Polymer Hybrid Nanocomposite Fibres
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Advancement in material sciences towards manufacturing facilities, interface engineering technologies, and analytical tools has enabled the researchers to explore the nanomaterials to form variety of polymer and polymer hybrid composites with novel structures and applications. This chapter presents a comprehensive study about polymer and hybrid nanocomposite fibres for academic and industrial research purposes. “Polymer hybrid nanocomposites” are a fascinating class of materials that combine polymers with other materials where one of the phases has nano-dimension to enhance optical, electrical, magnetic, and thermal properties. These materials can be fabricated as gel, particles, film, or fibres. Hybrid nanocomposites have shown a wide range of applications in the area of sensors, display, catalysts, energy storage and generation, filters, and separators.
The chapter begins with an introduction to polymer and polymer hybrid fibres followed by synthesis and characterization of different inorganic or organic material as well as their thermal, optical, electrical, and magnetic properties. It also reviews the preparation routes of polymer hybrid nanocomposite fibres with a detail analysis of physical and chemical properties for various applications such as energy and environment. It also discusses the current challenges in the area with perspectives on the new and futuristic application.
This chapter can provide a platform to the readers to get a better understanding of the basic methods and experimental procedure for synthesis, characterization, and applications of the polymer hybrid nanocomposite fibres.
KeywordsFibres Polymers Hybrid Composites Nanofibres
The fibres are elongated material with a high aspect ratio and some other unique features which make them interesting for many applications in textile, home furnishing, biomaterials, and composites (Jayaraman et al. 2004). The formation, structure, and properties of fibres are fundamental aspects to know details of fibre science, and a variety of synthetic fibres have been prepared since the last century such as polymer, carbon, silica, composites, etc. (Fourné and Hergeth 1999).
Depending on the base of their origin or structure, the fibres can be divided in different categories (Gohl and Vilensky 1983). Typically, the textile fibres are simply classified in natural and man-made fibres. The natural fibres are further divided into animal, vegetable, and mineral fibres. On the other side, the man-made fibres, also called artificial fibres, branch into polymer and non-polymer fibres. Usually, the polymer fibres are produced from low molecular weight substances converted into fibres at high pressure and temperature in the presence of catalysts. The polymer fibres are further divided into synthetic and natural polymer while non-polymer fibres into glass fibres, carbon, ceramic fibre, or metal fibre depending on the type of materials used. These fibres have been extracted by mechanical, (Deshpande et al. 2000) chemical, (Rao and Rao 2007) and water retting processes (Cater et al. 1974). Different morphologies, structures, and properties of the fibres can be achieved by these methods. The fabrication of hybrid fibres is always interesting because of better chemical, mechanical, and thermal properties of the hybrid materials compared to parent materials. The hybrid fibre can be a combination of organic with organic or inorganic materials depending on the end use of product. In recent time, different types of hybrid fibres have been synthesized including elastomeric fibres, core-sheath bicomponent fibres, lyocell fibres, stimuli-responsive fibres, and liquid crystal fibres. Polymer hybrids are multifunctional materials having two or more than two components in which one of the constituents is polymer. Polymer hybrid fibres have potential functional application in textile, households, and automotive industries.
This chapter emphasizes on the synthesis, characterization, and application of polymer and polymer hybrid fibres. The innovative polymer hybrid fibres can be prepared by versatile and cheap spinning techniques such as melt, wet, dry, and gel spinning (White and Cakmak 1986; Yudin et al. 2014; Anton 1944; White and Hancock 1981). Spinning method depends on the polymer characteristics and required fibre properties. However, these spinning methods can produce the fibre diameters in the micrometer range. In order to synthesize fibres in the nanometer range, a number of techniques such as self-assembly, template synthesis, phase separation, and electrospinning have been introduced (Huang et al. 2003). The increased surface area of nanofibres can make them an optimal candidate for many practical applications.
Fibre Formation Technology
Polymer and polymer hybrid fibres are prepared by spinning the polymer. The polymer molecule must move independently with one another to start the manufacturing of the fibre. Therefore, first polymer must be converted into a liquid or semisolid state either by heating until molten or by dissolving in a solvent. The polymer can be in either melted form or solution form depending on the polymer or manufacturing process (Ziabicki 1976). The resulting liquid is extruded through a spinneret to form a polymer fibre. The solvent is evaporated from the final spanned fibre.
Gel spinning is also known as semi-melt spinning process. The higher-strength fibres are manufactured from a solution of extremely high molecular weight (above 600 kg/mol) polymer in a solvent at low concentration (1–2%). It makes polymer in gel phase, and the polymer chains can be stretched to form highly oriented fibre of high strength (Kuo and Lan 2014). Gel spinning contains three steps: dissolution, spinning, and drawing. High stiffness polyethylene, PVA, and aramid fibres are produced via gel spinning.
Various hybrid nanocomposite fibres have been developed by combining synthetic fibres with natural fibres, metallic nanoparticles, epoxy or carbon fibres, etc. In the next section, some synthetic fibres especially polyolefin, polyacrylic, polyesters, polyamide fibres, and their nanocomposites fibres are discussed in more detail.
Polyolefin Nanocomposite Fibres
The olefin fibres are generally manufactured by melt spinning, and melted polymer is extruded through spinneret into fibre. Ultrahigh molecular weight polyethylene (UHMWPE) fibre is prepared by gel spinning process, and it has high strength with excellent mechanical properties (Weedon et al. 2005).
Polyolefin fibres can be combined with carbon nanotubes, natural fibres, or metallic particles in order to make polyolefin hybrid fibres. The synthesis of carbon nanotube-polyolefin composite fibre can enhance their performance and functionality in terms of better mechanical and conductivity properties (Liu and Kumar 2014). These hybrid fibres are manufactured from melt spinning, electrospinning, and solution spinning processes. Polypropylene fibres that are mixed with natural fibres such as flex or hemp can introduce biocompatibility and biodegradability to improve high mechanical properties, decrease cost, density and acoustic insulating properties. The combination of olefin fibre with metal significantly reduced the free shrinkage of hybrid fibre (Mesbah and Buyle-Bodin 1999).
Polyester Composite Fibre
Hybrid polyester fibres are formed by combining polyester fibres with natural fibres or metals, to produce a cloth with blended properties. Mixing with natural fibres increases their biodegradability, lightness, and favorable mechanical properties. For example, cotton-polyester blends (polycotton) can be strong, wrinkle-free, and tear-resistant and reduce shrinking (Harper et al. 1986). Higher-strength pineapple polyester composite fibre with varying fibre length and fibre volume fraction was fabricated by hand layup method (Devi et al. 1997). A modified electrospinning and wrapping system was used to fabricate polyester staple yarns nanowrapped with polysulfone amide fibres to improve mechanical, thermal, and hygroscopicity properties (Tong and Bin-Jie 2015). Surface properties of the polyester composite fibres have been modified using cellulose nanocrystal (Huang et al. 2017).
Polyamide and Composite Fibres
In order to obtain specific property, polyamide fibres can be combined with glass, carbon fibres, natural fibres, clay, or metals. Significant improvements in modulus, moisture resistance, and fast crystallization were achieved in polyamide-glass fibre composites (Akkapeddi 2000). To get additional mechanical properties of carbon reinforcement/polyamide composites, interfacial polymerization and hot compression molding techniques were employed (Botelho et al. 2003). Antimicrobial activity in the electrospun nylon nanofibres can be introduced by doping with silver ions (Cheng et al. 2018).
Large categories of metal-doped acrylic hybrid fibres have been fabricated by using electrospinning method. Different metallic nanoparticles (Ag, Pd, Au), bimetallic nanoparticles (Ag/Au, Ag/Pd), metallic oxide nanoparticles, and metal chloride nanoparticles embedded into acrylic fibre using photochemical reaction, microwave radiation, and gas solid reactions. The hybrid nanocomposites have lots of potential applications in electronic and sensing devices, gas phase catalytic applications, and conductivity enhancement (Qiao et al. 2018; Nirmala et al. 2012).
Characterization Techniques for Polymer Nanocomposite Fibres
Various characterization techniques are available to understand and explore the physical, mechanical, thermal, and chemical properties of polymer nanocomposite fibres. Physical characterization techniques especially scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are commonly used for evaluating the microstructural parameters of polymer nanofibres such as diameter, orientation, shape, and surface roughness. Mechanical properties are used to evaluate the impact of nanoparticles on the mechanical properties of polymer composites and are obtained by using ultimate tensile machine, dynamic mechanical analysis (DMA) measurements, and tensile testing. Generally, the elastic modulus of the sample is used to understand the behavior of the composites under mechanical stress. The thermal behavior of these composites can be studied using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).
Another technique is atomic force microscopy which is used to get the high-resolution three-dimensional image of the sample surface which is reconstructed from the intermolecular force of attraction between the sample and tip when it is moved in close proximity of the sample. It can be operated in different modes, i.e., contact, semi-contact, force modulation, and frictional force, to get the information about the fibres especially conformational and chain order, crystalline order, and polymer crystals. By controlling the force to deform the surface, it can also be used to understand the mechanical properties of the fibres. One of the major advantages of AFM is that it does not require vacuum environment and can operate in wet condition.
The insulating polymer can be made conductive by using nanoparticles for electronics and electrical applications. Electrospun nanocomposite fibres of poly(methyl methacrylate) and single-walled carbon nanotubes have shown significant improvement in the electrical conductivity compared to the polymer (Sundaray et al. 2008). MXene, a recently discovered family of two-dimensional (2D) transition metal carbides and/or nitrides is used to modify the electrical properties of the polymer film. It has been observed that a small percentage (1%) of Ti3C2Tx increases the electrical conductivity of poly(acrylic acid) (PAA), PEO, poly(vinyl alcohol) (PVA), and alginate/PEO nanofibres.
Most polymers exhibit low electrical conductivity; however, in the presence of conductive inclusions such as carbon nanotubes, graphene, or metal nanoparticles, e.g., gold or silver, the electrical conductivity can be increased. It was observed that resistance of the PVP fibres was decreased in the presence of MWCNT inclusions, and it was reduced from 50 MΩ to below 5 MΩ, which may be attributed to the higher electrical conductivities of CNT and fewer voids under the applied loads (Khan et al. 2013). The variation of electrical resistance of 1% SWCNT loading in PMMA at different temperatures was observed, and temperature-dependent electrical resistance shows 1-D VRH type conduction mechanism above room temperature (300 K) (Sundaray et al. 2008). One dimensional arrays of ordered electroactive nanostructures of crystallinepristine C60 and phenyl-C61-butyric acid methyl ester coated onto supramolecular fibres based on pentapeptides has been fabricated to make efficient photo-active materials (Alberto Insuasty et al. 2015)
Applications of Polymer Nanocomposite and Fibres
In the previous sections, we discussed the preparation and properties of some synthetic fibres especially polyolefin, polyacrylic, polyesters, polyamide, and its hybrid forms, which have potential applications in textile, households, and automotive. This section will follow applications of these synthetic fibres. Polyolefin fibres are having two important polymers, i.e., polyethylene and polypropylene. From these two, polyethylene fibres have found applications in twines and nets, ropes, cut and puncture resistance, and ballistic protection. On the other side, polypropylene fibre finds its utility in hygienic applications like food packaging, filters, diapers, automotive parts, hygiene bands, surgical masks, and medical devices. Polypropylene fibres also have applications in carpet backing, geotextiles, and upholstery fabrics, but applications of polypropylene fibres are limited in the apparel sector of the textile industry due to inability of polypropylene fibres to be colored by conventional dyeing techniques used for other synthetic fibres. This is due to polypropylene fibres’ nonpolar nature, high crystallinity, and lack of functional group to hold dye molecules. This is the reason why most of the commercially available polypropylene fibres are colored by mass pigmentation (Anand and Horrocks 2016). Polyolefin fibres also have limited applications in high-temperature engineering due to their low melting temperature and mechanical properties, which can be enhanced by doping of carbon nanotubes, nanosilicates, and nanosized metal oxides to make nanocomposite fibres (Ugbolue 2017).
Polyester or polypropylene fibres are mixed with neutral fibres to prepare hybrid fibres. Due to their better properties like lightweight, low cost, and easy processing, these fibres are advantageous. Some applications are as follows: in electric devices it is used for electrical appliances, pipes, etc.; in household, it is used for making table, shower, chair, bath units, etc.; in building and construction industry, it is used for making partition boards, floor, panels for partition and false ceiling, roof tiles, window and door frames, wall, etc.; in everyday applications, it is used to make suitcases, lampshades, helmets, etc.; in transportation industry, it is used for making boat, automobile and railway coach interior, gears, etc.; and in storage devices, it is used for making biogas containers, postboxes, grain storage silos, etc. (Sathishkumar et al. 2014). Mechanical strength of polypropylene is not good enough for engineering plastics that can be enhanced by mixing with multiwalled nanotubes (MWNTs) (Li 2017).
Polymers (polyamide, polyethylene, polypropylene, polystyrene, polyarylacetylene) embedded with nanoclays, montmorillonite, organically modified montmorillonite, Fe2O3 particles, carbon nano tube (CNT), single-walled nanotubes, multiwalled nanotubes, nano carbon fibre, nanoparticles of SiO2 and SiC to make nanocomposite hybrid fibres and have applications in medical field for the cure of wounds and burns of a humanoid skin, and also used to designed hemostatic procedures and devices with specific features. These biodegradable polymers fibres can directly be sprayed/spun on to the injured area of the skin to form a fibrous mat dressing, which can help the wounds to heal quickly and reduce the formation of scar tissue.
Moreover, these hybrid nanofibres can also be used in pulp and paper industry for making high-value printing and barrier packaging (Kamel 2007); in military protective clothing for minimal impedance to air, efficiency in trapping aerosol particles, and anti-biochemical gases; in filter media for liquid filtration, gas filtration, and molecule filtration; in nano-sensors for thermal sensor, piezoelectric sensor, biochemical sensor, and fluorescence optical chemical sensor; in tissue engineering scaffolding for porous membrane for skin, tubular shapes for blood vessels and nerve regenerations, and three-dimensional scaffolds for bone and cartilage regenerations; and in other industrial applications for micro-/nanoelectronic devices, electrostatic dissipation, electromagnetic interference shielding, photovoltaic devices (nano-solar cell), LCD devices, ultra-lightweight spacecraft materials, and higher efficient and functional catalysts (Saba et al. 2014).
Polyester fibre is an environmental friendly product that does not generate harmful gases such as dioxin or furan when burning. Moreover, the high mechanical strength, high quality, and good durability make polyester fibre ideal for high-stress outdoor uses. It is also hydrophobic in nature, wrinkle-free, and strain-resistant. It is used in the manufacturing of all kinds of clothes like pants, tops, skirts, and suits; in home furnishings such as bedspreads, sheets, pillows, furniture, carpets, and curtains; and for ropes, thread, hoses, sails, floppy disk liners, power belting, etc. Additionally, by making hollow polyester fibres, it is also possible to make insulation into the polyester fibre. The body is kept warm in winter season; when air is trapped inside these hollow fibres, it is warmed by the body heat (Khoddami et al. 2009). The polyester composite materials with natural fibres have high strength, high stiffness, high corrosion resistance, and lightweight and find its applications in construction, marine, electrical, household appliances, sporting goods, etc. (Athijayamani et al. 2010). Also polyester with natural fibre (kenaf, hemp, flax, jute, and sisal)-based nanocomposite are finding applications in automobile industries due to the following advantages, i.e., reductions in weight, cost, and CO2 emission (Holbery and H 2006).
Polyacrylonitrile fibre (PAN), more commonly known as acrylic fibre, has high resistance to UV degradation and also against the damage from mold, mildew, and microorganisms. It has major applications in the production of sweaters, knits, hosiery, apparels, rugs, and blankets, in which wool was the first choice. The acrylic fibre also finds its utility as primary precursor for the development of high-quality carbon fibres (Gupta and Afshari 2009). Moreover, acrylic fibres also doped with silver nanoparticles for antimicrobial properties (Hassan and K 2018).
High molecular weight polyamides are commonly known as nylon. Polyamide fibres have high strength, high toughness, and abrasion resistance which make it ideal for many military applications. Additionally, it has applications in stretch fabrics such as swimwear and in house furnishings like curtains and upholstery. Polyamide fibres have also been widely used in technical textiles especially vehicle tires, parachutes, nets, and tents (Gong et al. 2018).
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