Abstract
Carbon lives along with us in our daily life and has a vital role to play. It is present in the air and within all living organisms. Due to its handheld advantage in nano-properties that are utilized in many applications, carbon substrates came under limelight during the recent decades. Carbon substrates are most widely used in cancer detection, catalysis, bio-sensing, adsorption, drug delivery, carbon capture, hydrogen storage, and energy. Alongside, composite materials with carbon as an additive are also developing rapidly in applications like infrastructures, automobile, health care, consumer goods, etc. which became an integral chunk of our life. In this paper different types of carbon substrates and its applications, properties of the substrates were reviewed. The applications and methods of synthesis of carbon substrates are also dealt with a broad perspective.
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1 Introduction
Significant recent developments in the field of nanotechnology have been achieved in the last few years, especially in the fabrication of carbon substrates with a wide range of applications. The availability of carbon in abundance is the key to its presence in our lives. Carbon is contained in air and all living organisms. Alongside, composite materials with carbon as an additive are also developing rapidly in several industrial applications and play a vital role in our daily life due to its attractive attributes [1]. Carbon substrates have different characteristics, such as high elasticity, high thermal conductivity, low density, and chemical inertia, etc. These materials have played an important part in nanotechnology, electronics, optic-related applications and few other materials-oriented areas because of these fascinating properties [2]. High soluble materials could be obtained from the carbon substrates through surface functionalization and those functionalized materials were tailored and made compatible with biological systems through active molecules. Surface functionalization allows different molecules or antigens to be adsorbed or attached, which can further utilized to enhance the immune recognition or therapy effect through cell population appropriation.
Such a wide variety of materials allows various possibilities of getting different electrical, electronics, optical or mechanical properties. Various types of carbon substrates, applications, origin and their difference with other substrates according to their behaviour are dealt in this review. Some of the elements dealt here are graphite, molybdenum disulphide, graphene, graphene oxide (GO), carbon nano-tubes (CNTs), carbon nano-fibers (CNFs) and hornbeam leaves. Few central applications that pave way for newer industrial purposes, analysis of energy-efficient resources and techniques available to manufacture carbon substrates are discussed in detail in this article.
2 Carbon substrates
2.1 Carbon nano-tubes
CNTs are mostly applied, due to their high surface areas and appreciable physico-mechanical properties, in environmental pollution preventionand treatment, structural–functional integrated composites, energy conversion, and storage [3, 4]. During the initial stages, CNT powders were dispersed into matrix materials such as ceramics, resins and metals as nano- or micro-scale fillers for utilizing them in enhancing the conductive and mechanical performance of the substrates. Nevertheless, there are two common disadvantages in using CNTs: first is the presence of strong Van Der Waals forces in CNTs which makes them to entwine with one another resulting in agglomeration of formation of cable-like structure. Hence homogenous dispersion of CNTs into the matrix is largely impossible. Second is the increase in matrix viscosity due to difficulty in addition of CNTs into the matrix. This results in a constraint to produce the composite material with well-governed orientation. These are the reasons for the development of some novel assembly techniques, using CNT films, fibers, aerogels and 3D foams, to fabricate CNTs on macro-scale [5,6,7]. When these CNT macro-structures are used in the manufacturing of composites which contain governed orientation and dense CNT constituent, the resulting composite undoubtedly possesses all appreciable properties of monolithic CNTs. Table 1 enlists the enhancement of various properties and probable application areas of the composites when CNTs were used as reinforcements.
CNT films are widely used in warranted applications like air filtration and energy storage devices amongst all macro-architectures. For improving the conductivity of the composite material, CNT films may be used to modify the properties of the matrix material [8]. A thin film air filtration material was developed from CNTs due to their outstanding corrosion resistance and larger specific area. When compared with the conventional/traditional materials, the developed material had 99.9% filtering efficiency when used to filter 11 nm sized iron gel particles [9]. However, impedance to their usage is that these materials easily decompose and oxidize under aerobic conditions particularly over and above the temperatures of 450 °C [10]. Few studies stated that in air surroundings at 540 °C decomposition of CNTs were initiated which made the CNTs to possess 60% residual mass and thus the applications of CNTs for high-temperature gas filtration could not be accomplished. A revolutionary concept has been built that in lieu of CNT film, a porous ZrO2 sponge may be utilized in high-temperature applications as a filler material. But the manufacturing of sponge is time-consuming process and upon using CNT encapsulated in boron nitride nano-sheets, the oxidation temperature changed to 690 °C from 550 °C [11, 12]. Since the decomposition of H3BO3 in the ammonia atmosphere is required at 1050 °C, this process becomes complex to be materialized as such. It is suggested that encapsulation of CNT in silicon carbide (SiC) has increased the mechanical properties and oxidation resistance of the CNT thin films [13], but its grounding demands the usage of toxic reagents such as xylene and a high temperature of 1000 °C. Thus it is highly necessary to progress towards developing a CNT material which possesses upper hand mechanical properties, ability to withstand high temperature air environments and good oxidation resistance [14]. Figure 1 shows different biomedical applications of CNTs.
Biomedical applications of CNTs [2]
2.2 Carbon precursor
Acetylene, acetates, yeast alcohol dehydrogenase, oleates, polyurethane, low-density polyethylene, and nitro-phenol are some of the sources of carbon that were utilized for producing magnetic nano-structures based on carbon [15,16,17,18]. The novelty of combining carbon-based material with magnetic nano-particle is that it could be very well used as a raw material obtained from renewable biomass. This is possible when various organic residues like domestic, agricultural, and industrial biomass, which were underutilized, are used for preparation [19]. Advantages of agricultural biomass among these raw materials are: abundance in availability, feedstock linked functional groups range, low cost and as these materials were obtained from renewable sources they act as a recovered resources from wastes [20, 21]. A potential cradle for carbon sustenance is a carbonaceous material manufactured through pyrolysis of biomass, called bio-char, which is produced in an inert environment that is utilized for soil rehabilitation. Bio-char is also adept at removing pollutants and other heavy metals through adsorption from wastewater at a relatively lesser cost [22].
2.3 Graphene
Chemical vapour deposition (CVD) coating of graphene on substrates of solid metal was meticulously considered to fulfil numerous necessities such as transparent electrodes and electrical devices in recent years [63]. Regardless of abundant efforts, grain boundaries formed and minimizing defects during nucleation of grains [64] and imperfections caused during atomic transfers still endure as trials [65, 66]. In recent times, researchers made an effort to report the issues regarding the transfer imperfections (supporting polymer residue, wrinkles and cracks) and inadvertent organic adulteration by mounting target substrate with graphene. Earlier researches on the development of transfer-free graphene also has the finding of appropriate carbon pre-cursor, growth of graphene over the metal substrate through the solid carbon source diffusion without the involvement of catalyst depressing the growth temperature. Yet, crystallinity and the exposure of cultivated graphene remain unparalleled with the graphene cultivated on the metal substrate through a thick foil or pre-deposited thin film of metal along with catalytic action [67].
One of the noteworthy efforts for cultivating graphene could be through the use of metal vapour as catalyst on the substrate metallic element. Few experimenters tried to grow graphene initially from the off-site evaporation of floating copper from copper foil to produce decaying carbon from which the graphene layers could be made to grow directly on oxide substrates by means of remote catalytic process [68]. In later times, some other authors stated the ease of graphene growth on amorphous substrate with copper vapour assistance by the abundant feed of copper vapour. Nevertheless, graphene was obtained with a large crystalline index from the former case was on par with the latter case but the only lacuna is the coverage of surface area of grown graphene on the metal substrate. Though the cultivation of graphene on the metal substrate using catalyst was easier, very less understanding of the mechanism of graphene growth in terms of metal catalyst vapour pressure and the substrate-specific location at which the growth and reaction took place rendered lesser surface area of graphene [69, 70].
For understanding the graphene growth arising out of vapour-phase metal catalyst that enables the direct cultivation of graphene on several substrate surfaces, precise control of the environment of graphene growth and vapour pressure of metal has to be ensured [71]. Accordingly, an MHW-CVD system with dual heating entailed with a high temperature mobile wire at a temperature of 1250 °C and another heater in the substrate bottom at a temperature of 600–700 °C in a gas controlled environmental chamber was found to work as expected because of two advantages: (i) detailed and discrete control of the PNi of metal vapour by regulating the metal catalyst temperature executed as MHW at the time of attaining individual chamber pressure control in total, and (ii) controlling the growth temperature for obtaining low defect and high area coverage of graphene independently. With these advantages, it has been efficaciously verified the thorough process of growth of graphene nano-clusters recrystallization, nucleated on a catalyst metal surface which grow and combine through monitoring of the external process parameters one after the other including Tsub, Tw, and wire scan speed (Vw), that concluded normality of MHW-CVD to graphene growth on NCS also. Thermal performance, life, and durability of the materials used in electronic devices have been considered vital due to their miniaturization and integration. Thermally conductive polymer matrix composites reinforced with graphene or filled with thermally good graphene has a great potential to be used in electronic applications which could dissipate the heat produced in photonic, electronic, and optoelectronic systems with ease. Many studies focussed in analysing the performance of thermally conductive graphene-containing polymer composites and their influence over other properties of such composites [72,73,74,75,76]. Table 2 lists the thermal conductivity values and the increase of thermal conductivity of the composite materials containing graphene.
2.4 Graphite
Graphite is present in commercial lithium-ion batteries (LIBs) as dominant-negative electrode. The major constraint in large-scale usage of LIBs in energy storage systems and electric vehicles is that it has an unsatisfactory performance and very limited lifecycle. In view of obtaining an extraordinary performance graphite anode, surface modification that includes surface decoration and surface coating are the key strategies and these changes may cater the hostile need of large-scale utilization and longer lifecycle [81, 82]. Accommodating the electrode volume changes, shielding the electrodes against corrosion and impeding the electrolyte corrosion are the key functions of the interfacial decoration layer [83].
Based on the concept of lithium solid electrolyte interphase (SEI) was analysed for a long period, especially in advanced electro-chemical systems on the graphite surface. The active material surface containing ultra-thin functional film cannot have much importance. Mostly, SEI is a nano-sized layer developed naturally superficially on electrode through electrolyte components decomposition. Texture, stability, composition and conductivity of SEI film perform critical roles on overall electro-chemical performances for graphite anodes [84]. Over 10% of the graphite particles changes at the time of extraction and insertion of lithium is being reported. Appreciable flexibility and ductility of SEI film is necessary for it to remain undamaged during the volume change occurrence. Nevertheless, many inorganic salts like LiF and Li2CO contained in SEI film increases its brittle nature and hence coping to volume change of graphite particles is a crucial task for the film. This results in loss of lithium inventory in the cell, as the SEI film is influenced by continuous growth of mechanical crack and constant redisposition of SEI film. This is the root cause of commercial LIBs, for capacity-fading when deep charge–discharge cycles take place [85, 86].
It becomes very much necessary to form a tough and flexible SEI film to evade the lithium depletion and change of volume of graphite particles during lithium extraction and insertion. Nevertheless, rigorous attempts have been made to optimize the electrolyte by incorporating the film-forming electrolyte additives. But this strategy is least operative which increases the flexibility of SEI. In the interim, during prolonged cycles, an appreciable resistance is noted because of precipitation of unnecessary passivation species on graphite surface. Physical surface coating or alteration such as polymeric coatings [87], conductive Ag or Ni metals [88], inert metal oxide coatings with Al2O3 or ZrO2 and carbon layer coatings are some of the salient strategies to enhance the life of graphite anode. Many physical coating materials may not involve in the formation of SEI layer, since most of them are electro-chemically inert, as per studies. During cell operation, another problem of mechanical mismatch between the coating layer and graphite substrate arises [89]. Electro-active SEI template materials are used to improve the mechanics of SEI film which is a sporadic study performed in contrast to the previous fact. The accumulation of a flexible SEI layer to reduce the lithium consumption by commendably housing the volume change of the graphite is highly important to develop LIBs of appreciable durability and reliability. A new method to construct elastic and robust SEI on graphite surface through in-situ polymerization technique of sodium maleate on graphite powder particles as substrate has been projected earlier [90].
The unsaturated carbon bond in maleate substrate was converted into radical thus accommodating an electron and brought polymerization reaction in between monomer and maleate. The polymeric skeleton grown upon in-situ conditions turns into a SEI film reinforcing grid, thus rendering enhanced flexibility and strength of the electrolytic interphase film. The delicate scheme and parameter of the interphase film stimulate the change in volume of graphite particles from the extraction and insertion of lithium ions. Yet, the influence of the type of carbon bond formation over the SEI film that was grown by in-situ method with graphite anode as a substrate has not been explored to a larger extent. Undoubtedly an exhaustive study on the subject of the variant of carbon is of prodigiousworthto choose a nuptial SEI substrate over which the high performance graphite anode grows [91, 92].
Graphite is a capable material with applications such as field emission, solar cells, catalysis, batteries, membranes, dry lubricants and fuel cells has a two-dimensional (2D) layered structure like graphene [93]. Current research emphasizes the quest for the optimum morphology to uphold the superior along with unique characteristics. It is described that nano-particles with visible edges unveiled the absence of superior and unique properties in bulk material equivalent [94, 95]. Some metals, carbon, silicon, and sapphire are preferable nominees for utilizing as reference materials for making few exciting 2D materials [96]. Amongst these, carbon substrates are habitually used to produce MoS2 structures for numerous applications. Researchers stated that MoS2/CNT hybrid structures can be applied for the detection of NO2 gas [97, 98]. Validation of the probable employment of nano-sheet made using graphene materials for energy storage and conversion by utilizing those materials to manufacture rechargeable LIBs possessing enhanced performance was made in many experiments [99]. Amorphous MoS2 nano-sheet arrays were consolidated on carbon cloth substrates and they were used as potential catalysts in rigorous hydrogen evolution reaction.
Various techniques have been proposed to attain well-contained MoS2/carbon hybrid structures both physically and chemically, including solvo-thermal techniques, CVD, electrode position, sputtering, thermal pyrolysis and hydro-thermal methods [100,101,102,103]. To have the uniform development of carbon/MoS2 hybrids, solution-based techniques were found to be appropriate and highly operational but their production outcome is constrained by time-consuming and complicated processes. CVD methods were observed to be promising for directly synthesizing the MoS2 layers on the target carbon surfaces and the precise control upon the nucleation of thin-walled multi-layered or monolayer MoS2 on smooth or flat carbon surfaces was considered to be the key advantage [104]. Thus the quest to develop more naive strategies for producing uniform carbon/MoS2 hybrid structures over complex structured carbon substrates is still in progress using vast experimental strategies [105].
2.5 Graphene oxide
Monolayer and few-layer graphene from the family of graphene converted into exfoliated graphite/graphene nano-platelets (GNPs) have become the prime focus of research by many experimenters and their preparation methods and application to render enhanced performance composites were carried out [106]. Graphene oxide (GO), from which graphene is obtained, is a 2D material based on carbon comprising of various functional groups such as ketone, carboxyl, hydroxyl and epoxy along the edge and basal planes of its atomic arrangement. Bio-molecules were largely supported by GO owing to its rich π-conjugation structure, flat surface and high surface area. Besides, GO finds its applications in rendering uniform dispersion and stabilization of semiconductor nano-materials, metal oxides, and metals such as silver, platinum, zinc oxide and so on [107, 108].
Application of graphene in a variety of fields has been greatly supported by the formation of graphene-based derivative compounds like graphene-based nano-composites, GO, fluoro-graphene and graphane and these compounds could be formed by the incorporation of a functional group or proper defects into the basal plane of graphene [109]. Few experimental results portrayed that GO had less coefficient of friction compared to graphene in humid and N2 conditions while few other studies on micro/nano-scale graphene usage displayed contrasting results that graphene exhibited less coefficient of friction than GO. It is difficult to understand the role of chemical modification and immobilization of bio-molecules on graphene due to the scarce availability of oxygenated functional groups that restricts its utilization in electro-chemical biosensors design [107]. Graphene-related materials like GO or reduced GO (rGO) possess various beneficial characteristics so that they can be readily used in nanotechnology-based devices.
GO can be found mostly in sheet form and is the most highly used derivative form of graphene. This contains oxygen functional groups along its edge and basal planes and has seen wide spectrum of biological applications due to its salient properties including better solubility in water [109]. GO is normally prepared by the oxidation of chemically treated graphite followed by its dispersion in any organic solvent or water. When GO is further reduced through electro-chemical or chemical reactions with the aid of residual oxygen atoms or fewer defects, rGO could be obtained [110]. Most of the existed GO nano-sheet-based materials were applied in the fluorescent detection systems [111]. GO and amine-modified GO-NH2 are used as humidity sensing materials [110]. Size specific membranes can easily be obtained out of graphene owing to their chemically inert nature, better mechanical characteristics and appreciable thickness at the atomic level. Major applications of such graphene materials include their utilization in the membrane separation process and development of graphene membranes for desalination which were functionalized with nano-sized channels and pores through chemical and physical methods [112]. Graphene renders great support to surface plasma on polarization waves that were confined as graphene was characterized with permittivity and conductivity which can be fine-tuned through magneto-static or electro-static fields. This is considered to be the most significant application of graphene sheets or layers. Graphene-based waveguides, field-effect transistors, interconnects and antennas were given a strong research focus due to the high thermal conductivity, electron mobility and intrinsic strength of the graphene-based materials [113]. Such notable characteristics of GO make it as an effective initial material for fabricating cementitious composites with enhanced performance [114]. Graphene is in the current research trend due to its highly diversified properties including large electron mobility and high thermal conductivity which abundantly widen its scope of application [115, 116].
2.6 Carbon sheets based origami fold cores
Various human-made materials derived its initial form from the living organisms created by the nature [117, 118]. Few origami fold cores’ geometric parameters were the derivatives of Miura-ori tessellation which can be enumerated through the association between its kinematic deformation performance and through some sequential geometric factors which are completely independent [119, 120]. Morphological and structural competencies were observed to govern most of the origami structure’s applications [121]. Origami-based meta-materials, specifically ultra-light, strong, and stiff mechanical meta-materials are imparted with much importance. The frequently used structure of these meta-materials is frivolous sandwich materials with Miura-ori tessellation co-rearrangement and such materials are also termed as chevron origami fold core materials. Fold core structures with sandwich cross-sections have enlarged their capable applications in aircraft assemblies. Fold core sandwich structures are used as fuselage structures in Airbus aircrafts while VeSCo arrangement was taken into consideration by most of the German-based research organizations [122]. They are also used in preparing other aircraft structures like rudders, flaps, and spoilers [123]. Project CELPACT was initiated in European countries mainly to demonstrate the strong mechanical properties of chevron origami fold core sandwich structures. Few researchers studied the impact and quasi-static behaviour of chevron origami fold cores [124]. The intense anisotropy of in-plane mechanical behaviour of corrugated cores was possibly lessened by fold cores that are folded in two different directions [125]. Fold cores provide open channel for ventilation whereas the honeycomb structure has closed cells [126]. By strategic design for geometric parameters in the unit cell of fold cores, they may accommodate the complex curved surfaces. Sheet materials like aluminium sheet, aramid paper and composites reinforced with natural or artificial fibers were theoretically utilized for the construction of the fold cores [127,128,129].
Curved origami fold core comes under novel origami fold core structures. Very few studies are available on this structure and mainly focus was on the design, experimental and numerical investigation of the curved origami fold cores prepared from either plastic or metallic materials [118, 121, 130]. Alongside, only very few researches are available on the investigation of curved origami fold cores prepared from natural or synthetic fiber-reinforced composites and the analytical model to predict the performance of these structures are to be explored to a larger extent. When compared with the fold cores made of aluminium and paper, carbon fiber reinforced composite fold core materials were characterized by high strength and stiffness. It was also stated in various literature that chevron origami fold core pattern aroused from a conventional V-pattern. This pattern was developed specifically for paper or metallic materials and could not be suited for any fiber-reinforced composite materials. For fiber-reinforced composites to be used as parent material, the zig-zag crease pattern of the fold core could be converted into curved fold cores [131,132,133].
The main advantage of using curved-crease fold cores is that it avoids the breakage of fiber during the manufacturing of composites and loading them [134, 135]. It also minimizes the change of fiber direction abruptly. Variation of the presence of resin in a rich or meagre way was also addressed by the curved crease fold cores due to the smoother changes occurring in the cell wall of the materials. These curved-crease fold core materials possess better buckling strength and resistance when compared with chevron fold cores [136,137,138]. Due to the aforementioned potentialities, carbon fiber reinforced composite fold cores are currently in prime focus in terms of research [139]. Current day researches focus on developing structures that are self-folding which could be created by the action of external forces and moments thus kindling kinematic manipulations without adopting mechanical folding or unfolding. Such automatic folding of the structures is used in robotic applications, self-assembly operations and aerospace applications. Table 3 enlists the various types of external actuation forces and their processing time along with range of folding angle for different inherent fold core materials [140,141,142,143].
2.7 Carbon nano-fibers
CNFs gained increasing interest nowadays due to their noteworthy evolution in many applications of engineering and technology. Advanced composites could be manufactured by reinforcing CNFs with either natural or other synthetic fibers and these materials could be applied in numerous aircraft, military, and automobile applications. Apart from these applications, CNFs could also be employed as fuel cell catalysts, waterborne and airborne pollutants’ sorbent, tissue reconstruction, and renaissance for various bio-based materials. Different applications demand different forms of CNFs: in some applications, they are required as reinforcements or as individual fibers, in some other fields, it is required as a medium for adsorption, as energy storage and conversion materials, for stable and ease of handling bio-materials and as porous membrane in mass transfer applications [144]. Apart from the material form, various target applications demand the deployment of CNFs with variety of chemical structures and surface characteristics. From all the above facts, it could be stated that the fabrication of CNF based composites has to be planned sensibly in such a way that the specific application are catered without any lacuna. CNFs can be easily produced by electro-spinning of the polymer precursor and its carbonization. By controlling some important process variables, porous CNFs with necessitated characteristics can be fabricated [145, 146].
Among different precursors, polyacrylonitrile (PAN) was frequently used in the industrial scale. This relatively low-cost polymer might render a maximum carbon yield owing to the containment of intermittent constituents that influences the tailoring of CNFs in favour of its disintegration when they were heated. PAN rendered carbon fibers exhibit high mechanical, electrical, and thermal properties owing to the high amount of carbon output. Manufacturing of CNFs from PAN could be easily customized and a clear picture on the quality of CNF can be obtained by the influence of various process parameters on the properties of the final product. As the commercialization and application of nano-fibers has high scope, various researches were conducted upon the fabrication aspects of CNFs and their optimization. From such studies, various dimensional and structural aspects of CNFs such as its diameter, morphology, and structural arrangement were obtained. Yet, more explorations in terms of physico-chemical characteristics of CNFs and modified thermal transfer within those nano-scale fibers have to be done by systematic experimental investigations. Another possibility of diversification in the study could be the modification of CNF precursors by mixing them with different types of additives [147, 148].
Additives were employed for two primary cause. First, to stabilize and carbonize the fibers as catalysts to reduce the thermal treatment temperature and time, for the industrial scale fabrication at low cost. Second, additives might be influential in changing the material properties like thermal, surface chemistry, electrical conductivity and mechanical properties [149]. Introduction of the additive was expected to convert the process as simple one simultaneously when the precursor was also made. It was also stated that addition of additive should be carried out like post thermal treatment which might not have much reduction in process cost. Electro-spinning of the additive modified polymer matrix was considered to be the simple and one-stop solution for the aforesaid problem [150]. Transmission electron microscopy (TEM) images of single and double-layer CNF is presented in Fig. 2 [151].
TEM images of single and double layer CNF [151]
Amongst various additives of CNF, CNTs are important, because of contained graphene, it not only compromises some properties but also aids in enhancing a few of the end characteristics of fabricated material [151, 152]. Simultaneously, the mechanical characteristics of the available CNFs were assumed to be inherently better owing to their shape factor. Researches pertaining to the influence of the CNTs addition in PAN nano-fibers with respect tothermal transition process were noted [153]. Nevertheless the interaction mechanism of CNTs-polymer with reference tovarious characteristics and their effect on thermal transition process remains ambiguous even now. This unclear scenario arose due to the complex chemical composition of graphene and graphene plane transition in CNTs at the time of thermal processing [154]. It was also stated by few experimenters that the change in dimensions of CNT and the rate of homogeneity in the dispersion of CNT in polymer matrix could bring a change in transition mechanisms. Such unclear characterization at the time of their incorporation in polymer matrix gotten even more complicated during the earlier times as the purchase of materials by the experimenters were made from various vendors and the materials itself were different in nature [155, 156].
The difference of the CNT materials was not only present with respect to the various vendors but also with respect to various batches of material supplied. This forced the experimenters to carry out a complete characterization of CNT used in the experiment to have clarity in end material characteristics. Such usage of CNT as reinforcement in the polymer matrix and their prior characterization became a significant part of research and the availability of CNT commercially has also seen much growth due to high availability, price reduction and the availability of functionalized CNTs which has also amplified the applications ofCNF. Functional groups available at the peripheral walls may vary in terms of magnitudes and types and the usage of such CNTs have a significant influence upon the polymer matrix chain which aids in developing different materials with variable structural and surface properties to cater the precise requirements for the objective uses [157,158,159,160].
2.8 Activated carbon and carbon black
Activated carbon (AC) is a carbon-based material which is characterized with a large surface area and higher degree of porosity. It can also be termed as carbonaceous material with porous structure which is used in various applications including desalination and wastewater treatment and purification of air owing to its noteworthy characteristics [161]. It could also be used in various other applications pertaining to industrial scale and environmental-related applications such as separation, retrieval, modification, and removal of gas and liquid phases from different compounds. AC comprises of almost 90% of carbon while the prominent functional groups present in activated carbon including lactone, phenyl, quinine, carboxyl and carbonyl groups were responsible for contaminants absorption. AC structure consists of nitrogen, oxygen, sulphur, and hydrogen as functional groups in its chemical structure [162].
Specific adsorption characteristics of AC were due to the presence of functional groups within it, which were activated by various activation processes such as thermal and precursor purification. Applicability and performance of the activated carbon material purely depends on the choice of chemical activation agent [163]. Numerous alkaline-based chemical agents such as potassium carbonate, potassium hydroxide, calcium chloride, and sodium hydroxide, acidic chemical agents such as sulphuric acid and phosphoric acid and metal intermittent salts including zinc chloride were majorly used as activating agents for activated carbon [164]. Figure 3 depicts the activation process and chemical used for the activation of AC. Since various factors govern the activation degree of AC, numerous researchers are currently being conducted to clearly comprehend the mechanism of adsorption so that the process of adsorption can readily be employed in adsorbing the atmospheric pollutants using AC can be unveiled and developed for future purposes [165, 166].
Activation process and chemicals used to activate the AC [166]
Carbon black (CB) is manufactured by decomposing the carbon-rich ingredients in a completely controlled inert and oxygen deficit environment through partial combustion or through pyrolysis. In most of the applications, CB was used as filler reinforcement in many rubber-based composites and to enhance the overall characteristics of elastomer-based composites [167, 168]. It was found from various studies that CB filled in composites exhibited better dynamic, elastic, and enhanced mechanical characteristics along with good resilience and resistance towards scratch. Almost 92% of CB production in global basis is used in the manufacturing of tyres, especially some tyre elements including carcasses, inner layers and few other components like belts, vibration isolation devices, air springs and belts [169].
Yet, owing to top reasons like continuous non-renewable raw materials use and enhanced pressure developed from the unsustainable manufacturing methods of CB, the modification of CB and development of derivative substitution filler materials for rubber has been given the prime focus of research keeping in mind the future economy and environment concerns. Few more researches stated that CB based nanofluids exhibited enhanced IR absorption and the network formed with CB particles enhanced the fluid’s thermal conductivity. Such highly thermally conductive fluids are currently employed in solar distillation and heaters which have the potential to render water vapour while the heating of working fluid is no longer necessary [170, 171]. Figure 4 depicts the transmission electron microscopic images of CB and the CB exfoliated for 20 min.
TEM images of a CB; and b exfoliated CB for 20 min [170]
3 Fabrication processes
3.1 Pyrolysis
Pyrolysis is a thermo-chemical technique that decomposes carbon-based material in an inert atmosphere at a temperature of 400 °C and transforms them into bio-char, bio-gas and bio-oil [172,173,174]. It is extensively adopted and deliberated as a capable process due.
to its simplicity and low cost [175, 176]. It consists of two steps: first, removal of moisture and the second, production of bio-gas, through conduction and convection, due to increase in temperature and further breaking down of cellulose and hemi-cellulose contents which results involatile components removal [177,178,179]. Volatile material removal from the biomass surface indices pores on the surface of biomass which was due to the degradation of cellulosic and hemicellulosic micro-constituents from the biomass surface during the initial stage. The combined effects of constant heat transfer and auxiliary volatilization increases the pore size thereby enhancing the carbon content during the subsequent process stages. Magnetic component integration occurs by post-coating or pre-coating pyrolysis process [180]. Figure 5 depicts the schematic setup of pyrolysis with various components in it.
Schematic setup of pyrolysis method [173]
3.2 Chemical co-precipitation process
Chemical co-precipitation technique is a widely used one for manufacturing nano-materials and the key motive is parting of grain growth and grain size of the product may also be obtained as an outcome due to the sluggish nuclei growth [181,182,183]. In this method, solute precipitation occurs, segregating it, and ultimately binds with the solution without dissolving. Solute binding marks one among the following three methods of precipitation which are surface adsorption, inclusion, and occlusion [184]. When the carrier is completely surrounded by the solute at the time of formation of crystal lattice it is called occlusion whereas during inclusion solute crystal matrix mixes partly along with the matrix of carrier crystal. Nonetheless, solute surface adsorption is superficially carried out which completely leaves the solution generating a huge surface area in the substrate [185, 186]. This technique is effectual to manufacture extremely ultrafine grains of size ranging between 5 and 8 nm and any size in this range of nano-material could be fabricated through the chemical co-precipitation technique [187].
3.3 Hydrothermal carbonization
Hydrothermal carbonization (HTC) is a well-organized technique for the manufacturing of nano-materials [174, 188, 189]. Nowadays it has concerned more about the development of multifaceted nano-sized structures with dissimilar properties. As a matter of fact, HTC technique falls back to yester-century in time with the objective of charcoal manufacturing [190]. Substantial advances of the HTC techniques were executed from the earlier time so that it transforms into a potential processing technique to convert polysaccharide complexes into solid products at different range of temperatures. The temperature range for this technique was determined to be in between 150 to 350 °C and the pressure range was in between 2 and 10 MPa with the processing time-spanning for few hours and all the parameters dependent on the end product needed along with the type of material used [191]. Usually, HTC technique water as catalyst due to its higher constant of ionization and so this process has a high rate of hydrolysis which would not assist material disintegration. As the HTC technique is a wet process, drying of raw materials becomes unnecessary which turns HTC process to be energy efficient. Features of HTC treatment techniques listed by earlier researchers were carbon content promotion in the final product, solubility improvement, complex acid–base reaction promotion, crystalline matrix melting and acceleration of solvent-carbon physio-chemical interactions [174, 192]. Few experimenters stated that HTC technique was widely employed for the manufacturing of carbonaceous nano-sphere mono dispersion from initial ingredients in a controlled environment which ensures homogenous dispersion through aromatization, condensation, dehydration and polymerization of the materials [193]. This technique promotes a high reaction rate by means of generating high oxygenated functional group which ultimately renders higher porosity that is considered to be a key factor in reactions like carbon capture, catalysis, super capacitance and adsorption. Few experimenters stated that the porosity of the material was dependent on temperature of the process and was found to increase at 240 °C. Beyond this temperature, porosity of the material drops but the mechanical characteristics of the material improved greatly [194].
Many researchers emphasized that the role of catalysts in the HTC method was highly significant. Experiments with iron oxide nano-particles used in the HTC process rendered hollow carbonaceous spheres formation [195]. Some authors analysed that usage of iron oxide and glucose rendered magnetic nano-materials of uniform particle size for the designing of quasi-static spherical structures. These materials enabled the capability of adsorption of polycyclic aromatic hydrocarbon to be maximum [196]. A 3D porous nano-sized composite electrode was formed using the same material by some researchers. Nano-sized material produced by the above method had symmetric size and shape with a capacitance value of 259.3 F/g, surface area of the material was noted to be 1712.8 m/g and a window voltage potential of 1.8 V [197]. Nano-sized hydro-char particles incorporated in nickel–iron-based alloy was manufactured using HTC and recorded a high adsorption of lead with 99.5%. Particle size of the nano-material developed through HTC depends on precursor concentration, microwave power, time of processing, and catalyst used [198]. Figure 6 illustrates the setup used for the hydrothermal treatment method of production of CNFs.
Schematic setup used for HTC process [174]
3.4 Cold compression process
Continuous folding machines with the arrangement of cold compression were designed to manufacture chevron origami fold cores (COFC) from paper or metal sheet [124]. Few trials were performed with aluminium COFC erected with sporadically gradual stamping technique and with the aid of cold gas pressure as a novel processing method; the metallic sheets were folded into COFC [125, 199]. Researches were enormous efforts implemented few novel methods to evaluate the compression strength of the COFC sandwich structures formed from aramid papers both by numerical simulation and experimental methods. Few other experimenters examined the failure behaviour and stiffness characteristics of aramid COFC under combined shear and compression loads [131, 200,201,202]. Cold compressed aramid sandwich COFC were subjected to the evaluation of combined bending and in-plane compression analysis through experiments by many authors. In addition to the above studies, aluminium COFC sandwich materials were used in experiments to determine their mechanical behaviour specifically under compression by few researchers [134, 203]. Yet, exploration of cold compressed fold core materials in terms of analytical models to evaluate the quasi-static mechanical characteristics were to be made and such lacuna was presumed to be due to the structural complexity of the sandwich fold core structures. Besides the advantageous mechanical properties, some other characteristics such as thermal and acoustic characteristicsare the inherent meritorious features of chevron origami fold core structures [204]. Table 4 encompasses various fabrication methods used to extract CNFs and their process parameters along with the energy consumed in Frigoria (F/g).
4 Characterization
Figure 7 illustrates the hierarchical photo-resist structures of micro- and nano-size fabricated by varying the height of the substrate and also the etching time. SU8 photo-resists comprising of antimony along with a minimal quantity of aluminium scrunched out of chamber of plasma masks the vicinity of SU8 photo-resists. During etching, it is perhaps,substrate iron will be a mask of the photo-resist. Additionally, the travelling direction of oxygen plasma etch induces nano-sized wires upon the peripheral boundaries of photo-resist over the cylindrical structure during etching [214, 215]. Figure 7a, b, c, e, f, g, i, j and k depicts that the increase in etching time using oxygen plasma reduced the cylindrical structure diameter and when the depth of photo-resist nano-wire etching increases, thinning of nano-wire surface also occurred. It could also be noted that the edge of photo-resist nano-wire was distorted owing to uninterrupted etching, resulting in a ring-shaped structure as shown in Fig. 7i–k. Additionally, as the time of etching increased, the micro/nano-structures of the photo-resist surface turned into flurry, and also enlargement of side walls pores occurred, as shown in Fig. 7d, h and l [215,216,217].
a–c, e–g, i–k SEM images of the photo-resist structures with varying height and etching time; d, h, l magnified views of (c, g, k) [215]
The representative Fig. 8 denotes of MnO2/carbon micro- and nano-structures manufactured through mechanisms like electro-chemical deposition and carbonization. Figure 8a–c illustrates the photo-resistant structures of MnO2 materials that were fabricated in various heights and their time of etching was maintained as 10, 20, and 30 min in order. Figure 8a, d and e denotes the deposition of MnO2 particles over the substrates when they were exposed to an etching time of 5 min which was lesser among all other durations. When the exposure time is increased, the deposited MnO2 particles were of larger particles as seen in Fig. 8b and c. The XPS spectrum of MnO2 structures, depicted in Fig. 8f, exhibits two major peaks at two values of binding energy such as 642.6 and 653.9 eV. The peak values were analogous to the earlier MnO2 values thus depicting the dominant presence of Mn4+ [215,216,217,218].
a–c SEM micrograph of MnO2/carbon structures with varying deposition rates, d magnified top surface of the material (a); e magnified MnO2 nanostructure from (d); f XPS curves of the material [215]
5 Applications
Production of magnetic property-rich carbon substrates from the abundantly available agricultural waste may pave way for the effective utilization of wastes. In addition to the utilization, harmful gases liberated from those wastes were also reduced when the wastes are reused properly [219]. Though the nano-materials deal with the environmental hazards effortlessly, their disposal effects and exposing to the environments pose threat towards the environment and health [220]. Owing to their ultra-fine sizes, their mixture into the stream of wastes may end up damaging human health and the life of sea species. Nevertheless, such magnetic property-rich nano-materials could be recovered with the help of a magnetic field which makes the technology more efficient and safer. Few experimenters removed the arsenic contaminates from water using an innovative mesoporous magnetic encapsulated carbon while the thiazole fungicides were effectively absorbed by the graphene-based magnetic nano-composites from water [221, 222]. Many organic compounds like chloro-benzene, phenol, dyes, and chloroform can be absorbed from water by using the enhanced absorption potential of magnetic activated carbon and these elements need not be separated from water [223]. Many experimenters demonstrated that gases like methane, nitrogen and carbon dioxide can be absorbed by carbon nano-materials doped with iron oxide nano-particles and polypyrrole. This worked perfectly even under variations of pressures [224]. Separation capability and absorption using carbon nano-particles to adsorb and separate heavy metal ions from water are shown in Fig. 9.
Adsorption phenomenon using carbon nano-particles [223]
An effectual completion of 5000 lifecycles with almost 95% retention of capacitance was done by carbon nano-wires that possess a power density of 1.2 kW/kg, specific capacitance of 259 F/g and a maximum energy density of 30Wh/kg because of their good electrical durability [225, 226] which performed in lithium-ion batteries also as an anode. High surface area, lower cost, super electro-magnetic properties, and non-toxic nature are some of the advantages of carbon substrate materials apart from high energy capacity [227, 228] which approve their usage in energy storage applications. Hydrogen storage can also be done using carbon substrates as experiments focus on manufacturing flower-like structures with magnetic microspheres utilizing L-cysteine [229].
Nano-sized materials are highly used in health care applications potentially for more than three decades. An important problem in the usage of orthodox nano-materials is making them work in the areas of target in the human body. The induction of magnetic nano-particles expedites management to explicit are as by the meek practice of a magnetic field all through treatment process, trailed by delivery and then by capable removal of the field [227,228,229]. One well-established area is the visualization of musculoskeletal structure along with soft tissue using magnetic resonance imaging (MRI) technique that utilizes differently natured materials like iron oxide-based nano-material for obtaining high-quality images [230]. Due to higher retention time and higher permeability, these nano-particles can detect tumours efficiently (Fig. 10). Some other researches focus on using the nano-materials as drug carriers and for gene therapy in which the nano-magnetic transfection into the cells is made non-virally [211,212,213,214]. Using nano-materials, effective cytotoxic drug delivery has been stated on various animals [214, 215, 220]. Improvement in novel nano-material carrier systems is the key area of current researchers and drug delivery can be materialized by the application of surface engineering techniques. Alongside the field of bio-sensor and bio-chips using nano-material are also under development [231].
MRI images of detection of the tumour through magnetic particles [217]
6 Conclusion
In this article, a complete outline about the properties and manufacturing methods of newer carbon substrates were discussed in detail. Details of carbon substrates used to produce lightweight fiber reinforced plastics and other areas where reduction of weight is needed without compromising the strength were also enumerated. Extraction methods, developments and other supportive data of carbon substrates like graphite, molybdenum disulphides, hornbeam leaves, CNTs, AC, CB and CNFs were dealt in detail. These materials have wider applications in fields like environmental remediation, catalysis, bio-medical and supercapacitance. Observations revealed that the MnO2 and carbon micro- and nano-structured electrodes display exceptional performance in terms of electro-chemical factors and a capacitance per specific gravimetry of 454 Frigori at 0.051 mA/cm2 of current density and capacitance maintenance of about 94% even beyond 6000 lifecycles. Manufacturing of magnetic carbon substrates having largely controlled morphology and properties and uniformly dispersed nano-structures were slightly complex. On contrast, in applications of optical imaging in which contrasting image method in inert nitrogen atmosphere spins with diamond is castoff and designed optimally rendered tremendous results.
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Ramesh, M., Rajeshkumar, L. & Bhoopathi, R. Carbon substrates: a review on fabrication, properties and applications. Carbon Lett. 31, 557–580 (2021). https://doi.org/10.1007/s42823-021-00264-z
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DOI: https://doi.org/10.1007/s42823-021-00264-z