to neat epoxy or epoxy/graphene oxide nanofiber coated samples. The superior anticorrosion performance of epoxy/polyaniline/graphene oxide nanofiber can be attributed to the involvement of in situ generated conducting polymer on graphene oxide surfaces causing better electrical conductivity and electrochemical performances, desirable for efficient corrosion protection. Next, Figure 5(E) shows Bode-phase plots for epoxy/polyaniline/graphene oxide nanofiber coated samples tested up to 120 h. According to the study, an increase in impedance was observed due to the presence of conjugated polyaniline with superior corrosion inhibition sites and barrier effects. Furthermore, Yu et al.⁹¹ reported graphene oxide reinforced cellulose nanofibers for corrosion protection coatings of stainless steel substrate. Herein, 40 wt% loaded nanofibers revealed fine anticorrosive features during prolonged corrosion tests of 1 week and more.

Besides, few reports can be seen regarding self healing anticorrosion coatings of polymer/carbon nanotube nanofibers.^92,93 For instance, Wang et al.⁹⁴ formed electrospun thermoplastic polyurethane nanofibers and coated with poly (dimethyl siloxane)/carbon nanotube hybrid using solution method. Owing to the synergistic effects between polyurethane-poly (dimethyl siloxane)-carbon nanotube phases, superior electrical conductivity, barrier, and superhydrophobic features were perceived.

Similarly, few scientific exertions have been noticed for self healing nanofibers and nanocomposite nanofibers of biodegradable polymers; thereby indicating future sustainable anticorrosion technologies for defense, space, and engineering sectors.^95,96,97

High performance nanocomposite nanofibers for nuclear/electromagnetic shielding

To eradicate the nuclear and electromagnetic interference related pollution hazards towards devices, living beings, and environment, polymer and nanocomposite shields have revealed technical worth.⁹⁸ Recently, in spite of using customary nanocomposites, one dimensional nanostructures of polymers and nanocomposites have attained notable research curiosities.^99,100 Actually, polymeric nanofibers and polymeric nanocomposite nanofibers own better capability to shield nuclear/electromagnetic interference, relative to pristine materials.^101,102,103 Subsequently, applications of nanofibrous shielding materials have been scrutinized for electronics, energy devices, and defense and space structures.^104,105 Mechanism of radiation shielding via nanomaterials usually involves phenomenon of reflection, multiple internal reflections, and absorption processes, as portrayed in Figure 6.¹⁰⁶ Out of all these processes, shielding mechanism of nanofibers or hybrid nanofibers seems to be directly related to impedance matching and absorption of nuclear/electromagnetic radiations.¹⁰⁷ Despite the efficiency of nanocomposite nanofibers as radiation defense shields, nanofiller dispersion in matrices may result in complex shielding mechanisms.¹⁰⁸ In other words. radiation shielding phenomenon critically depends upon electrical conductivity, dielectric properties, and magnetic permittivity of the polymeric or hybrid nanomaterials. For nanocomposites, adding nanoparticles has been observed to enhance the radiation shielding effectiveness of the matrices by enhancing surface-to-volume ratio, electron transfer, magnetic properties and the like. In this way, metallic nanofillers have been valuably explored to improve electromagnetic wave attenuation and radiation absorption features of polymeric matrices.

Figure 6.

A snapshot of basic mechanisms involved in electromagnetic (EM) interference shielding using nanomaterials.¹⁰⁶ Reproduced with permission from Elsevier.

As an important category of nanocomposite nanofibers, inorganic nanoparticles have been reinforced in polymeric matrices.^109,110 In a previous attempt, Ji et al.¹¹¹ manufactured silver nanoparticles filled polyacrylonitrile nanofibers by electrospinning and electroless deposition tactics. Owing to consistent dispersion of silver nanoparticles in polyacrylonitrile matrix, the resulting nanocomposite nanofibers depicted considerably high electrical conductivity and electromagnetic interference shielding effectiveness of ∼90 dB. Later, Özcan et al.¹¹² developed elemental boron doped poly (vinyl alcohol) nanofibers using electrospinning method. The poly (vinyl alcohol)/boron nanocomposite nanofibers were explored for microstructures, thermal stability, and neutron shielding properties. Figure 7(A) shows scanning electron microscopy micrograph for poly (vinyl alcohol)/boron nanoparticle (0.1 wt%) nanocomposite nanofibers. On smooth and aligned nanofiber surfaces, embedded boron nanoparticles of ∼240 nm were noticed. Figure 7(B) displays thermogravimetric analysis thermograms of the pristine poly (vinyl alcohol) nanofibers and poly (vinyl alcohol)/boron nanoparticle (0.1–0.5 wt%) nanocomposite nanofibers. As per results, a four stage weight loss was observed, including moisture removal (100°C), poly (vinyl alcohol) backbone breakage (230–350°C), carbonaceous oxidation (350–450°C), major nanocomposite degradation (450–850°C). Notably, higher boron doping contents of up to 0.5 wt% revealed superior thermal stability features, relative to neat nanofibers as well as other nanocomposite nanofiber compositions. It can be stated that elemental boron was remarkably competent to enhance the oxidation resistance of electrospun polymeric nanofibers. Additionally, Figure 7(C) scans neutron shielding competence of pristine metal, neat poly (vinyl alcohol) nanofibers, and boron doped poly (vinyl alcohol) nanocomposite nanofibers. Herein, adding 0.1–0.5 wt% of boron dopant content enhanced neutron absorption from ∼5.6% to ∼6.0%, relative to neat poly (vinyl alcohol) nanofiber (∼1.6%). Thus, the poly (vinyl alcohol)/boron nanocomposite nanofibers were observed as low weight, low density, and low cost solution for neutron shielding purposes.

Figure 7.

(A) Scanning electron microscopy image for poly (vinyl alcohol)/boron nanoparticle nanocomposite nanofibers; (B) thermal analysis results of pristine poly (vinyl alcohol) and boron doped (0.1–0.5 wt%) poly (vinyl alcohol) nanocomposite nanofibers; (C) neutron shielding of noncoated metal, pristine poly (vinyl alcohol), and boron doped (0.1–0.5 wt%) poly (vinyl alcohol) nanocomposite nanofibers.¹¹² PVA: poly (vinyl alcohol). Reproduced with permission from Wiley.

Zhang et al.¹¹³ reported polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers via electrospinning practice. Accordingly, Figure 8(A) illustrates scanning electron microscopy image of polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers. The micrograph showed uniform nanofibers having diameters, in the range of 20–30 nm. Figure 8(B) demonstrates a snapshot of probable electromagnetic interference shielding mechanism for polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers. Herein, dominating mechanisms include outer surface reflections and internal multireflections between nanofiber for efficient electromagnetic radiation absorption.

Figure 8.

(A) Scanning electron microscopy image of polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers; (B) schematic representation of the electromagnetic interference shielding mechanism for polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers; (C) The flexibility testing of the polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibrous membrane upon bending and folding; (D) Variation in the electromagnetic interference shielding effectiveness of the polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibrous membrane (frequency 8–26.5 GHz).¹¹³ P@Ni-Co: polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers; SE_T: shielding effectiveness by transmittance; SE_R: shielding effectiveness by reflection; SE_A: shielding effectiveness by absorption; EMI SE: electromagnetic interference shielding effectiveness. Reproduced with permission from Elsevier.

Figure 8(C) presents a photograph of actual polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibrous membrane sample showing fine structural flexibility. Furthermore, Figure 8(D) scans electromagnetic interference shielding effectiveness of polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibrous membrane (thickness ∼0.18 mm). Herein, the average and absolute electromagnetic interference shielding effectiveness features were observed ∼78 dB and >7300 dB cm² g⁻¹, respectively. Main reason for superior electromagnetic interference shielding seemed to be linked to enormously high electrical conductivity (∼1140 S cm⁻¹) of polyaniline/polyurethane/nickel-cobalt nanoparticle nanocomposite nanofibers. Hence, nickel-cobalt alloy nanoparticles key role to enhance the electrical percolation, dielectric, and permittivity properties of hybrid nanofibers.

As a most important type of nanofillers, carbonaceous nanoparticles have been reinforced in polymeric nanofibers, aiming radiation shielding application.^114,115,116 Guo et al.¹¹⁷ industrialized graphene nanoplatelets filled polystyrene nanocomposite nanofibers by electrospinning and cold/hot pressing strategies. Including 35 wt% of graphene nanoplatelets resulted in 11 times increase in electromagnetic interference shielding effectiveness of polystyrene nanocomposite nanofibers (33 dB), compared with the unfilled polystyrene nanofibers (3 dB). As per analysis, graphene nanoplatelets were capable of developing consistent electron conducting network throughout the matrix; thereby leading to superior electrical conductivity and radiation absorption properties. Yuan et al.¹¹⁸ formed core shell polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers by template based in situ and solution routes (Figure 9(A)). The magnetite-silica nanofibers were used as a template as well as core material, whereas polypyrrole formed shell by in situ and solution processes. Figure 9(B) shows transmission electron microscopy micrograph of polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers. Here, dispersed magnetite nanoparticles can be seen on nanofiber surfaces. Figure 9(C) depicts scanning electron microscopy micrograph of fracture surfaces of core shell polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers. Distinct core shell boundaries can be seen with internal reduced graphene oxide/magnetite-silica and outer polypyrrole shell. Moreover, Figure 9(D) demonstrates a comparison of electromagnetic interference shielding effectiveness of polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers (9 GHz). The electromagnetic interference shielding effectiveness was analyzed in terms of transmittance, reflection, and absorption characteristics. An absorption dominant electromagnetic interference shielding mechanism was observed with >87 % contribution to the over all effectiveness. Accordingly, Figure 9(E) suggests an overview of the electromagnetic interference shielding mechanism involved.

Figure 9.

(A) Schematic for the formation of core shell polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers; (B) transmission electron microscopy image polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers; (C) scanning electron microscopy image of fracture surfaces of core shell nanocomposite nanofibers; (D) comparison of electromagnetic interference shielding effectiveness performance of polypyrrole/reduced graphene oxide/magnetite-silica nanoparticle nanocomposite nanofibers (9 GHz); (E) electromagnetic interference shielding mechanism of nanocomposite nanofibers.¹¹⁸ GO: graphene oxide; rGO: reduced graphene oxide; Fe₃O₄: magnetite; PPy: polypyrrole; Fe₃O₄@SiO₂: magnetite-silica nanoparticles; SE_T: shielding effectiveness by transmittance; SE_R: shielding effectiveness by reflection; SE_A: shielding effectiveness by absorption; EMI: electromagnetic interference shielding. Reproduced with permission from Elsevier.

In recent years, Kim et al.¹¹⁹ fabricated electrospun polyacrylonitrile nanofibers reinforced with carbon nanotubes for electromagnetic interference shielding application. Figure 10(A) displays fabrication of electrospun polyacrylonitrile nanofibers, carbon nanotube bucky paper, and derivative nanocomposite membranes by electrospinning, thermal rolling, and vacuum assisted filtration methods. Figure 10(B) a & b (surface and cross section, respectively) show scanning electron microscopy images of polyacrylonitrile nanofibers and carbon nanotube buckypaper based membrane (annealing 130°C). The buckypaper and nanofiber based membrane exhibited a unique layered nanofibrous nanostructure. Additionally, Figure 10(B) c & d illustrate photographs (top and bent views) of the nanocomposite membrane. Figure 10(C) shows an interfacial view of polyacrylonitrile nanofibers and carbon nanotube bucky layers used for electromagnetic interference shielding. Figure 10(D) depicts a comparison between the specific shielding efficiency/thickness of the as designed polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane with literature reported radiation shielding nanocomposites^{120,121,122,123,124,125,126}). Consequently, polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane displayed superior specific shielding efficiency/thickness (13,734 dB cm² g⁻¹/100 μm), than that of the previously reported polystyrene, polypropylene, poly (methyl methacrylate), acrylonitrile-butadiene-styrene, polycarbonate, waterborne polyurethane, and bisphenol based nanofibrous systems.^{120,121,122,123,124,125,126} The overall superior radiation shielding efficiency of polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane can be attributed to the unique design combination of one dimensional nanostructures with carbon nanoparticles.

Figure 10.

(A) Designing of electrospun polyacrylonitrile nanofibers filled with carbon nanotubes and derived nanocomposite buckypaper membranes; (B) (a & b) scanning electron microscopy micrographs (surface and cross section, respectively) of polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane annealed at 130°C; (c & d) (top and bent views) of polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane; (C) (left) interfacial structure and (right) electromagnetic interference shielding mechanism of polyacrylonitrile nanofibers/carbon nanotube buckypaper membrane; (D) comparison between specific shielding efficiency/thickness of the hybrid membranes (annealed at different temperatures) with the reported (Refs. 120–126) equivalent systems.¹¹⁹ MWCNT: multi walled carbon nanotube; BP/NF: carbon nanotube bucky paper and polyacrylonitrile nanofibers based membrane; BP: buckypaper; NF: nanofiber; SSE/t: specific shielding efficiency/thickness; PS: polystyrene; PP: polypropylene; PMMA: poly (methyl methacrylate); ABS: acrylonitrile-butadiene-styrene; PC: polycarbonate; WPU: waterborne polyurethane; BP: bisphenol. Reproduced with permission from ACS.

Anju et al.¹²⁷ fabricated poly (vinyl alcohol)/polyaniline/carbon nanofibers and hybrid membranes using electrospinning and solution casting methods. The nanocomposite nanofibrous system had valuable electromagnetic shielding effectiveness and specific electromagnetic shielding efficiency of ∼34 dB and ∼177 dB cm³/g, respectively.

Into the bargain, a few more literature efforts have been noticed for polyurethane, epoxy, and cellulose based nanofibrous materials revealing nuclear and electromagnetic interference shielding competence.^128,129,130

Existing outlook and future applications

As conversed in above sections of this article, multifunctional nanofibers and nanocomposite nanofibers form a unique class of one dimensional nanomaterials with valuable structure-characteristics-applications attributes. More to the point, this novel field review focuses three important aspects of nanofibrous nanostructures as:

(i) High performance polymeric nanocomposite nanofiber designs with superior integrity, corrosion resistance, and related high end properties (as summarized in Table 1).¹³¹

(ii) Relevant exploration of self healing potential of hybrid nanofibers for next level industrial applications.¹³²

(iii) Nanocomposite nanofibrous materials with nuclear and electromagnetic shielding competence for technical engineering structures (as potted in Table 2).¹³³

Table 1.

Specifications of corrosion protective nanocomposite nanofibers with inorganic and carbonaceous nanofillers.

Nanofiber matrix	Nanofiller	Fabrication	Physical properties/application	Ref.
Poly (dimethyl siloxane); polyacrylonitrile	-	Coaxial electrospinning method	Core shell microstructures, intrinsic self healing; superior anticorrosion performance than pristine homopolymer nanofibers	⁸³
Polyurethane	Aluminum nanoparticle	Solution/coating routes	1–10% polymer coating contents; microstructures with reduction in diameter after corrosion test; 100% corrosion resistance with higher nanoparticle loading	⁸⁵
Polyamide	Silica	Electrospinning technique	1 wt% silica nanoparticles; increase in tensile strength and abrasion resistance by 15% and 33%, respectively; self-healing anticorrosion efficiency 99%	^87,88
Epoxy	Graphene	Electrospinning tactic	Diffusion model studies for anticorrosion assessments; 1 wt% graphene loading; reduced diffusion coefficient; interconnecting percolation network; efficient electron transfer; barrier effects; by a factor of 2.2, than neat epoxy	⁹⁰
Epoxy; epoxy/polyaniline	Graphene oxide	Electrospinning route	Salt spray tests (450 h); 2 mm scars on metal surfaces; lesser damaged area with blisters and delamination, relative to neat epoxy; Bode-phase plots; increase in impedance properties	⁸⁶
Cellulose	Graphene oxide	Electrospinning process	40 wt% loaded nanofibers; prolonged corrosion protection >1 week	⁹¹
Thermoplastic polyurethane; poly (dimethyl siloxane)	Carbon nanotube	Electrospinning/solution methods	Superior electrical conductivity, barrier properties; superhydrophobicity; corrosion defiance	⁹⁴

Table 2.

Stipulations of radiation shielding hybrid nanofibers with inorganic and nanocarbon nanoadditives.

Nanofiber matrix	Nanoadditive	Manufacturing	Physical attributes/applications	Ref.
Polyacrylonitrile	Silver nanoparticles	Electrospinning; electroless deposition tactics	High electrical conductivity; electromagnetic interference shielding effectiveness ∼90 dB	¹¹¹
Poly (vinyl alcohol)	Elemental boron	Doping/electrospinning methods	Smooth and aligned nanofibers; surfaces, boron nanoparticles ∼240 nm; major thermal decomposition 450–850°C; oxidation resistance; 0.1–0.5 wt% boron dopant; enhanced neutron absorption from ∼5.6 % to ∼6.0%, than neat poly (vinyl alcohol) nanofiber (∼1.6%); low weight; low density; low cost neutron shield	¹¹²
Polyaniline; Polyurethane	Nickel-cobalt alloy nanoparticles	Electrospinning route	Uniform nanofibrous microstructures; diameters ∼20–30 nm; radiation shielding mechanisms via outer surface reflections/internal multireflections/radiation absorption; structural flexibility; shield thickness ∼0.18 mm; average electromagnetic interference shielding effectiveness ∼78 dB; absolute electromagnetic interference shielding effectiveness >7300 dB cm² g⁻¹; electrical conductivity ∼1140 S cm⁻¹	¹¹³
Polystyrene	Graphene nanoplatelets	Electrospinning; cold/hot pressing strategies	35 wt% graphene nanoplatelets; 11 times increase in electromagnetic interference shielding effectiveness of nanocomposite nanofibers (33 dB), compared with unfilled nanofibers (3 dB)	¹¹⁷
Polypyrrole	Reduced graphene oxide/magnetite-silica nanoparticle	Template technique; in situ method; solution route	Core shell microstructures; transmittance, reflection, and absorption based electromagnetic interference shielding mechanisms; higher radiation absorption contribution >87% to overall electromagnetic interference shielding effectiveness	¹¹⁸
Polyacrylonitrile	Carbon nanotubes	Electrospinning process	Nanofibers and nanocomposite buckypaper membranes; superior specific shielding efficiency/thickness of ∼13,734 dB cm² g⁻¹/100 μm, than previously reported polystyrene, polypropylene, poly(methyl methacrylate), acrylonitrile-butadiene-styrene, polycarbonate, waterborne polyurethane, and bisphenol based nanofibrous systems^{120,121,122,123,124,125,126}	¹¹⁹
Poly(vinyl alcohol; Polyaniline	Carbon nanofibers	Electrospinning; solution casting methods	Electromagnetic shielding effectiveness ∼34 dB; specific electromagnetic shielding efficiency ∼177 dB cm³/g	¹²⁷

Figure 11 shows a scheme portraying design—to—features—to-—industries/future aspects of polymer nanofibers and polymer nanocomposite nanofibers. In these scientific meadows, polymer nanofibers and hybrid nanofibers accomplished noteworthy research curiosities. Not unlike customary polymers or nanocomposites, these property-performance relationships depend upon the type of polymeric materials, nanoadditives (nanocarbons or inorganic), nanofiller contents, synthesis techniques, and synthesis parameters. Accordingly, a number of thermoplastic, thermosetting, and conductive matrices have been employed along with carbonaceous (graphene, graphene oxide, carbon nanotube, fullerene, and the like) and inorganic (metal, metal oxide, silica, titania, magnetite, and more) nanofillers. The final texture of as designed nanofibers, shape of nanofibers (smooth, round, flattened, wrinkled) also affect the overall integrity of nanofibrous materials. Particularly, explicit characteristics of multifunctional nanofibers and nanocomposite nanofibers seem to be reliant on microstructural contours, interfacial compatibility, and nano-level interactions. Herein, the most preferred practices for multifunctional nanofibers and nanocomposite nanofibers include spinning techniques, like electrospinning. As proved by wide ranging literature reports to date, electrospinning can be named as one of the most frequently used synthesis method for these one dimensional nanostructures.

Figure 11.

Corrosion protection, radiation shielding and industrial scenarios of polymer nanocomposite nanofibers.

First essential technical application of hybrid nanofibers covered in this article pertains to corrosion resistance. In general, electrical conductivity of nanofibers significantly reduce the electrical resistance, so allowing efficient current flow through the system. In this regard, choice of appropriate conductive matrices and carbon or metal nanoparticles were proved to be efficient to improve electrical percolation/conductivity, electrochemical behavior, and corrosion confrontation by overcoming the surface defects and overpotential. Another important application of nanofibrous nanomaterials is the nuclear shielding and electromagnetic interference shielding efficiencies. The radiation absorption features of these nanostructures visibly depend upon superior electrical conductivity features. Actually, electron conduction through percolation networks of the nanomaterials supports magnetic field strength, which is desirable for radiation defense purposes. For this purpose, research trends have been observed for using conjugated polymers and conductive nanocarbon phases to form advanced nanofibrous nanomaterial based shields. Herein, uniform nanoparticle dispersion and interactions (van der Waals, hydrogen bonds, electrostatic) with macromolecular chains have brought about valuable features for engineering grade radiation protective hybrid nanofibers.

Looking at the current anticorrosion and antiradiation research scenarios, various research gaps have been identified for successful implication of nanocomposite nanofibers in anticorrosion coatings and radiation defense shields. Firstly, the use of electrospinning technique for nanofiber formation has disadvantages of improper and undefined nanofiller dispersion, processing expense, and lack of predefined processing parameters for reproducibility. Poor nanofiller dispersion in turn may disturb nanofiber surface texture, quality, matrix-nanofiller synergies, interfacial adhesion, and desired high end properties (especially electrical conductivity and percolation networking) and applications. To overcome these fabrication related encounters, modified spinning techniques need to be devised with facile optimization of parameters for industrially demanded reproducibility. Oher challenges can be listed as the lack of dedicated theoretical investigations for accurate understanding of corrosion and radiation defiance mechanisms. In addition, very few scientific articles seen so far regarding the development of green, biodegradable, and sustainable nanofibrous designs in these areas.^31,133 Use of ecological materials and life cycle assessments for hi-tech nanofibers may open future paths for sustainable and reproducible multifunctional industrial scale prototypes.

Although, this review is dedicated to the technical significance of radiation shielding and anticorrosion polymeric nanocomposite nanofibers, however, these high performance materials can be beneficially used to further expand the industrial level significance of nanocomposites for aerospace, defense, electronics, and energy industries.¹³⁴ In nanofibrous form, polymeric nanocomposites can better stand out for their exceptional potential to protect against space radiations, as compared with the conventional hybrids.¹³⁵ As discussed in former sections of this review, nanocomposite nanofibers can offer an innovative approach to overcome the challenges faced by traditional polymeric materials, so demonstrating notable radiation absorption/scattering, anticorrosion, flexibility, lightness, durability, and heat stability for the development of protective clothing and equipment. Polymer nanocomposite nanofibers can therefore offer superior attenuation/shielding for neutrons, gamma rays, and ionized photons.¹³⁶ All these features ensure structural integrity (mechanical, thermal, corrosion) and shielding performance of nanocomposite nanofibers based aerospace structures during space missions involving intense radiations and extreme environmental conditions.¹³⁷

In defense sector, polymer nanocomposite nanofibers, can be valuably integrated into multifunctional structures for crewless aerospace vehicles.¹³⁸ In addition, hybrids nanofibers have been intended to offer remarkable fatigue/fracture and extreme temperatures resistances; thereby, enhancing ballistic features for designing military armaments.¹³⁹ Moreover, woven or non-woven nanocomposite nanofibers can be applied as durable materials in vehicle liners, gas tight containers, fuel containers to replace traditional polymers or rubbers.¹⁴⁰ Further recompenses of robust, lightweight and flexible polymer nanocomposite nanofibers in defense sectors include high strength military suits and body armors to stop bullets, intelligent attires to monitor vital signs, and protection from environmental effects.^141,142

In electronics and energy sectors, increasing global use of devices in industries, vehicles, home appliances, communication systems, and countless portable devices led to an irrefutable necessity of high performance radiation shielding materials to protect these manoeuvrers from internal and external radiation hazards.¹⁴³ In this concern, competent electromagnetic/nuclear shielding nanofibers based on conductive polymers have been observed competent to protect electronics/energy devices by blocking or grounding the undesirable radiations.¹⁴⁴ Consequently, it is necessary for all the electronic designers/engineers to have a beforehand knowledge of device sensitivity from outer and inner radiations. Notably, focused future exertions and expert solutions seems indispensable for choosing appropriate shielding materials, like nanocomposite nanofibers, to design reliable and outperforming industrial scale electronics and energy systems.

Conclusions

Downright, this radical review article outlines the potential of polymeric nanofibers and derived hybrid nanofibers for anticorrosion and radiation shielding applications. In this concern, specifications of innumerable nanocarbon and inorganic nanofiller filled nanofiber designs have been reviewed, in the light of recent research reports. For these corrosion and radiation defense applications of advanced nanofibers, microstructures, electron transference, self healing, barrier, percolation, structural integrity, dielectric, permittivity, shielding effectiveness, and related physical attributes of distinct nanofiber designs have explored. According to the literature reports hitherto on anticorrosion and radiation shielding nanocomposites, we came to following concluding remarks regarding these materials.

(i) Nanocarbons (carbon nanotube, graphene, graphene oxide, reduced graphene oxide), inorganic (silica, silver, aluminium, cobalt), as well as hybrid organic-inorganic nanoreinfocements revealed invaluable aspects for anticorrosion and radiation shielding applications.

(ii) Use of conjugated polymeric matrices (polyaniline, polypyrrole, or blends with thermoplastics) for nanofibers was noticed to remarkably enhance the electrical conductivity properties desirable for corrosion and radiation n protection applications.

(iii) Electrospinning has appeared as the most widely employed technique for the fabrication of high performance nanocomposite nanofibers for technical utilizations.

(iv) For industrial level radiation shielding applications, corrosion resistance and mechanical durability appeared as equally important factors as radiation attenuation/absorption.

(v) No focused scientific endeavours seen so far regarding the use of ecological green polymers, green nanoadditives, ecological processing routes, and sustainability and life cycle assessments for radiation defensive nanocomposite nanofibers.

Eventually, multifunctional nanofibers and nanocomposite nanofibers appeared as a scorching area of research for future sustainable high tech devices and aeronautical grade engineering structures. Notwithstanding, the scientific progress hitherto, industrial level demands for precise designs, optimized synthesis, reproducibility, scalability, economics, sustainability, and environmental need to be considered yet. Owing to all inclusive coverage of fundamentals to specific applications and field challenges of nanofibers, this ground-breaking manuscript will definitely serve as a valuable source for scientific literates towards future green industrial revolutions.

Footnotes

Declaration of conflicting interests

The author declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding

The author received no financial support for the research, authorship, and/or publication of this article.

ORCID iD

Ayesha Kausar

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Polymer nanofibers to multifunctional nanocomposite nanofibers—transfiguring corrosion protection and radiation shielding capacities

Abstract

Keywords

Introduction

Polymer nanofibers and nanocomposite nanofibers

Corrosion protection aspects of nanocomposite nanofibers

High performance nanocomposite nanofibers for nuclear/electromagnetic shielding

Existing outlook and future applications

Conclusions

Footnotes

Declaration of conflicting interests

Funding

ORCID iD

References