FIELD

[0001] The present application relates to the transformation of asphaltenes to fibres and, more particularly, carbon fibres.

BACKGROUND

[0002] Asphaltenes are known as the most problematic fraction of crude oil; negatively affecting the petroleum processing on production, transportation, refining and storage. Asphaltenes are a solubility class corresponding to the toluene-soluble, but n-alkane- insoluble (e.g. pentane- or heptane-insoluble), fraction of bitumen (e.g. from crude oil, especially heavy crude oil, oilsands bitumen and coal liquefaction). With little market value, asphaltenes are considered as a substantive by-product but high hydrocarbon content in the petroleum industry. To date, this undesired waste is disposed of and combusted to generate energy, which can result in negative environmental impacts. Various studies on the nature of asphaltenes, such as chemical compounds, adsorption and aggregation, have been investigated to attempt to mitigate such problems and maximize the yield of valuable products from crude oil. The chemical compounds and components, as well as aggregation mechanisms, are still unclear, as asphaltenes are a complicated mixture of polycyclic aromatic hydrocarbons, metals, sulphur and other elemental components. Numerous structure models of asphaltenes have been reported among which island and archipelago configurations are two major classifications reported in the literature. In both classifications, the complex structures are dominated by carbon and hydrogen. As for nitrogen content, aromatic formations of pyrrole, pyridine and their derivatives are common and metals usually form a complex with the polycyclic aromatic rings.

[0003] The compounds, average molecular weight, and components of asphaltenes may vary according to its source and separation techniques. Chemical analysis of Turkish asphaltenes derived from six sources indicated the variety of asphaltene proportions (from 1.48 to 28.11% of crude oils). Additionally, the reported sulfur content in Maya asphaltenes is 7.10%, whereas 2.13% in Batman Celikli asphaltenes. Alberta oilsands asphaltenes (AOA) derived from bitumen contained in Alberta oilsands has been observed as containing about 8 wt% sulphur, about 2 wt% nitrogen and variable levels of metals. Alberta oilsands are amongst the world’s largest hydrocarbon resources. A large fraction (15 to 20 by weight) of the bitumen is asphaltenes.

[0004] Transforming asphaltenes into value-add products may have economic, social and environmental impacts and benefits. [0005] The background herein is included solely to explain the context of the application. This is not to be taken as an admission that any of the material referred to was published, known, or part of the common general knowledge as of the priority date.

[0006] SUMMARY

[0007] In an aspect, there is a method for making a precursor fibre composition, the method comprising: combining asphaltenes and at least one of acrylonitrile and acrylonitrile derivative(s); forming free radical(s) of the at least one of acrylonitrile and acrylonitrile derivative(s), and coupling with compound(s) of the asphaltenes to form the precursor fibre composition. In a further aspect, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) couple to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes to form secondary free- radical intermediate(s).

[0008] In another aspect, there is a precursor fibre composition made by the method disclosed herein. In another aspect, the precursor fibre composition is capable of forming a fibre. In yet another aspect, the precursor fibre composition is capable of forming an asphaltenes green fibre. In another aspect, the precursor fibre composition is capable of forming a carbon fibre.

[0009] In a further aspect, there is a precursor fibre composition comprising free-radical intermediate(s) coupled to compound(s) of asphaltenes, wherein the free radical intermediate(s) is formed from the coupling of free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s). In another aspect, the intermediate(s) coupled with the compound(s) of the asphaltenes to form secondary free-radical intermediate(s), which are coupled to one another.

[0010] In another aspect, there is a fibre made from the precursor fibre composition disclosed herein. In yet another aspect, the fibre comprises an asphaltene green fibre. In a further aspect, the fibre comprises a carbon fibre.

[0011] In another aspect, there is a use of the precursor fibre composition disclosed herein for making fibres.

[0012] Other features and advantages of the present application will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments, but should be given the broadest interpretation consistent with the description as a whole. DRAWINGS

[0013] Certain embodiments of the application will now be described with reference to the drawings in which:

[0014] Figure 1(a) shows elemental analysis of raw, purified AOA and unmodified AOA- green fibre examples;

[0015] Figure 1(b) shows elemental analysis comparison of raw and purified AOA with chemically modified AOA examples;

[0016] Figure 1(c) shows FTIR spectroscopic fingerprinting of raw AOA, in-situ polymerized polyacrylonitrile (in situ PAN), and chemically modified AOA examples;

[0017] Figure 2 shows an example of a modified AOA-S1 slurry with commercial PAN in a solvent system and drop-casting on a glass slide;

[0018] Figure 3 shows examples of the raw and purified AOA, and the chemically modified AOA casted-films on glass slides and illustration of their dry surface morphology and visual mechanical behaviors;

[0019] Figure 4(a) shows SEM image of an example of chemically modified AOA-S1 composite green fibres with integration of commercial PAN (a digital image inserted);

[0020] Figure 4(b) shows an example of an unmodified AOA-S1 green fibres;

[0021] Figure 5 shows SEM images of an example of thermally treated chemically modified AOA-S1 green fibres;

[0022] Figure 6 shows SEM morphology comparison between examples of asphaltene droplet/beads and beads existing in chemically modified AOA-S1-Pent green fibres, indicating that the beads in the fibres are from commercial PAN;

[0023] Figure 7 shows digital photos and SEM image of an example of chemically modified AOA-S1 green fibres from xylene;

[0024] Figure 8 shows wet-spinning of an example of a chemically modified AOA-S1 composite slurry/solution in xylene at various spinning rates, draw ratios and a long-last spinning duration;

[0025] Figure 9 shows electrospinning of an example of a chemically modified AOA-S1 composite slurry/solution in pyridine and DMF solvent system and short AOA-green fibres were generated; [0026] Figure 10 shows wet-spinning of an example of a chemically modified AOA-S1 composite slurry/solution in pyridine and DMF solvent system in a double-layered coagulation bath of hexane and water;

[0027] Figure 11 (a) shows a visual bending test for an example of a piece of a chemically modified AOA-S1 green fibre prepared from the wet-spinning shown in Figure 10;

[0028] Figure 11 (b) shows a visual bending test for an example of a piece of a wet-spun unmodified AOA-S1 green fibre;

[0029] Figure 12 shows an example of an unmodified AOA-S1 green fibre from toluene;

[0030] Figure 13 shows an example of an unmodified AOA-S1 green fibre from xylene;

[0031] Figure 14 shows an example of a purified AOA -S1 (maltenes-free S1) fibres from xylene; and

[0032] Figure 15 shows SEM images of an example of thermally treated modified AOA-S1 green fibres.

DETAILED DESCRIPTION

Definitions

[0033] Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art.

[0034] It is to be understood that all amounts are approximate and are provided for description. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this application, suitable methods and materials are described below.

[0035] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. Patent applications, patents, and publications are cited herein to assist in understanding the aspects described. All such references cited herein are incorporated herein by reference in their entirety and for all purposes to the same extent as if each individual publication or patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety for all purposes. To the extent publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to supersede and/or take precedence over any such contradictory material. [0036] In understanding the scope of the present application, the articles “a”, “an”, and “the” are intended to mean that there are one or more of the elements. Additionally, the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of, for example, the stated features, elements, compounds/molecules, components, groups, integers, and/or steps, but do not exclude the presence, for example, of other unstated features, elements, compounds/molecules, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives.

[0037] It will be understood that any aspects described as “comprising” certain, for example, features, elements, compounds/molecules, components, groups, integers, and/or steps may also “consist of or “consist essentially of,” wherein “consisting of has a closed-ended or restrictive meaning and “consisting essentially of means including, for example, the stated features, elements, compounds/molecules, components, groups, integers, and/or steps specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide, for example, the stated features, elements, compounds/molecules, components, groups, integers, and/or steps, and components added for a purpose other than achieving the technical effect of the invention. For example, a composition defined using the phrase “consisting essentially of” encompasses any known acceptable additive, excipient, diluent, carrier, and the like. Typically, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1%, and even more typically less than 0.1% by weight of non-specified component(s).

[0038] Terms of degree such as “substantially”, “about” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.

[0039] The abbreviation, “e.g.” is derived from the Latin exempli gratia and is used herein to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example.”

[0040] The term “asphaltenes" and “asphaltene” are used interchangeably and refer to, for example, the fraction of petroleum from any source including coal liquefaction, crude oil such as heavy oil, and oilsands bitumen. Because asphaltenes are defined by solubility, there is no single molecule/compound (“molecule” and “compound” can be used interchangeably) or chemical composition that defines an “asphaltene”. Asphaltenes can be isolated from bitumen using various solvents. Different solvents give rise to different asphaltene yields from bitumen. Asphaltenes are a solubility class corresponding to, for example, the toluene- soluble, but n-alkane-insoluble (e.g. pentane- or heptane-insoluble), fraction. Asphaltene isolation as standardized by American Society for Testing and Materials (ASTM), uses n- pentane (C5) and n-heptane (C7). Raw Athabasca bitumen contains about 15% by weight of asphaltenes insoluble in n-heptane, and 20% by weight of asphaltenes insoluble in n- pentane. Asphaltenes may also be separated from partially upgraded bitumen.

[0041] The carbon to hydrogen atomic ratio of asphaltenes is greater than about 1 corresponding to a highly unsaturated molecular environment on average. Asphaltenes can have multi-ringed aromatic molecules/compounds often with aliphatic chains on the periphery. Heteroatoms can be found both within the aromatic rings (mainly S and N) and as part of the peripheral chains (mainly sulphur and oxygen). Two predominant motifs may dominate the structure of asphaltenes, as illustrated as follows:

Bridged Island [0042] Molecules/compounds exemplifying the bridged and island motif found in the structure of asphaltene constituents (Strausz, O.P., and Lown, E.M., (2003). “The Chemistry of Alberta Oil Sands, Bitumens, and Heavy Oils”. Page 495. Calgary: Alberta Energy Research Institute).

[0043] Multiple aromatic cores joined by bridging groups dominate in Athabasca bitumen, while the island motif of large aromatic rings with alkyl groups is less abundant (Chacon- Patino et al. “Advances in Asphaltene Petroleomics. Part 3. Dominance of Island or Archipelago Structural Motif Is Sample Dependent”, Energy & Fuels, 2018, 32, 9106-9120). Schuler, B., etal., (Energy & Fuels, 2017, 31, 6856-6861) have reported structures of single molecules/compounds found in asphaltenes that have been characterized by atomic force microscopy. The abundance of different structures depends on the source of the asphaltene and any prior processing of the bitumen. Asphaltene molecules/compounds tend to aggregate strongly in bitumen and solution, giving apparent molecular weights that are higher than the true range of about 400 to about 1 ,000 Da.

[0044] Asphaltenes can be a glassy solid at ambient temperature. Depending on preparation methods, asphaltenes may either be a powder or large lumps. As complex mixtures, asphaltenes may exhibit no defined melting point. The softening point depends on the composition of the mixture, ranging from about 100°C for some industrial asphaltene-rich fractions to over about 200°C for n-heptane insoluble asphaltenes.

[0045] The apparent viscosity of asphaltenes may be dependent on temperature, above the softening point, and its composition. A small amount of bitumen components that are soluble in n-pentane may significantly reduce the apparent viscosity at a given temperature. The apparent viscosity may decrease rapidly as the temperature is increased from the softening point. Asphaltenes can exhibit viscoelastic behavior depending on temperature and composition.

[0046] The composition of Alberta Oilsands asphaltenes (AOA) can vary depending on the solvent used to isolate the asphaltenes but the asphaltenes are similar. Example of the chemical compositions (by weight) for n-pentane precipitated asphaltenes is about 79% to about 80% (C); about 8% (H); about 1% to about 2 % (N); about 3% to about 4% (O); and about 7% to about 8% (S), and n-heptane precipitated asphaltenes is about 78% to about 79% (C); about 7% to about 8% (H); about 1% to about 2% (N); about 4 % to about 5% (O); and about 8% (S). The asphaltenes also contain about 800 to about 1 ,000 parts per million by weight of vanadium and about 400 to about 600 parts per million of nickel, as organometallic compounds. Processing of bitumen by thermal, catalytic or oxidative reactions may change the asphaltene content, and may also change the elemental composition of the asphaltene fraction.

[0047] As mentioned, asphaltenes are in general from any source including coal liquefaction, heavy oil, and oilsands bitumen. Examples used herein are from Alberta Oilsands bitumen, where the alkanes portion of maltenes to the aromatic-containing portion is about 20 to about 80 wt%. Purified asphaltene can have about 15 to about 25 wt% of maltenes removed. The structures, average molecular weight, and components of asphaltenes may vary according to its source and separation techniques. Chemical analysis of Turkish asphaltenes derived from six sources indicated the variety of asphaltene proportions (from about 1 wt% to about 28 wt% of crude oils). Additionally, the reported sulfur content in Maya asphaltenes is about 7 wt%, whereas its about 2 wt% in Batman Celikli asphaltenes. Alberta oilsands asphaltenes (AOA) derived from bitumen contained in Alberta oilsands has been observed as containing about 8 wt% sulphur, about 2 wt% nitrogen and variable levels of metals. Alberta oilsands are amongst the world’s largest hydrocarbon resources. A large fraction (about 15 to about 20 wt%) of the Alberta oilsand bitumen is asphaltenes.

[0048] The term “acrylonitrile derivative" refers to, for example, a derivative of acrylonitrile that is polymerizable. Examples may include acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, or a combination thereof. Other examples may include substituted acrylonitrile, substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, or a combination thereof. The term “substituent” or “substituted” used in conjunction with the groups described herein refers to a chemically acceptable group, i.e., a moiety that maintains utility. It is understood that substituents and substitution patterns may be selected by one of ordinary skill in the art to provide chemically stable derivatives and that can be synthesized by techniques known. If a substituent is itself substituted with more than one group, it is understood that these multiple groups may be on the same carbon/member atom or on different carbons/member atoms, as long as a stable structure results. Illustrative examples of some suitable substituents include alkyl, alkenyl, alkynyl, hydroxy, thio, alkylthio, alkoxy, cycloalkyl, heterocyclyl, hydroxyalkyl, benzyl, carbonyl, halo, haloalkyl, perfluoroalkyl, perfluoroalkoxy, aryl or heteroaryl, aryloxy or heteroaryloxy, aralkyl or heteroaralkyl, aralkoxy or heteroaralkoxy, H0--(C=0)--, amido, amino, alkyl- and dialkylamino, cyano, nitro, carbamoyl, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylcarbonyl, aryloxycarbonyl, alkylsulfonyl, and arylsulfonyl. Typical substituents include hydrocarbon groups including alkyl groups such as methyl groups, substituted hydrocarbon groups such as benzyl, aromatic groups, and substituted aromatic groups.

[0049] The term “polyacrylonitrile derivative" refers to, for example, a polymer of acrylonitrile derivatives, a copolymer of acrylonitrile and acrylonitrile derivatives, a copolymer of acrylonitrile and a vinyl-based monomer, wherein the vinyl-based monomer is copolymerizable with acrylonitrile, and the like.

[0050] The term “free radical initiator” refers to any chemical species which, upon exposure to sufficient energy (e.g., light, heat, or the like), decomposes into two parts which are uncharged, but which each possess at least one unpaired electron. Some examples of free radical initiators are free-radical initiator(s) which decompose at temperatures in the range of about 20 °C to about 180°C. These initiators may be peroxides, such as alkali metal peroxides (e.g. lithium or sodium peroxides), alkyl alkali metals (e.g. n-butyl lithium), ammonium peroxodisulfates, organic hydroperoxides, organic peroxides, hydrogen peroxide, azo compounds, and/or water-soluble azo compounds. Exemplary free radical initiators include ammonium persulphate and/or peroxides (e.g. lauroyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5- bis(tert-butylperoxy)-2,5-dimethylhexane, bis(tert-butyl peroxyisopropyl)benzene, and tert- butyl hydroperoxide), azo compounds (e.g., 2,2’-azobis(2-methyl-propanenitrile), 2,2’- azobis(2-methylbutanenitrile), and 1,1’-azobis(cyclohexanecarbonitrile)). Other free-radical initiators that will be well-known in the art may also be suitable for use in the compositions disclosed herein.

[0051] The term “coupling”, “coupled” or “couple” is understood to provide a covalent bond.

[0052] The term “green fibre” is understood to be a fibre before thermal treatment.

[0053] A “minor amount” or related term means less than about 50 wt % based on the total weight of the composition.

[0054] A “major amount” or related term means an amount greater than about 50 wt % based on the total weight of the composition.

[0055] The use of “(s)” at the end of a term is understood to mean one or more.

[0056] The term “and/or” as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that “at least one of or “one or more” of the listed items is used or present.

[0057] The phrase “at least one of is understood to be one or more. The phrase “at least one of... and...” is understood to mean at least one of the elements listed or a combination thereof, if not explicitly listed. For example, “at least one of A, B, and C” is understood to mean A alone or B alone or C alone or a combination of A and B or a combination of A and C or a combination of B and C or a combination of A, B, and C. “At least one of at least one of A, at least one of B, and at least one of C” is understood to mean at least one of A alone or at least one of B alone or at least one of C alone or a combination of at least one of A and at least one of B or a combination of at least one of A and at least one of C or a combination of at least one of B and at least one of C or a combination of at least one of A, at least one of B, and at least one of C.

[0058] It will be understood that any component defined herein as being included may be explicitly excluded from the claimed invention by way of proviso or negative limitation.

[0059] In addition, all ranges given herein include the end of the ranges and also any intermediate range points, whether explicitly stated or not. [0060] In general, the disclosure is directed to the transformation of asphaltenes into value- add products. In embodiments, the disclosure is directed to compositions, methods and various uses of transformed asphaltenes. For example, the asphaltenes can be used in precursor fibre compositions, which can be made into fibres, such as asphaltenes green fibre and/or carbon fibres. Thermally treated green fibres, which can provide oxidation, chemical crosslinking and/or stabilization of the fibres.

[0061] Carbon fibres are applicable to many fields including, for example, aeronautics, automotive, wind energy, naval, building construction, and sports. Carbon fibres generally have excellent tensile properties, high thermal and chemical stability, good thermal and electrical conductivities, and excellent resistance to deformation. They may be used as reinforcements for composite materials which usually comprise a polymer resin (matrix). The composite materials thus reinforced can exhibit excellent physical properties while being lightweight.

I. Precursor Fibre Compositions and Methods for Making the Same i) Methods

[0062] Precursor fibre compositions are provided. In an embodiment, a method for making the precursor fibre composition comprises combining asphaltenes and at least one of acrylonitrile and acrylonitrile derivative(s). Free radical(s) of the at least one of acrylonitrile and acrylonitrile derivative(s) are formed and couple with the compound(s) of the asphaltenes to form the precursor fibre composition.

[0063] In another embodiment, a method for making the precursor fibre composition comprises combining asphaltenes and acrylonitrile, substituted acrylonitrile, or a combination thereof. Free radical(s) of the acrylonitrile, substituted acrylonitrile, or a combination thereof are formed and coupled with the compound(s) of the asphaltenes to form the precursor fibre composition.

[0064] In a further embodiment, a method for making the precursor fibre composition comprises combining asphaltenes and acrylonitrile. Free radical(s) of the acrylonitrile are formed and coupled with the compound(s) of the asphaltenes to form the precursor fibre composition.

[0065] In further embodiments, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) can form and couple to the asphaltenes as a single free-radical monomer and/or couple to itself to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes. For example, i) a free- radical acrylonitrile can couple directly to the asphaltenes; ii) a free-radical acrylonitrile derivative(s) can couple directly to the asphaltenes; iii) the free-radical acrylonitrile monomers can couple to form free-radical intermediate(s), for example, one or more acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), ora combination thereof, which couple directly to the asphaltenes; iv) a free-radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, one or more acrylonitrile dimer derivative(s), acrylonitrile trimer derivative(s), acrylonitrile oligomer derivative(s), polyacrylonitrile (PAN) derivative(s), or a combination thereof, which couple directly to the asphaltenes; and/or v) a combination of free radical acrylonitrile and free- radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, dimers of a combination of acrylonitrile and acrylonitrile derivative(s), trimers of a combination of acrylonitrile and acrylonitrile derivative(s), a combination of oligomers of acrylonitrile and acrylonitrile derivative(s), copolymers of acrylonitrile and acrylonitrile derivative(s), or a combination thereof, which couple directly to the asphaltenes.

[0066] In further embodiments, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) can form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes. For example, i) free-radical acrylonitrile monomers can couple to form free-radical intermediate(s), for example, one or more acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), ora combination thereof, which couple directly to the asphaltenes; ii) a free-radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, PAN derivative(s) or a combination thereof, which couple directly to the asphaltenes; and/or iii) a combination of free radical acrylonitrile and free-radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, dimers of a combination of acrylonitrile and substituted acrylonitrile, trimers of a combination of acrylonitrile and substituted acrylonitrile, a combination of oligomers of acrylonitrile and substituted acrylonitrile, copolymers of acrylonitrile and substituted acrylonitrile, or a combination thereof, which couple directly to the asphaltenes.

[0067] In other embodiments, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) can form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes. For example, i) free-radical acrylonitrile monomers can couple to form free-radical intermediate(s), for example, one or more acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), ora combination thereof, which couple directly to the asphaltenes; ii) a free-radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, PAN derivative(s) or a combination thereof, which couple directly to the asphaltenes; and/or iii) a combination of free radical acrylonitrile and free-radical acrylonitrile derivative(s) can couple to form free-radical intermediate(s), for example, dimers of a combination of acrylonitrile and substituted acrylonitrile, trimers of a combination of acrylonitrile and substituted acrylonitrile, a combination of oligomers of acrylonitrile and substituted acrylonitrile, copolymers of acrylonitrile and substituted acrylonitrile, or a combination thereof, which couple directly to the asphaltenes.

[0068] In another embodiment, the free radical(s) of acrylonitrile can form and couple to the asphaltenes as a single free-radical monomer and/or couple to itself to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes. For example, i) a free-radical acrylonitrile can couple directly to the asphaltenes; and/or ii) the free-radical acrylonitrile monomers can couple to form free-radical intermediate(s), for example, one or more acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), or a combination thereof, which couple directly to the asphaltenes. In a typical embodiment, the intermediate comprises PAN; therefore, forming in-situ PAN.

[0069] In view of the embodiments disclosed herein, the coupling of the free-radical monomers and/or free-radical intermediate(s) with the compound(s) of asphaltenes can also result in free-radical intermediate(s) of asphaltenes coupled to acrylonitrile, acrylonitrile derivatives, a combination thereof, free-radical intermediate(s) of acrylonitrile, acrylonitrile derivatives, or a combination thereof. In an embodiment, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) couple to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes to form secondary free-radical intermediate(s). For example, the secondary free-radical intermediate(s) comprise asphaltenes-acrylonitrile radical(s), asphaltenes-acrylonitrile dimer radical(s), asphaltenes-acrylonitrile trimer radical(s), asphaltenes-acrylonitrile oligomer radical(s), asphaltenes-PAN radical(s), or a combination thereof.

[0070] In view of the embodiments disclosed herein, the coupling of the free-radical monomers and/or free-radical intermediate(s) with the compound(s) of asphaltenes can result in cross-linking. The precursor fibre composition may comprise macromolecules having a linear and/or hyperbranched polymer assembly. In typical embodiments, the precursor fibre composition comprises macromolecules having a PAN-asphaltene linear and/or hyperbranched polymer assembly. [0071] In embodiments, the precursor fibre composition is homogeneous/homogeneous phase and, in specific embodiments, can be a homogeneous solution or slurry. The homogeneous/ homogeneous phase can be a stable and/or meta-stable homogenous mixture. The precursor fibre composition disclosed here is capable of forming a fibre. In certain embodiments, the precursor fibre composition is capable of forming a green fibre. In other embodiments, the precursor fibre composition is capable of forming a carbon fibre. In examples, the carbon fibre may undergo further heat treatment. The precursor fibre composition can be concentrated to a suitable viscosity for making fibres. The green fibres can be treated at elevated temperatures (e.g. less than about 400 °C (e.g. in air)) for initiation of the “cyano-chemistry” for cyclization / condensation / aromatization along, for example, the PAN polymer backbones (including in-situ polymerized PAN and PAN- additive). The operational temperature profiles for the thermal treatment may be determined according to the thermal decomposition profiles of the fibre itself. Additional aromatization/condensation can be established with temperature profiles in the temperature range from about 400 °C to about 1000 °C, followed by the carbonization/graphitization up to 3000 °C in an inert atmosphere (e.g. N2/Ar).

[0072] In further embodiments of the method for making the precursor fibre composition, the method disclosed herein further comprises a first solvent. The first solvent may be selected such that the asphaltenes are soluble therein. The method may also comprise a second solvent. The second solvent may be selected such that at least one of polyacrylonitrile (PAN) and PAN derivative(s) are soluble. In a typical embodiment, the second solvent is selected such that polyacrylonitrile (PAN) is soluble. The amounts of the first and/or second solvents can vary; however, a major amount of the first solvent and a minor amount of the second solvent present in the combination step(s) is typical. In the method disclosed herein, the first solvent and the second solvent may be miscible, more specifically, to form a homogenous phase. In further embodiments, the solvent(s) may be selected such that the asphaltenes and at least one of acrylonitrile and acrylonitrile derivative(s) remain substantially in solution (e.g. precipitation free).

[0073] In examples, the first solvent is an organic solvent. The solubility of the asphaltenes in the first solvent can be as follows: at least about 70 wt% of the asphaltenes is soluble; at least about 80 wt% of the asphaltenes is soluble; at least about 90 wt% of the asphaltenes is soluble; at least about 99 wt% of the asphaltenes is soluble; or about 100 wt% of the asphaltenes is soluble. Typical examples of first solvents may include pyridine, pyrrole, toluene, benzene, xylene, tetrahydrofuran (THF), acetonitrile, anisole, quinoline, or a combination thereof. [0074] In examples, the second solvent is an organic solvent, inorganic solvent, or a combination thereof. The solubility of the at least one of polyacrylonitrile (PAN) and PAN derivative(s), more typically, polyacrylonitrile (PAN), in the second solvent can be as follows: at least about 70 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble; at least about 80 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble; at least about 90 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble; at least about 99 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble; or about 100 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble. Typical examples of second solvents may include dimethyl formamide (DMF), dimethyl sulphoxide (DMSO), N-methyl-2- pyrrolidon (NMP), propylene carbonate, ionic liquid, such as pyridinium benzylchloride or any suitable salt in a liquid state, aqueous solutions thereof, aqueous sodium thiocyanate, or a combination thereof.

[0075] With respect to the embodiments of the method disclosed herein, the combining can include any suitable permutations of combinations to form the precursor fibre composition. Examples include, i) the combining comprises combining the asphaltenes, the first solvent, and the at least one of acrylonitrile and acrylonitrile derivative(s); ii) the combining comprises combining the asphaltenes, the first solvent, the at least one of acrylonitrile and acrylonitrile derivative(s), and the second solvent; iii) the combining comprises combining the asphaltenes, the first solvent, and the second solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) to the mixture; iv) the combining comprises combining the asphaltenes and the first solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) and the second solvent to the mixture; v) the combining comprises combining the asphaltenes, the first solvent, and acrylonitrile; vi) the combining comprises combining the asphaltenes, the first solvent, acrylonitrile, and the second solvent; vii) the combining comprises combining the asphaltenes, the first solvent, and the second solvent to form a mixture and adding the acrylonitrile to the mixture; and/or viii) the combining comprises combining the asphaltenes and the first solvent to form a mixture and adding the acrylonitrile and the second solvent to the mixture.

[0076] With respect to the embodiments of the method disclosed herein, the method can further comprise the inclusion of a free-radical initiator. The combining can include any suitable permutations of combinations with the free-radical initiator to form the precursor fibre composition. Examples include, i) the combining comprises combining the asphaltenes, the free-radical initiator, and the at least one of acrylonitrile and acrylonitrile derivative(s); ii) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, and the at least one of acrylonitrile and acrylonitrile derivative(s); iii) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, the at least one of acrylonitrile and acrylonitrile derivative(s), and the second solvent; iv) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, and the second solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) to the mixture; v) the combining comprises combining the asphaltenes, the free- radical initiator, and the first solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) and the second solvent to the mixture; vi) the combining comprises combining the asphaltenes, the free-radical initiator, and the acrylonitrile; vii) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, and the acrylonitrile; viii) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, the acrylonitrile, and the second solvent; ix) the combining comprises combining the asphaltenes, the free-radical initiator, the first solvent, and the second solvent to form a mixture and adding the acrylonitrile to the mixture; and/or x) the combining comprises combining the asphaltenes, the free-radical initiator, and the first solvent to form a mixture and adding the acrylonitrile and the second solvent to the mixture.

[0077] With respect to the embodiments of the method disclosed herein, the method can further comprise the inclusion of PAN, PAN derivative(s), or a combination thereof. In particular embodiments, PAN is used and more typically, commercial PAN. In examples, the PAN, PAN derivative(s), or a combination thereof is considered to be an additive/reinforcement filler for enhancing spinnability and providing high performance fibres. In the method, the combining can include any suitable permutations of combinations with PAN, PAN derivative(s), or a combination thereof (typically, PAN) to form the precursor fibre composition. Examples include, i) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), and the at least one of acrylonitrile and acrylonitrile derivative(s); ii) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), the free-radical initiator, and the at least one of acrylonitrile and acrylonitrile derivative(s); iii) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), the free-radical initiator, the first solvent, and the at least one of acrylonitrile and acrylonitrile derivative(s); iv) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), the free-radical initiator, the first solvent, the at least one of acrylonitrile and acrylonitrile derivative(s), and the second solvent; v) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), the free-radical initiator, the first solvent, and the second solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) to the mixture; vi) the combining comprises combining the asphaltenes, the at least one of PAN and PAN derivative(s), the free-radical initiator, and the first solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) and the second solvent to the mixture; vii) the combining comprises combining the asphaltenes, PAN, and the acrylonitrile; viii) the combining comprises combining the asphaltenes, PAN, the free-radical initiator, and the acrylonitrile; ix) the combining comprises combining the asphaltenes, the PAN, the free-radical initiator, the first solvent, and the acrylonitrile; x) the combining comprises combining the asphaltenes, the PAN, the free- radical initiator, the first solvent, the acrylonitrile, and the second solvent; xi) the combining comprises combining the asphaltenes, the PAN, the free-radical initiator, the first solvent, and the second solvent to form a mixture and adding the acrylonitrile to the mixture; and/or xii) the combining comprises combining the asphaltenes, the PAN, the free-radical initiator, and the first solvent to form a mixture and adding the acrylonitrile and the second solvent to the mixture.

[0078] In the methods disclosed herein, the PAN, PAN derivative(s), or a combination thereof can instead be added during the formation of the precursor fibre composition and/or after the formation of the precursor fibre composition. In particular embodiments, PAN is used and more typically, commercial PAN.

[0079] With respect to the PAN, PAN derivative(s), or a combination thereof, these may comprises a high molecular weight PAN, a high molecular weight PAN derivative(s), or a combination thereof. In typical embodiments, the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight PAN and, more typically, high molecular weight commercial PAN. The PAN may have an average molecular weight (M _w ) of from about 2000 to 250,000, from about 20,000 to about 180,000, or from about 100,000 to about 150,000.

[0080] In other embodiments, the methods disclosed herein may further comprise heating to initiate the free radical(s) formation. The heating can include any suitable temperature to generate the free radical(s) formation of the at least one of acrylonitrile and acrylonitrile derivative(s). Some examples include heating to a temperature from about 15 °C to about 130 °C, from about 25 °C to about 100 °C, from about 35 °C to about 80 °C, from about 45 °C to about 70 °C, or from about 50 °C to about 65 °C. In typical embodiments, heating to a temperature from about 45 °C to about 70 °C or from about 50 °C to about 65 °C.

[0081] Other embodiments, the method can comprise A) chemical bridging/crosslinking compound(s) of asphaltene through reactive/radical coupling (e.g. acrylonitrile monomer, dimer, trimer, oligomer and/or polymer backbones). Radical coupling of a variety of components (alkyl and aromatic fragments) contained in AOA, to each other, through the active/radical polymeric acrylonitrile backbones formed by in-situ polymerization of acrylonitrile monomers in a homogenous AOA solution within a major amount of the first solvent (e.g. AOA is more soluble), and with a minor amount of a second solvent (e.g. PAN is more soluble), so that a homogenous composition of AOA (or other asphaltene source) and polymerized acrylonitrile (in-situ PAN); B) optionally, adding commercially high molecular PAN as an additional additive/reinforcement filler for enhancing spinnability and high performance fibres (e.g. carbon fibres). For example, PAN (Mw 150,000) in dimethylformamide (DMF), the second solvent or alternative solvent, is added to the homogenous composition to obtain a stable and/or meta-stable homogenous mixture, where the resultant composition can be concentrated through solvent evaporation without substantially precipitation of components (e.g. AOA and/or PAN itself) in the mixture and form a homogenous and spinnable slurry, which is spun into a fibre (e.g. fibre); and C) initiating “cyano-chemistry” at elevated temperature for cyclization and aromatization. The green fibre can be thermally treated to any suitable temperature. Examples include heating at a temperature from about room temperature to about 400 °C, about 380 °C, about 350 °C; and/or ramping from about 250 °C to about 350 °C or from about 280 °C to about 330 °C. Such thermal treatment can provide oxidative stabilization of the fibre. In embodiments, the heating of the fibre (e.g. in air) promoted cyano-chemistry for cyclization such as and without being limited thereto, cyclization and cross-linking of linear molecular chains and/or hyperbranched molecular chains via dehydration and polycondensation, and/or forming longitudinally oriented polyaromatic structures along the fibre axis. In other embodiments, the oxidized and stabilized fibre can be further thermally treated in N2 and/or Ar for carbon fibre formation with high graphitic crystallinity to any suitable temperature. Examples include heating in N2 and/or Ar at a temperature from about 350 °C to about 3500 °C; or about 3000 °C. In another embodiment, heating in N ₂ to about 1200 °C. In another embodiment, heating in N ₂ to about 1500 °C. In another embodiment, heating in N ₂ to about 1800 °C. In another embodiment, heating in N2 to about 2000 °C. In another embodiment, heating in N2 to about 2500 °C. In another embodiment, heating in Ar to about 3000 °C.

[0082] In the schematic below, and without being bound by theory, Box A shows examples of the cross-linking between the asphaltene compound(s) and the acrylonitrile polymeric backbones polymerized in-situ through free radical chemistry, wherein free radical initiation and propagation occur amongst different species and fragments while the polymeric acrylonitrile backbones are forming; Box B illustrates the combination of commercial PAN, which can enhance spinnability, polycyclization and aromatization, and higher mechanical strength for the final carbon fibres, to form a homogenous composition and spinnable system Box C.

ii) Substrates in the Methods for Making the Precursor Fibre Composition

[0083] As outlined under the definition section, the asphaltenes have been defined. Any suitable asphaltenes may be used. For example, any asphaltenes that can be derived from crude oil, heavy crude oil, bitumen, coal tar through liquefaction, plant(s), or a combination thereof. In certain embodiments, the asphaltenes are derived from oilsands bitumen, such as Alberta oilsands bitumen. In a specific embodiment, the asphaltenes are about 15 wt% fraction from Alberta oilsands bitumen insoluble in heptane and about 20 wt% insoluble in pentane. The asphaltenes may be Alberta Oilsands Asphaltenes (AOA). The Alberta Oilsands Asphaltenes (AOA) may have a fraction containing about 20 to about 22 wt% maltenes. In other embodiments, the asphaltenes are Alberta Oilsands Asphaltenes (AOA) comprising a maltenes-free fraction.

[0084] The asphaltenes can have at least one of:

; and

[0085] As outlined under the definition section, the acrylonitrile derivative(s) have been defined. Any suitable acrylonitrile derivative(s) may be used. Examples may include acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, or a combination thereof. Other examples may include substituted acrylonitrile, substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, or a combination thereof. The term “substituent” or “substituted” used in conjunction with the groups described herein refers to a chemically acceptable group, i.e., a moiety that maintains utility.

[0086] As outlined under the definition section, the polyacrylonitrile derivative(s) have been defined. Any suitable polyacrylonitrile derivative(s) may be used. Examples may include a polymer of acrylonitrile derivatives, a copolymer of acrylonitrile and acrylonitrile derivatives, a copolymer of acrylonitrile and a vinyl-based monomer, wherein the vinyl-based monomer is copolymerizable with acrylonitrile, and the like.

[0087] As outlined under the definition section, the free-radical initiator(s) have been defined. Any suitable free radical initiator(s) may be used. Examples of free radical initiators may include free-radical initiator(s) which decompose at temperatures in the range of about 20 °C to about 180°C. These initiators may be peroxides, such as alkali metal peroxides (e.g. lithium or sodium peroxides), alkyl alkali metals (e.g. n-butyl lithium), ammonium peroxodisulfates, organic hydroperoxides, organic peroxides, hydrogen peroxide, azo compounds, and/or water-soluble azo compounds. Exemplary free radical initiators include ammonium persulphate and/or peroxides (e.g. lauroyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-bis(tert- butylperoxy)-2,5-dimethylhexane, bis(tert-butyl peroxyisopropyl)benzene, and tert-butyl hydroperoxide), azo compounds (e.g., 2,2’-azobis(2-methyl-propanenitrile), 2,2’-azobis(2- methylbutanenitrile), and 1,1’-azobis(cyclohexanecarbonitrile)). Other free-radical initiators that will be well-known in the art may also be suitable for use in the compositions disclosed herein.

[0088] Any suitable amount of asphaltenes may be used. Examples of the amount of asphaltenes that may be used is from about 0.1 wt% to about 90 wt%; from about 0.1 wt% to about 80 wt%; from about 0.1 wt% to about 70 wt%; from about 0.1 wt% to about 60 wt%; from about 1 wt% to about 90 wt%; from about 1 wt% to about 80 wt%; from about 1 wt% to about 70 wt%; from about 1 wt% to about 60wt%; from about 5 wt% to about 90 wt%; from about 5 wt% to about 80 wt%; from about 5 wt% to about 70 wt%; or from about 5 wt% to about 60 wt%, based on the total weight of based on the total weight of the asphaltenes, the at least one of acrylonitrile and acrylonitrile derivative(s), and, optionally, the free radical initiator and/or PAN, PAN derivative(s), or a combination thereof.

[0089] Any suitable amount of the at least one of acrylonitrile and acrylonitrile derivative(s) may be used. Examples of the amount of at least one of acrylonitrile and acrylonitrile derivative(s) that may be used is from about 0.1 wt% to about 90 wt%; from about 0.1 wt% to about 80 wt%; from about 0.1 wt% to about 70 wt%; from about 0.1 wt% to about 60 wt%; from about 1 wt% to about 90 wt%; from about 1 wt% to about 80 wt%; from about 1 wt% to about 70 wt%; from about 1 wt% to about 60 wt%; from about 5 wt% to about 90 wt%; from about 5 wt% to about 80 wt%; from about 5 wt% to about 70 wt%; or from about 5 wt% to about 60 wt%, based on the total weight of the asphaltenes, the at least one of acrylonitrile and acrylonitrile derivative(s), and, optionally, the free radical initiator and/or PAN, PAN derivative(s), or a combination thereof.

[0090] Any suitable amount of the free radical initiator(s) may be used. Examples of the amount of the free radical initiator(s) that may be used is less than about 15 wt%, less than about 10 wt%, less than about 5 wt%, less than about 4.5 wt%, less than about 4.0 wt%, less than about 3.5 wt%, less than about 3.0 wt%, less than about 2.5 wt%, less than about 2.0 wt%, less than about 1.5 wt%, less than about 1.0 wt%, less than about 0.9 wt%, less than about 0.5 wt%, less than about 0.1 wt%, less than about 0.09 wt%, less than about 0.08 wt%, less than about 0.07 wt%, less than about 0.06 wt%, less than about 0.05 wt%; about 15 wt%, about 10 wt%, about 5.0 wt%, about 4.5 wt%, about 4.0 wt%, about 3.5 wt%, about 3.0 wt%, about 2.5 wt%, about 2.0 wt%, about 1.5 wt%, about 1.0 wt%, about 0.9 wt%, about 0.5 wt%, about 0.1 wt%, about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.06 wt%, or about 0.05 wt% based on the total weight of the asphaltenes, the at least one of acrylonitrile and acrylonitrile derivative(s), the free radical initiator, and, optionally, PAN, PAN derivative(s), or a combination thereof. [0091] Any suitable ratios of the substrates may be used. The weight ratios of asphaltenes to at least one of acrylonitrile and acrylonitrile derivative(s) is from about 1:99 to about 99:1; from about 50:50 to about 80:20, or from about 70:30 to about 85:15.

[0092] Any suitable amount of PAN, PAN derivative(s), or a combination thereof may be used. Examples of the amount of the PAN, PAN derivative(s), or a combination thereof that may be used is as follows: about 0.1 wt% to about 50% wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, or less than about 20 wt% based on the total weight of asphaltenes. iii) Precursor Fibre Composition

[0093] In embodiments, the precursor fibre composition is made by the method disclosed herein.

[0094] In other embodiments, a precursor fibre composition comprises free-radical intermediate(s) coupled to compound(s) of asphaltenes, wherein the free radical intermediate(s) are formed from the coupling of free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s). The at least one of acrylonitrile and acrylonitrile derivative(s) may comprise acrylonitrile, substituted acrylonitrile, or a combination thereof.

[0095] In further embodiments, the free radical intermediate(s) may comprise i) acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, PAN derivative(s) or a combination thereof; ii) acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, a copolymer of acrylonitrile and acrylonitrile derivative(s), or a combination thereof; iii) acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, PAN, ora combination thereof; and/or iv) PAN.

[0096] In view of the embodiments disclosed herein, the coupling of the free-radical monomers and/or free-radical intermediate(s) with the compound(s) of asphaltenes can also result in free-radical intermediate(s) of asphaltenes coupled to acrylonitrile, acrylonitrile derivatives, a combination thereof, free-radical intermediate(s) of acrylonitrile, acrylonitrile derivatives, or a combination thereof. In an embodiment, the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) couple to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes to form secondary free-radical intermediate(s). For example, the secondary free-radical intermediate(s) comprise asphaltenes-acrylonitrile radical(s), asphaltenes-acrylonitrile dimer radical(s), asphaltenes-acrylonitrile trimer radical(s), asphaltenes-acrylonitrile oligomer radical(s), asphaltenes-PAN radical(s), or a combination thereof. [0097] The coupling of the free-radical intermediate(s) with the compound(s) of asphaltenes can result in cross-linking. The precursor fibre composition may comprise macromolecules having a linear and/or hyperbranched polymer assembly. In typical embodiments, the precursor fibre composition comprises macromolecules having a PAN-asphaltene linear and/or hyperbranched polymer assembly.

[0098] In other embodiments, the composition further comprises a first solvent. In further embodiments, the composition further comprises a second solvent. The embodiments disclosed herein above with respect to the first and second solvent are similarly applicable.

[0099] The precursor fibre composition disclosed herein can further comprise PAN, PAN derivative(s), or a combination thereof. The embodiments disclosed herein above with respect to the PAN, PAN derivative(s), or a combination thereof are similarly applicable. With respect to the PAN, PAN derivative(s), or a combination thereof, and as outlined above, these may comprises a high molecular weight PAN, a high molecular weight PAN derivative(s), or a combination thereof. In typical embodiments, the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight PAN and, more typically, high molecular weight commercial PAN. The PAN may have an average molecular weight (M _w ) of from about 2000 to 250,000, from about 20,000 to about 180,000, or from about 100,000 to about 150,000.

[0100] As outlined under the definition section and section ii) above, the asphaltenes, acrylonitrile derivative(s), and PAN derivative(s) disclosed herein are similarly applicable.

[0101] In embodiments, the precursor fibre composition is homogeneous (e.g. homogeneous phase) and, in specific embodiments, can be a homogeneous solution or slurry. The homogeneous/ homogeneous phase can be a stable and/or meta-stable homogenous mixture. The homogenous composition can, therefore, be spinnable. The precursor fibre composition disclosed here is capable of forming a fibre. In certain embodiments, the precursor fibre composition is capable of forming a green fibre. In other embodiments, the green fibre is pre-requisition of forming a carbon fibre. The precursor fibre composition can be concentrated to a suitable viscosity for making fibres.

[0102] In more specific embodiments, the precursor fibre composition disclosed here is capable of being spun into fibres. In certain embodiments, the precursor fibre composition is capable of being spun into fibres using electrospinning, melt-spinning and/or wet-spinning. The fibres can be green fibres. The fibres can be carbon fibres. The green fibre can be thermally treated to form carbon fibre. The green fibre can be thermally treated to any suitable temperature. Examples include heating at a temperature from about room temperature to about 400 °C, about 380 °C, about 350 °C; and/or ramping from about 250 °C to about 350 °C or from about 280 °C to about 330 °C. Such thermal treatment can provide oxidative stabilization of the fibre. In embodiments, the heating of the fibre (e.g.in air) promoted cyano-chemistry for cyclization such as and without being limited thereto, cyclization and cross-linking of linear molecular chains via dehydration and polycondensation, and/or forming longitudinally oriented polyaromatic structures along the fibre axis. In other embodiments, the oxidized and stabilized fibre can be further thermally treated in N ₂ and/or Ar for carbon fibre formation with high graphitic crystallinity to any suitable temperature. Examples include heating in N ₂ and/or Ar at a temperature from about 350 °C to about 3500 °C; or about 3000 °C. In another embodiment, heating in N ₂ to about 1200 °C. In another embodiment, heating in N ₂ to about 1500 °C. In another embodiment, heating in N ₂ to about 1800 °C. In another embodiment, heating in N ₂ to about 2000 °C. In another embodiment, heating in N ₂ to about 2500 °C. In another embodiment, heating in Ar to 3000 °C.

II. Fibers and Methods for Making Fibres from a Precursor Fibre Composition

[0103] The precursor fibre composition disclosed herein may be concentrated to a suitable viscosity for making fibres. As disclosed above, the precursor fibre composition can be spun into an asphaltenes green fibre. The green fibres can be treated in air at elevated temperatures (e.g. less than about 400 °C) for promoting the “cyano-chemistry” for cyclization / condensation / aromatization along, for example, the PAN polymer backbones (including in-situ polymerized PAN and PAN-additive) and oxidative stabilization. The operational temperature profiles for the heat treatment may be determined according to the thermal decomposition profiles of the fibre itself. Additional aromatization/condensation can be established with temperature profiles in the temperature range from about 400 °C to about 1000 °C, followed by the carbonization/graphitization up to 3000 °C in an inert atmosphere (e.g. N ₂ /Ar).

[0104] The precursor fibre composition is capable of being spun into fibres using electrospinning, melt-spinning, and/or wet-spinning. The fibres (e.g. green fibres) can be heated to form carbon fibres. The fibre can be heated to any suitable temperature in air for oxidative stabilization. Examples include heating at a temperature from about 200 °C to about 450 °C, from about 250 °C to about 400 °C, or from about 260 °C to about 350 °C. In embodiments, the heating of the fibre promoted cyano-chemistry cyclization such as and without being limited thereto, cyclization and cross-linking of linear molecular chains via dehydration and polycondensation. In other embodiments, further heat treatment in inert atmosphere up to about 3000 °C, whereby the stabilized fibre can be converted into carbon fibre with the formation of longitudinally oriented graphitic crystallites along the fibre axis [0105] The precursor composition can be spun into fibres using any suitably available technology. Examples of spinning technology include electrospinning, melt-spinning, and/or wet-spinning.

[0106] Traditional industrial processes for synthetic polymer microfiber spinning can be classified as either solvent-based or melt-based. Solvent processing involves the spinning of a polymer solution with solidification of the fiber either through coagulation in a non-soluble solvent(s) bath (wet-spinning) or solvent evaporation (dry-spinning). In contrast, melt spinning produces fibers via the spinning of molten polymer that solidifies upon cooling; drawing usually accompanies this spinning process to induce chain orientation and enhance mechanical properties.

[0107] Electrospinning is perhaps the most well-known, and one of the oldest techniques for generating sub-micron fibers in lab-scale from a polymer solution, or less commonly, a polymer melt via the application of a large electric field. This charged polymer jet is subjected to electrostatic forces, which act to elongate, thin, and solidify the polymer fiber in the characteristic "whipping instability" region.

[0108] Certain aspects are provided as follows:

Aspect 1. A method for making a precursor fibre composition, the method comprising: combining asphaltenes and at least one of acrylonitrile and acrylonitrile derivative(s); forming free radical(s) of the at least one of acrylonitrile and acrylonitrile derivative(s), and coupling with compound(s) of the asphaltenes to form the precursor fibre composition.

Aspect 2. The method of aspect 1 , wherein the at least one of acrylonitrile and acrylonitrile derivative(s) comprise acrylonitrile, substituted acrylonitrile, or a combination thereof.

Aspect 3. The method of aspect 1 or 2, wherein the at least one of acrylonitrile and acrylonitrile derivative(s) comprise acrylonitrile.

Aspect 4. The method of any one of aspects 1 to 3, wherein the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) couple to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes.

Aspect 5. The method of any one of aspects 1 to 4, wherein the free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s) couple to form free-radical intermediate(s), whereby the intermediate(s) couple with the compound(s) of the asphaltenes to form secondary free-radical intermediate(s). Aspect 6. The method of any one of aspects 1 to 5, wherein the free-radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, PAN derivative(s) or a combination thereof. Aspect 7. The method of any one of aspects 1 to 5, wherein the free-radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, a copolymer of acrylonitrile and acrylonitrile derivative(s), or a combination thereof. Aspect 8. The method of any one of aspects 1 to 7, wherein the free-radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, or a combination thereof.

Aspect 9. The method of any one of aspects 5 to 8, wherein the secondary free-radical intermediate(s) comprise asphaltenes-acrylonitrile radical(s), asphaltenes-acrylonitrile dimer radical(s), asphaltenes-acrylonitrile trimer radical(s), asphaltenes-acrylonitrile oligomer radical(s), asphaltenes-PAN radical(s), or a combination thereof.

Aspect 10. The method of any one of aspects 1 to 9, wherein the intermediate comprises PAN, asphaltenes-PAN radical(s), ora combination thereof.

Aspect 11. The method of any one of aspects 1 to 10, wherein the coupling is covalent bonding through C-C bond formation.

Aspect 12. The method of any one of aspects 1 to 11 , wherein the coupling of the intermediate(s) with the compound(s) of asphaltenes comprises cross-linking.

Aspect 13. The method of any one of aspects 1 to 12, wherein the precursor fibre composition comprises macromolecules having a linear and/or hyperbranched polymer assembly.

Aspect 14. The method of any one of aspects 1 to 13, wherein the precursor fibre composition comprises macromolecules having a PAN-asphaltene linear and/or hyperbranched polymer assembly.

Aspect 15. The method of any one of aspects 1 to 14, wherein the precursor fibre composition is homogeneous.

Aspect 16. The method of any one of aspects 1 to 15, wherein the precursor fibre composition is a homogeneous solution or slurry. Aspect 17. The method of any one of aspects 1 to 16, wherein the precursor fibre composition is a stable and/or meta-stable homogenous mixture.

Aspect 18. The method of any one of aspects 1 to 17, wherein the combining further comprises a first solvent, wherein the asphaltenes are soluble in the first solvent. Aspect 19. The method of any one of aspects 1 to 18, wherein the combining further comprises a second solvent, wherein the second solvent is selected such that at least one of polyacrylonitrile (PAN) and PAN derivative(s) are soluble.

Aspect 20. The method of aspect 19, wherein the second solvent is selected such that polyacrylonitrile (PAN) is soluble. Aspect 21. The method of any one of aspects 18 to 20, wherein a major amount of the first solvent and a minor amount of the second solvent is present.

Aspect 22. The method of any one of aspects 18 to 21 , wherein the first solvent and the second solvent are miscible.

Aspect 23. The method of any one of aspects 18 to 22, wherein the first solvent and the second solvent form a single phase.

Aspect 24. The method of any one of aspects 1 to 23, wherein the asphaltenes and at least one of acrylonitrile and acrylonitrile derivative(s) remain substantially in solution (e.g. precipitation free).

Aspect 25. The method of any one of aspects 1 to 24, wherein the first solvent is an organic solvent.

Aspect 26. The method of any one of aspects 1 to 25, wherein at least about 70 wt% of the asphaltenes is soluble in the first solvent; at least about 80 wt% of the asphaltenes is soluble in the first solvent; at least about 90 wt% of the asphaltenes is soluble in the first solvent; at least about 99 wt% of the asphaltenes is soluble in the first solvent; or about 100 wt% of the asphaltenes is soluble in the first solvent.

Aspect 27. The method of any one of aspects 1 to 26, wherein the first solvent comprises pyridine, pyrrole, toluene, benzene, xylene, acetonitrile, tetrahydrofuran (THF), anisole, quinoline, or a combination thereof.

Aspect 28. The method of any one of aspects 1 to 27, wherein the second solvent is an organic solvent, inorganic solvent, ionic liquid (IL) or a combination thereof.

Aspect 29. The method of any one of aspects 1 to 28, wherein at least about 70 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 80 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 90 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 99 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; or about 100 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent.

Aspect 30. The method of any one of aspects 1 to 29, wherein the second solvent comprises dimethyl formamide (DMF), dimethyl sulphoxide (DMSO), N-methyl-2-pyrrolidon (NMP), propylene carbonate, ionic liquid, such as pyridinium benzylchloride or any suitable salt in a liquid state, aqueous solutions thereof, aqueous sodium thiocyanate, or a combination thereof.

Aspect 31. The method of any one of aspects 1 to 30, wherein the combining comprises combining the asphaltenes, the first solvent, and the at least one of acrylonitrile and acrylonitrile derivative(s).

Aspect 32. The method of any one of aspects 1 to 31 , wherein the combining comprises combining the asphaltenes, the first solvent, the at least one of acrylonitrile and acrylonitrile derivative(s), and the second solvent.

Aspect 33. The method of aspect 32, wherein the combining comprises combining the asphaltenes, the first solvent, and the second solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) to the mixture.

Aspect 34. The method of any one of aspects 1 to 33, wherein the combining further comprises a free radical initiator.

Aspect 35. The method of aspect 34, wherein the combining comprises combining the asphaltenes, the first solvent, and the free radical initiator to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) and the second solvent to the mixture.

Aspect 36. The method of aspect 34, wherein the combining comprises combining the asphaltenes, the first solvent, the free radical initiator, and the second solvent to form a mixture and adding the at least one of acrylonitrile and acrylonitrile derivative(s) to the mixture.

Aspect 37. The method of any one of aspects 1 to 36, wherein the method further comprises heating to initiate the free radical(s) formation.

Aspect 38. The method of aspect 37, wherein the heating includes heating to a temperature from about 15 °C to about 130 °C, from about 25 °C to about 100 °C, from about 35 °C to about 80 °C, from about 45 °C to about 70 °C, or from about 50 °C to about 65 °C. Aspect 39. The method of any one of aspects 1 to 38, wherein the combining further comprises PAN, PAN derivative(s), ora combination thereof.

Aspect 40. The method of any one of aspects 1 to 39, further comprising adding PAN, PAN derivative(s), ora combination thereof to the precursor fibre composition.

Aspect 41. The method of aspect 39 or 40, wherein the amount of PAN, PAN derivative(s), or a combination thereof has a concentration from about 0.1 wt% to about 50% wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, or less than about 20 wt% based on the total weight of asphaltenes.

Aspect 42. The method of any one of aspect 39 or 41 , wherein the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight PAN, a high molecular weight PAN derivative(s), or a combination thereof.

Aspect 43. The method of any one of aspects 39 to 42, wherein the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight commercial PAN.

Aspect 44. The method of any one of aspects 1 to 43, wherein the PAN has an average molecular weight (M _w ) of from about 2000 to 250,000, from about 20,000 to about 180,000, or from about 100,000 to about 150,000.

Aspect 45. The method of any one of aspects 1 to 44, wherein the precursor fibre composition is in a homogenous phase.

Aspect 46. The method of any one of aspects 1 to 45, wherein the precursor fibre composition is capable of forming a fibre.

Aspect 47. The method of any one of aspects 1 to 46, wherein the precursor fibre composition is capable of forming an asphaltenes green fibre.

Aspect 48. The method of any one of aspects 1 to 47, wherein the precursor fibre composition is capable of forming a carbon fibre.

Aspect 49. The method of any one of aspects 1 to 48, wherein the asphaltenes are derived from crude oil, heavy crude oil, bitumen, coal tar through liquefaction, plant(s), or a combination thereof.

Aspect 50. The method of aspect 49, wherein the asphaltenes are derived from oilsands bitumen.

Aspect 51. The method of aspect 49, wherein the asphaltenes are derived from Alberta oilsands bitumen. Aspect 52. The method of any one of aspects 1 to 51 , wherein the asphaltenes are about 15 wt% fraction from Alberta oilsands bitumen insoluble in heptane and about 20 wt% insoluble in pentane.

Aspect 53. The method of any one of aspects 1 to 52, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA).

Aspect 54. The method of any one of aspects 1 to 52, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA) comprising a fraction containing about 20 to about 22 wt% maltenes.

Aspect 55. The method of any one of aspects 1 to 52, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA) comprising a maltenes-free fraction.

Aspect 56. The method of any one of aspects 1 to 55, wherein the asphaltenes comprises at least one of:

; and Aspect 57. The method of any one of aspects 1 to 41 , wherein the amount of asphaltenes is from about 0.1 wt% to about 90 wt%; from about 0.1 wt% to about 80 wt%; from about 0.1 wt% to about 70 wt%; from about 0.1 wt% to about 60 wt%; from about 1 wt% to about 90 wt%; from about 1 wt% to about 80 wt%; from about 1 wt% to about 70 wt%; from about 1 wt% to about 60wt%; from about 5 wt% to about 90 wt%; from about 5 wt% to about 80 wt%; from about 5 wt% to about 70 wt%; or from about 5 wt% to about 60 wt%, based on the total weight of based on the total weight of the asphaltenes, the at least one of acrylonitrile and acrylonitrile derivative(s), and the free radical initiator. Aspect 58. The method of any one of aspects 1 to 42, wherein the amount of at least one of acrylonitrile and acrylonitrile derivative(s) is from about 0.1 wt% to about 90 wt%; from about 0.1 wt% to about 80 wt%; from about 0.1 wt% to about 70 wt%; from about 0.1 wt% to about 60 wt%; from about 0.1 wt% to about 50 wt%; from about 0.1 wt% to about 40 wt%; from about 0.1 wt% to about 30 wt%; from about 0.1 wt% to about 20 wt%; from about 0.1 wt% to about 15 wt% based on the total weight of the asphaltenes.

Aspect 59. The method of any one of aspects 1 to 58, wherein the amount of the free radical initiator is less than about 15 wt%, less than about 10 wt%, less than about 5 wt%, less than about 4.5 wt%, less than about 4.0 wt%, less than about 3.5 wt%, less than about 3.0 wt%, less than about 2.5 wt%, less than about 2.0 wt%, less than about 1.5 wt%, less than about 1.0 wt%, less than about 0.9 wt%, less than about 0.5 wt%, less than about 0.1 wt%, less than about 0.09 wt%, less than about 0.08 wt%, less than about 0.07 wt%, less than about 0.06 wt%, less than about 0.05 wt%; about 15 wt%, about 10 wt%, about 5.0 wt%, about 4.5 wt%, about 4.0 wt%, about 3.5 wt%, about 3.0 wt%, about 2.5 wt%, about 2.0 wt%, about 1.5 wt%, about 1.0 wt%, about 0.9 wt%, about 0.5 wt%, about 0.1 wt%, about 0.09 wt%, about 0.08 wt%, about 0.07 wt%, about 0.06 wt%, or about 0.05 wt% based on the total weight of the asphaltenes, the at least one of acrylonitrile and acrylonitrile derivative(s), and the free radical initiator.

Aspect 60. The method of any one of aspects 1 to 59, wherein the weight ratio of asphaltenes to at least one of acrylonitrile and acrylonitrile derivative(s) is from about 1 :99 to about 99: 1 ; from about 50:50 to about 80:20, or from about 70:30 to about 85: 15.

Aspect 61. The method of any one of aspects 1 to 60, wherein the precursor fibre composition is concentrated to a suitable viscosity for making fibres.

Aspect 62. The method of any one of aspects 1 to 61 , wherein the precursor fibre composition is spun into fibres.

Aspect 63. The method of any one of aspects 1 to 62, wherein the precursor fibre composition is spun into fibres using electrospinning, melt-spinning, wet-spinning or a combination thereof.

Aspect 64. The method of any one of aspects 1 to 63, wherein the fibre comprises an asphaltenes green fibre.

Aspect 65. The method of any one of aspects 1 to 64, wherein the fibre comprises a carbon fibre precursor.

Aspect 66. The method of any one of aspects 1 to 65, wherein heating the fibre to form carbon fibres. Aspect 67. The method of any one of aspects 1 to 66, wherein the fibre is heated to less than about 400 °C (e.g. in air) for initiation of the “cyano-chemistry” for cyclization / condensation / aromatization.

Aspect 68. The method of any one of aspects 1 to 67, wherein the fibre is heated further in the temperature range from about 400 °C to about 1000 °C in inert atmosphere, followed by the carbonization/graphitization up to about 3000 °C in an inert atmosphere (e.g. N ₂ /Ar).

Aspect 69 The method of any one of aspects 1 to 68, wherein the heating the fibre includes heating to a temperature from about 200 °C to about 450 °C, from about 250 °C to about 400 °C, or from about 260 °C to about 350 °C in air for oxidative stabilization.

Aspect 70. The method of any one of aspects 1 to 69, wherein the heating of the fibre promotes cyano-chemistry cyclization.

Aspect 71. The method of any one of aspects 1 to 70, wherein the heating of the fibre promotes cyclization and cross-linking of linear molecular chains via dehydration, cyclization through CºN functional group from PAN and polycondensation, forming longitudinally oriented graphitic crystallites along the fibre axis.

Aspect 72. A precursor fibre composition made by the method of any one of aspects 1 to 71.

Aspect 73. A precursor fibre composition comprising free-radical intermediate(s) coupled to compound(s) of asphaltenes, wherein the free radical intermediate(s) is formed from the coupling of free radical(s) of at least one of acrylonitrile and acrylonitrile derivative(s).

Aspect 74. The precursor composition of aspect 73, wherein the intermediate(s) coupled with the compound(s) of the asphaltenes to form secondary free-radical intermediate(s), which are coupled to one another.

Aspect 75. The precursor fibre composition of aspect 74, wherein the at least one of acrylonitrile and acrylonitrile derivative(s) comprise acrylonitrile, substituted acrylonitrile, or a combination thereof.

Aspect 76. The precursor fibre composition of any one of aspects 73 to 75, wherein the free radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, PAN derivative(s) or a combination thereof.

Aspect 77. The precursor fibre composition of any one of aspects 73 to 75, wherein the free radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, polyacrylonitrile (PAN), substituted acrylonitrile dimers, substituted acrylonitrile trimers, substituted acrylonitrile oligomers, a copolymer of acrylonitrile and acrylonitrile derivative(s), or a combination thereof.

Aspect 78. The precursor fibre composition of any one of aspects 73 to 75, wherein the free radical intermediate(s) comprise acrylonitrile dimers, acrylonitrile trimers, acrylonitrile oligomers, PAN, or a combination thereof.

Aspect 79. The precursor fibre composition of any one of aspects 73 to 78, wherein the secondary free-radical intermediate(s) comprise asphaltenes-acrylonitrile radical(s), asphaltenes-acrylonitrile dimer radical(s), asphaltenes-acrylonitrile trimer radical(s), asphaltenes-acrylonitrile oligomer radical(s), asphaltenes-PAN radical(s), ora combination thereof.

Aspect 80. The precursor fibre composition of any one of aspects 73 to 79, wherein the intermediate comprises PAN, asphaltenes-PAN, or a combination thereof.

Aspect 81. The precursor fibre composition of any one of aspects 73 to 80, wherein the coupling is covalent bonding through C-C bond formation.

Aspect 82. The precursor fibre composition of any one of aspects 73 to 81 , wherein the coupling of the intermediate(s) with the compound(s) of asphaltenes comprises cross-linking.

Aspect 83. The precursor fibre composition of any one of aspects 73 to 82, wherein the precursor fibre composition comprises macromolecules having a linear and/or hyperbranched polymer assembly.

Aspect 84. The precursor fibre composition of any one of aspects 73 to 82, wherein the precursor fibre composition comprises macromolecules having a PAN-asphaltene linear and/or hyperbranched polymer assembly.

Aspect 85. The precursor fibre composition of any one of aspects 73 to 84, wherein the precursor fibre composition is homogeneous.

Aspect 86. The precursor fibre composition of any one of aspects 73 to 85, wherein the precursor fibre composition is a homogeneous solution or slurry.

Aspect 87. The precursor fibre composition of any one of aspects 73 to 86, wherein the precursor fibre composition is a stable and/or meta-stable homogenous mixture.

Aspect 88. The precursor fibre composition of any one of aspects 73 to 87, wherein the composition further comprises a first solvent, wherein the asphaltenes are soluble in the first solvent. Aspect 89. The precursor fibre composition of any one of aspects 73 to 88, wherein the composition further comprises a second solvent, wherein the second solvent is selected such that at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble.

Aspect 90. The precursor fibre composition of aspect 89, wherein the second solvent is selected such that polyacrylonitrile (PAN) is soluble.

Aspect 91. The precursor fibre composition of any one of aspects 88 to 90, wherein the first solvent and the second solvent are miscible.

Aspect 92. The precursor fibre composition of any one of aspects 88 to 91 , wherein the first solvent and the second solvent form a single phase.

Aspect 93. The precursor fibre composition of any one of aspects 88 to 92, wherein the first solvent is an organic solvent.

Aspect 94. The precursor fibre composition of any one of aspects 88 to 93, wherein at least about 70 wt% of the asphaltenes is soluble in the first solvent; at least about 80 wt% of the asphaltenes is soluble in the first solvent; at least about 90 wt% of the asphaltenes is soluble in the first solvent; at least about 99 wt% of the asphaltenes is soluble in the first solvent; or about 100 wt% of the asphaltenes is soluble in the first solvent.

Aspect 95. The precursor fibre composition of any one of aspects 88 to 94, wherein the first solvent comprises pyridine, pyrrole, toluene, benzene, xylene, acetonitrile, tetrahydrofuran (THF), anisole, quinoline, ora combination thereof.

Aspect 96. The precursor fibre composition of any one of aspects 88 to 95, wherein the second solvent is an organic solvent, inorganic solvent, Ionic liquid, or a combination thereof.

Aspect 97. The precursor fibre composition of any one of aspects 88 to 96, wherein at least about 70 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 80 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 90 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; at least about 99 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent; or about 100 wt% of the at least one of polyacrylonitrile (PAN) and PAN derivative(s) is soluble in the second solvent.

Aspect 98. The precursor fibre composition of any one of aspects 88 to 97, wherein the second solvent comprises dimethyl formamide (DMF), dimethyl sulphoxide (DMSO), N- methyl-2-pyrrolidon (NMP), propylene carbonate, ionic liquid, such as pyridinium benzylchloride or any suitable salt in a liquid state, aqueous solutions thereof, aqueous sodium thiocyanate, or a combination thereof. Aspect 99. The precursor fibre composition of any one of aspects 73 to 98, further comprising PAN, PAN derivative(s), ora combination thereof.

Aspect 100. The precursor fibre composition of any one of aspects 73 to 99, wherein the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight PAN, a high molecular weight PAN derivative(s), ora combination thereof.

Aspect 101. The precursor fibre composition of any one of aspects 73 to 100, wherein the PAN, PAN derivative(s), or a combination thereof comprises a high molecular weight commercial PAN.

Aspect 102. The precursor fibre composition of any one of aspects 73 to 101, wherein the PAN has an average molecular weight (M _w ) from about 2000 to 250,000, from about 20,000 to about 180,000, or from about 100,000 to about 150,000.

Aspect 103. The precursor fibre composition of any one of aspects 73 to 102, wherein the precursor fibre composition is in a homogenous phase.

Aspect 104. The precursor fibre composition of any one of aspects 73 to 103, wherein the precursor fibre composition is capable of forming a fibre.

Aspect 105. The precursor fibre composition of any one of aspects 73 to 104, wherein the precursor fibre composition is capable of forming an asphaltenes green fibre.

Aspect 106. The precursor fibre composition of any one of aspects 73 to 105, wherein the precursor fibre composition is capable of forming a carbon fibre.

Aspect 107. The precursor fibre composition of aspect 106, wherein the asphaltenes green fibre is capable of forming a carbon fibre through thermal treatment.

Aspect 108. The precursor fibre composition of any one of aspects 73 to 107, wherein the asphaltenes are derived from crude oil, heavy crude oil, bitumen, coal tar through liquefaction, plant(s), ora combination thereof.

Aspect 109. The precursor fibre composition of aspect 108, wherein the asphaltenes are derived from oilsands bitumen.

Aspect 110. The precursor fibre composition of aspect 108, wherein the asphaltenes are derived from Alberta oilsands bitumen.

Aspect 111. The precursor fibre composition of any one of aspects 73 to 110, wherein the asphaltenes are about 15 wt% from the Alberta oilsands bitumen insoluble in heptane and about 20 wt% insoluble in pentane. Aspect 112. The precursor fibre composition of aspect 111, wherein the asphaltenes are about 15 wt% from the Alberta oilsands bitumen insoluble in heptane and about 20 wt% insoluble in pentane.

Aspect 113. The precursor fibre composition of any one of aspects 73 to 112, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA).

Aspect 114. The precursor fibre composition of any one of aspects 73 to 113, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA) comprising a fraction containing about 20 to about 22 wt% maltenes.

Aspect 115. The precursor fibre composition of any one of aspects 73 to 113, wherein the asphaltenes are Alberta Oilsands Asphaltenes (AOA) comprising a maltenes-free fraction.

Aspect 116. The precursor fibre composition of any one of aspects 73 to 115, wherein the asphaltenes comprises at least one of:

; and

Aspect 117. The precursor fibre composition of any one of aspects 72 to 116, wherein the precursor fibre composition has a concentration that has a suitable viscosity for making fibres.

Aspect 118. The precursor fibre composition of any one of aspects 72 to 117, wherein the precursor fibre composition is capable of being spun into fibres.

Aspect 119. The precursor fibre composition of any one of aspects 72 to 118, wherein the precursor fibre composition is capable of being spun into fibres using electrospinning, meltspinning, wet-spinning, and/or a combination thereof. Aspect 120. The precursor fibre composition of any one of aspects 117 to 119, wherein the fibre comprises an asphaltene green fibre.

Aspect 121. The precursor fibre composition of any one of aspects 117 to 120, wherein the fibre comprises a carbon fibre.

Aspect 122. The precursor fibre composition of any one of aspects 117 to 119, wherein the fibre comprises an asphaltenes green fibre that can be converted into a carbon fibre through thermal treatment.

Aspect 123. The precursor fibre composition of any one of aspects 117 to 119, wherein the fibre is heated to form carbon fibres.

Aspect 124. The precursor fibre composition of any one of aspects 117 to 123, wherein the fibre is heated to less than about 400 °C (e.g. in air) for initiation of the “cyano-chemistry” for cyclization / condensation / aromatization.

Aspect 125. The precursor fibre composition of any one of aspects 117 to 124, wherein the fibre is heated in an inert atmosphere further in the temperature range from about 400 °C to about 1000 °C, followed by the carbonization/graphitization up to about 3000 °C in an inert atmosphere (e.g. N ₂ /Ar).

Aspect 126. The precursor fibre composition of any one of aspects 117 to 125, wherein the fibre is heated at a temperature from about 200 °C to about 450 °C, from about 250 °C to about 400 °C, or from about 260 °C to about 350 °C for oxidative stabilization.

Aspect 127. The precursor fibre composition of any one of aspects 122 to 126, wherein the heated fibre promoted cyano-chemistry cyclization below about 400 °C (e.g. in air).

Aspect 128. The precursor fibre composition of any one of aspects 122 to 127, wherein the heated fibre promoted cyclization and cross-linking of linear molecular chains via dehydration, cyclization and polycondensation, forming longitudinally oriented graphitic crystallites along the fibre axis.

Aspect 129. A fibre made from the precursor fibre composition of any one of aspects 72 to 128.

Aspect 130. The fibre of aspect 129, wherein the fibre comprises an asphaltene green fibre.

Aspect 131. The fibre of aspect 129 or 130, wherein the fibre comprises a carbon fibre.

Aspect 132. The fibre of aspect 130, wherein the asphaltene green fibre is converted to a carbon fibre through thermal treatment. Aspect 133. Use of the precursor fibre composition of any one of aspects 72 to 128 for making fibres.

[0109] The above disclosure generally describes the present invention. A more complete understanding can be obtained by reference to the following specific Examples. These Examples are described solely for purposes of illustration and are not intended to limit the scope of the invention. Changes in form and substitution of equivalents are contemplated as circumstances may suggest or render expedient. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.

EXAMPLES

[0110] The following non-limiting examples are illustrative of the present application: i) Materials

[0111] Raw asphaltenes (AOA- S1) were supplied by InnoTech Alberta. Toluene (99.5%) and xylenes (99.9%) were purchased from EMD Chemicals (USA) and Fisher Scientific (USA), respectively. Commercial polyacrylonitrile (PAN, Mw: 150,000) was purchased from Sigma-Aldrich and used as received. Acrylonitrile (>99%, Merck, Germany) containing 35-45 ppm monomethyl ether hydroquinone inhibitor was purchased from Aldrich and used as received. All other chemicals used were purchased from Aldrich and VMR and used as received. ii) Modification of Asphaltenes

[0112] Examples of Chemical Modification of Asphaltenes:

[0113] Example 1 (CF-131:

[0114] About 200 mg of asphaltenes (S1) and 115 mg of lauroyl peroxide (FRI, free radical initiator) were dissolved in about 2.0 g of pyridine and then about 2.0 g of dimethylformamide (DMF) was added. The mixture was warmed up to about 48 °C with a hot-water bath under magnetic stirring. About 1.24 g of acrylonitrile monomer (used as purchased, without any distillation or drying) was injected into the mixture. The mixture was stirred at about 50 °C for about 1 h under an argon atmosphere and then about 1 h at about 60 °C, about 30 min at about 65 °C, about 30 min at about 70 °C, about 30 min at about 75 °C, about 30 min at about 85 °C, and about 1 h at about 95 °C.

[0115] After the reaction mixture was cooled to room temperature, the mixture had a viscous appearance and no visual solid/particles were observed. The mixture was stirred at room temperature overnight. The mixture was warmed up to about 75 °C and air was blown into the mixture for a few minutes. A homogenous and viscous slurry was obtained. The slurry was used for AOA green fibre spinning using an electrospinning process.

[0116] The weight ratio of the reagents was: S1:FRI:AN (acrylonitrile monomer) =200:115:1240 = 1.74:1:10.8; pyridine:DMF = 1:1.

[0117] Example 2 (CF-13. 2 ^nd parti:

[0118] About 80% of the slurry from Example 1 was dried to a wet-solid by air-blowing into the slurry, and then the wet-solid was re-dissolved in about 2.0 g DMF (easily dissolved) to form a mixture. To the mixture, an additional 500 mg of S1 in about 5.5 g pyridine was added. After stirring for a while, about 1.0 g of about 10 wt% commercial PAN solution in DMF was diluted to about 5 wt% using DMF and added to the mixture whereby the total solution volume was about 20 ml_. The mixture was heated to 80 °C under magnetic stirring and concentrated to about 10 mL by air-blowing into the mixture. About 1.0 g of about 10 wt% PAN solution in DMF was added. The mixture was stirred at about 80 to about 85 °C for about 30 min and then concentrated to about 5 to about 7 mL by blowing nitrogen into the mixture at about 80 °C.

[0119] About 1.0 mL of the resultant solution/slurry was used for electrospinning at the following spinning conditions: spinning distance at about 25 cm, electrical field at about 20 kV, solution feeding rate at about 3 pL/min, and the solution concentration was at about 28 wt%.

[0120] The solution/slurry was further concentrated to about 35 wt%. The concentrated slurry was used over a variety of electrospinning conditions for a continuing spinning process over about 20 minutes without clogging the spinneret; at drum collection speeds from about 380 RPM to about 1020 RPM).

[0121] Example 3 (CF-141:

[0122] About 800 mg of asphaltenes (S1) and about 50 mg of lauroyl peroxide was dissolved in about 8.0 g of pyridine at about 65 °C and then about 2.0 g of DMF was mixed with magnetically stirring in a round bottom flask. At this temperature and while stirring, about 860 mg of acrylonitrile monomer was quickly added and a short air-condenser was placed on the flask, and then the reaction system was connected to an argon atmosphere. The initial reddish solution became black-reddish. Some solid particles were observed on top of the reaction mixture within about a 3 hour period at 65 °C. The mixture was further heated up to about 75 °C for about 1 h and up to about 85 °C for another 1 h, and the solid particles disappeared. [0123] The reaction mixture was then concentrated at about 85 °C, by blowing nitrogen into the mixture, to about half of its original volume. About 1.0 g of about 10 wt% of commercial PAN solution in DMF was first diluted to the concentration of about 2.5 wt% by adding about 3.0 g of DMF. The diluted PAN solution was added dropwise to the reaction mixture at about 85 °C. The mixture was stirred at room temperature overnight. There was solid on the flask wall and magnetic stirring bar. Ultra-bath sonication was applied for a few minutes to take the solid back into solution. An additional about 1.0 g of about 10 wt% PAN solution in DMF was diluted first by adding about 2.0 g of DMF, and then the diluted PAN solution was added to the reaction mixture. The reaction mixture was first heated with a mineral oil bath up to about 75 °C for about 20 min, up to about 90 °C for about 20 min, up to about 100 °C for about 20 min, and then up to about 130 °C for about 1 h. The mixture was concentrated to remove partial solvent, and then the bath temperature was increased to about 160 °C and the mixture was refluxed for about 3 hours. Then the reaction mixture was concentrated at about 85 °C to avoid solid formation.

[0124] Example 4 (CF-161:

[0125] About 850 mg of purified asphaltenes (~22 wt% of maltenes were removed from S1) was dissolved in about 8.0 g of pyridine. About 60 mg of lauroyl peroxide was dissolved in about 3 mL of toluene and then added to the asphaltenes solution. About 2.0 g of DMF was added to the asphaltenes solution under stirring, some solid particles precipitated immediately. The mixture was heated up on a heating plate under magnetic stirring until the solid particles were back into solution, and then about 877 mg of acrylonitrile monomer was injected. The mixture was warmed up to about 55 °C in a mineral oil bath and the reaction flask had a condenser that connected to a vacuum line with a constant argon-flow. After about 2.5 h, the bath temperature was increases to about 65 °C for about 2 h and to about 75 °C for about 2 h, and then the mixture was stirred over a weekend at room temperature.

[0126] The reaction mixture was then re-heated to about 80 °C for about 1 h, about 100 °C for about 2 h and about 135 °C for about 1 h, then cooled down to 110 °C. About 2.0 g of about 10 wt% PAN solution in DMF was diluted to about 2.5 wt% (by adding additional DMF to a total volume of about 8.0 g). The diluted PAN solution was added dropwise to the reaction mixture. The mixture was re-heated to about 135 °C (reflux) for about 2 h and then further heated to an oil bath temperature up to about 160 °C, so partial solvents were evaporated through an air-cooling condenser. Once the desired volume of the reaction mixture is reached, the heating bath was removed to keep the reaction mixture at the desired concentration and viscosity.

[0127] Example 5 (CF-181: [0128] The solvent system was selected with DMF and quinoline. Quinoline was mixed in a 1:1 weight ratio with about a 2.5 wt% commercial PAN solution in DMF, and the system maintained a clear solution. More quinoline was added causing the clear solution to become turbid and/or translucent. About 2.0 g of about 10wt% commercial PAN solution in DMF was first diluted to the concentration of about 2.5 wt% by adding about 6.0 g of DMF in a round bottom flask with magnetic stirring bar. To the diluted solution, about 954 mg of acrylonitrile monomer was injected. A solution of about 72 mg of lauroyl peroxide in about 1.5 g quinoline and a solution of about 1.3 g of purified asphaltenes (maltenes removed) in about 5.0 g of quinoline were separately prepared. The PAN solution with acrylonitrile monomer was heated up to about 55 °C, and then the asphaltenes solution and the free radical initiator solution were added sequentially. About 1.5 g of quinoline was added to the mixture. The reaction mixture was stirred at about 60 °C for about 2 h, at about 70 °C for about 2 h, at about 100 °C for about 1 h, and then at room temperature over a weekend. The mixture was concentrated to a slurry by partially removing solvents with heating and blowing air into the mixture.

[0129] The slurry is promising for wet-spinning with a proper coagulation solution, such as a diethyl ether and water double layer coagulation bath.

[0130] Example 6 (CF-19, Three times scale up of CF-141:

[0131] About 2.40 g of purified asphaltenes (maltenes removed) and about 150 mg of lauroyl peroxide were dissolved in about 24.0 g of pyridine in a round bottom flask with a magnetic stirring bar. After the asphaltenes were dissolved, about 6.0 g of DMF was mixed at about 60 °C and about 2.58 g of acrylonitrile monomer was added dropwise. After the addition, an air-condenser was connected to the flask, along with a nitrogen gas line. The mixture was stirred at about 60 °C for about 2h, at about 65 °C for about 1 h, about 75 °C for about 2 h and then at about 60 °C overnight, and then at about 80 °C for about 30 min, at about 120 °C for about 15 min, at about 130 °C for about 15 min, and then cooled to about 110 °C. About 6.0 g of about 10 wt% PAN solution in DMF was first diluted to about 3.33 wt% (by adding about 12 g of DMF) and then dropwise added to the reaction mixture. The mixture was heated up again to about 130 °C for about 2 h, about 165 °C for about 20 min and then at about 60 °C overnight. The mixture was then concentrated by air-blowing into the mixture.

[0132] Example 7 (CF-201:

[0133] About 405 mg of asphaltenes (S1) and about 32 mg of lauroyl peroxide were dissolved in about 4.5 g of pyridine, and then about 654 mg of acrylonitrile monomer was added under magnetically stirring and then about 200 mg of DMF was added. The flask was connected to an air-condenser with a rubber septum on top. The mixture was warmed up to about 50 °C for about 3 h, to about 65 °C for about 2 h, to about 70 °C for about 1 h, and then at room temperature overnight. It was then re-heated at about 80 °C for about 1 h, about 90 °C for about 2 h, about 95 °C for about 1.5 h, about 115 °C for about 2 h, and about 125 °C for about 2 h. Partial solvent removal was achieved by blowing nitrogen into the mixture to provide a viscous/concentration of about 30 wt% to about 40 wt%.

[0134] Example 8 (CF-22, repeating CF-20 but in different solvents and scale-up):

[0135] About 1.22 g of asphaltenes (S1) and about 100.3 mg of lauroyl peroxide were dissolved in about 14 g of xylene at about 55 °C and then mixed with about 632 mg of DMF. About 1.96 g of acrylonitrile monomer was quickly injected into the reaction mixture. The mixture was stirred at about 55 °C for about 4 h, at about 65 °C for about 2 h, and then at room temperature overnight. The following day, the mixture was re-heated to about 85 °C for about 2 h, about 100 °C for about 1.5 h, and about 130 °C for about 2 h. Partial solvent removal was achieved by blowing nitrogen into the mixture. The residue was stirred at about 50 °C overnight, and further concentrated at 80 °C by blowing nitrogen into the residue to form a slurry.

[0136] The slurry was used at about 52 to about 55 wt% for electrospinning with the following spinning conditions: spinning distance at about 15 cm, electric field at about 10 to about 12 kV, feeding rate at about 2 to about 3 pg/m, drum collect speed at about 250 to about 300 RPM. The obtained modified S1 asphaltene composite slurry/solution was successfully electrospun into an aligned-fibre mat and able to be spun for any large size of mat sample as shown in Figure 7. These fibres showed no beads and were produced without the incorporation of commercial high molecular weight PAN.

[0137] The slurry was also applied to wet-spinning with a 22G3/4 (0.7 mm x 19 mm) needle spinneret, feeding rate at about 5 to about 10 pL/min and/or higher into a hexane/ethanol coagulation double-layered bath for any arbitrary duration without a break in continuing fibre formation. An example illustration is shown in Figure 8, where a consecutive 5 hours of spinning with adjustable spinning rates and draw ratios was done.

[0138] Example 9 (CF-21, 3 times scale up CF-201:

[0139] About 1.23 g of asphaltenes (S1) and about 101 mg of lauroyl peroxide were dissolved in about 14.0 g of pyridine at about 55 °C and about 634 mg of DMF was added. About 1.69 g of acrylonitrile monomer was then added. The flask was assembled with an air- condenser with a rubber septum on top. The mixture was stirred at about 55 °C for about 4 h, at about 65 °C for about 2 h and at room temperature overnight. The following day, the mixture was re-heated to about 85 °C for about 2h, at about 100 °C for about 1.5 h, at about 110 °C for about 2 h. Partial solvent removal was achieved by blowing nitrogen into the mixture to provide a viscous/concentrated slurry. The resulting slurry was used for both electrospinning and wet-spinning processes.

[0140] Example 10 (CF-23, confirmation of in-situ polymerization):

[0141] This example was to confirm the PAN formation through in-situ polymerization at the same reaction conditions and in the same solvent system as applied in the previous examples, without adding asphaltenes.

[0142] About 14.2 g of pyridine and about 102 mg of lauroyl peroxide solution were mixed with about 670 mg DMF, and then about 2.04 g of acrylonitrile monomer was added. The mixture was warmed up to about 55 °C and stirred for about 4 h, and then heated up to about 65 °C for about 1 h, and at about 70 °C overnight. The mixture became orange yellow, and was heated further to about 80 °C for about 2h, at about 100 °C for about 1.5 h, at about 120 °C for about 1h, and then concentrated to about 5 to about 8 ml_. The residue was viscous and deep orange-red. The dried sample was characterized with FT-IR showing the exact same fingerprinting signals as commercial PAN as shown in Figure 1 (c). iii) Electrospinning

[0143] Electrospinning includes a syringe pump, a high voltage power supply and a rotating drum. A syringe was mounted on the syringe pump to control the infusion rate and it was connected to a positive terminal of the high voltage power supply through a stainless-steel spinneret with an internal diameter of about 0.84 mm. The rotating drum that was connected to the negative terminal of the power supplier was covered by aluminum foil to collect fibre products.

[0144] Electrospinninq Conditions:

A. Non-Modified Asphaltenes a) Example I: A mass quantity of AOA-S1 was dissolved in toluene to provide a concentration of about 50 wt% solution. This solution was warmed up to about 50 °C and used for AOA-S1 green fibre formation through an electrospinning process at the following spinning conditions: electrical field at about 60 kV/m, spinning distance at about 25 cm, feeding rate at about 5 pL/min and drum collect speed at about 280 rpm. b) Example II: A mass quantity of AOA-S1 was dissolved in xylene to provide a concentration of about 50 wt% solution. This solution was warmed up to about 50 °C and used for AOA-S1 green fibre formation through an electrospinning process at the following spinning conditions: electrical field at about 60 kV/m, spinning distance at about 25 cm, feeding rate at about 3 pL/min and drum collect speed at about 520 rpm. c) Example III: A mass quantity of purified asphaltenes (maltenes-free S1) was dissolved in xylene to provide a concentration of about 40 wt% solution. This solution was warmed up to about 50 °C and used for AOA-S1 green fibre formation through an electrospinning process at the following spinning conditions: electrical field at about 60 kV/m, spinning distance at about 25 cm, feeding rate at about 3 pL/min and drum collect speed at about 520 rpm.

[0145] Table 1 shows the released volatiles divided into three weight loss categories, including their thermal weight loss, the weight loss that resulted from the oxidation stage and the final weight of residual ashes. S1 was AOA as received from InnoTech Alberta sample bank. S1-T/W was the fractions soluble in toluene and extracted from S1 and a water mixture. S1-Pent was prepared from a S1 -toluene solution by using a pentane drip to provide maltene-free asphaltenes precipitate (pentane:toluene was about 40:1). The maltene-free asphaltenes were sequentially extracted with dichloromethane, and after removal of dichloromethane, the solid residue was dissolved in toluene again (toluene:asphaltenes was about 10:1) and centrifuged at about 366,000 g for about 30 minutes. The toluene solution (top layer) was separated and S1-pent solid was obtained after removal of the toluene solvent.

[0146] Table 1 Weight loss obtained from TGA on SI, Sl-T/W and SI -pent samples for different temperature ranges weight loss ± SD (%) Weight ± SD (%) sample 20 - 350°C 350 - 500°C 500 - 800°C 20 - 800°C Oxidation Residual ashes

_S1 6.6 ± 0.1 55.0 ± 0.4 4.5 ± 0.4 66.2 ± 0.1 32.5 ± 0.1 1.0 ± 0.1

Sl-T/W-1 9.6 ± 0.2 52.3 ± 0.3 5.1 ± 0.7 67.0 ± 0.4 32.1 ± 0.4 0.36 ± 0.09

SI -pent- 1 5.1 ± 0.2 51.7 ± 0.4 5.4 ± 0.3 62.1 ± 0.2 37.1 ± 0.3 0.33 ± 0.05

[0147] The weight losses reported in Table 1 were split into three categories identified as volatiles 1 , 2 and 3. Within the temperature range from about 20 °C to about 350 °C, volatiles 1 was attributed to the low boiling point hydrocarbons. Within the temperature range from about 350 °C to about 500 °C, volatiles 2 was attributed to the decomposition of the weaker bonds holding the components of asphaltenes which were not part of the main aromatic systems. The main weight loss was due to the release of volatiles 2, meaning that the non-aromatic components were dominating the main mass percentage of Alberta oilsand asphaltenes. The weight loss which occurred at high temperatures (volatiles 3, about 500 °C to about 800 °C) was likely the result of more bond cleavage resulting in re-arrangements in the aromatic core. The weight loss resulting from the oxidation step, at about 800°C, revealed the percent of fixed carbon (solid carbon residue) remaining after the volatiles were expelled and leaving the residual ash content. The comparison of the TGA results in Table 1 shows some of the differences between the raw asphaltenes S1 as received and the processed ones (S1-T/W and S1-pent). The toluene/water interfacial separation was done in order to remove some of the solid content from asphaltenes and the results show a decrease in solids content from about 1.0 to about 0.36 %. The pentane induced precipitation sample also had low solids content at about 0.33 % but also had more carbon residue at about 37.1 % compared to about 32 % for S1 and S1-T/W hence an increase in the more aromatic core structures and a decrease in the lower molecular weight species such as maltenes. The pentane purification resulted in low molecular weight species removal while concentrating more thermally stable, high molecular weight aromatic species.

[0148] TGA experiments run in air purge showed the same first stage of degradation between about 375 °C and about 470°C as seen in nitrogen and resulting from decomposition of the weaker bonds holding the components of asphaltenes which are not part of the main aromatic fragments. Temperature, more than the nature of the purge gas, was therefore causing bond cleavage. The presence of oxygen had an effect on the aromatic fragments as opposed to the previous nitrogen purged experiments where a stabilization of the char’s weight loss was observed. The second stage of degradation in air showed a faster rate of weight loss than the first stage. The samples tended to generate bubbles in air near the degradation temperature (about 375°C); the bubbles interfered with the purge gas flow resulting in an unstable balance hence irregular weight loss was observed at about 375 °C to about 400°C.

[0149] B. Chemically Modified Asphaltenes with Commercial PAN Additive: a) CF-13 (Example 2 above, ~30 wt%) was electrospun: i) at about 3 pL/min, about 20 kV, about 20 cm, and drum rotation speeds were adjusted from about 0 to about 200, about 280, about 360, or about 520 rpm. ii) Voltages were adjusted from about 8, about 10, about 12, about 15, or about 20 kV, at about 3 pL/min, at about 20 cm, and at about 200 rpm. iii) Feeding rates were adjusted from about 0.5, about 1 , or about 1.5 pL/min, at about 20 cm, and at about 50 or about 60 kV/m, respectively.

[0150] CF-13 was further concentrated to about 35 wt% for electrospinning i) Voltages were adjusted from about 12, about 15, or about 18 kV, when other parameters were set at about 20 cm, about 1 pL/min, and about 0 rpm. ii) Rotation speed was adjusted at about 0, about 280, about 360, about 520, about 760, or about 1080 rpm, at about 15 kV, about 20 cm, and about 1 pL/min..

[0151] b) CF-14 (Example 3 above) was electrospun: i) at about 1 pL/min, about 20 cm, about 15 kV or about 520 rpm. ii) Feeding rate was then increased to about 2 pL/min. iii) Other parameters: about 15 kV, about 20 or about 25 cm were adjusted accordingly using about 520 or about 760 rpm, respectively iii) Other parameters: about 20 kV, about 25 cm were also adjusted accordingly using about 520 or about 760 rpm, respectively.

[0152] c) CF-16 (Example 4 above) was electrospun: i) at about 15 kV, about 20 cm, about 1 pL/min, about 0, about 280, or about 760 rpm, respectively ii) Voltages were adjusted to about 10, about 12 or about 20 kV, at about 20 cm, about 1 pL/min, and about 280 rpm.

[0153] C. Chemically Modified Asphaltene Without Commercial PAN Additive:

[0154] CF-20 (Example 7 above) was electrospun by adjusting voltages from about 6 to about 30 kV, a distance from about 8 to about 20 cm, a feeding rate from about 1 to about 20 pL/min, and a rotation rate from about 0 to about 240 rpm. Short-ribbon-like fibres formed due to high polarity of pyridine in the electrical field as shown in Figure 9. This phenomena was reported in the literature for obtaining small electrospun fibres by adding a trace amount of a high polar solvent.

[0155] CF-22 (Example 8 above) was adjusted similarly and was tuned to about 3 pL/min, at about 15 cm, at about 10 kV, and at about 280 rpm for the final fibre sample shown in Figure 7.

[0156] CF-21 (Example 9 above) was adjusted similarly and was tuned to about 10 pL/min, at about 15 cm, and at about 12 kV. The observation was similar to CF-20 above, the resulting short-ribbon-like fibres were mostly collected at the apex while elongated- droplets/fibres were formed as shown in Figure 9. The slurry was excellent for wet-spinning as described below. iv) Wet-spinning

[0157] Wet-spinning includes a syringe pump (KD scientific, power input: 0.25 A, 250 V), a plastic syringe with a metallic spinneret (22G3/4, internal diameter of 0.7 mm), and a coagulation bath with double-layered coagulants. In examples, the coagulants were at least one ofhexane, pentane, heptane, diethyl ether, petroleum ether, chloroform, dichloromethane, methanol, ethanol, ethylene glycol, water and/or any combination that forms a double-layered coagulation bath. The syringe was vertically mounted on the syringe pump on an adjustable stage. The spinneret tip was immersed below the coagulant surface as illustrated in Figures 8 and 10.

[0158] CF-22 (Example 8 above), the same slurry as used for the electrospinning process, was wet-spun as shown in Figure 8. The AOA-S1 green fibres were spun with different feeding rates from slow (at about 1 pL/min) to high (about 60 pL/min), and for any suitable duration. The wet fibre tolerated different levels of stretching through visual observation. [0159] CF-21 (Example 9 above), the same slurry as used for the electrospinning process, was wet-spun as shown in Figure 8. Short fibres were obtained when various spinning conditions were applied. The slurry was wet-spun with an adjustable feeding rate into a hexane and ethanol coagulation double-layered bath and the wet fibre can be easily picked up and wound manually as demonstrated in Figure 10.

[0160] A bending test was conducted to qualitatively and visually compare mechanical strength between chemically modified asphaltene fibres from the wet-spinning process above, as shown in Figure 11(a), and the unmodified S1 asphaltene fibre, as shown in 11(b). Without being bound by theory, it is believed to be attributable to the lengthened molecular chain assemblies of the modified S1 asphaltene fibres during in-situ polymerization through chemical crosslinking. v) Thermal Treatment

[0161] Thermal treatment was conducted by placing fibre samples in furnaces (Thermo Scientific, Vacu Therm VT6060 P, up to 300 °C; Thermo Scientific, Barnstead Thermolyne, 30400 Furnace, for above 300 °C). The asphaltene fibres were treated at about 150°C for about 2 h, about 200°C for about 2 h, about 250°C for about 7 h, about 300°C for about 7h, about 350°C for about 1h and about 400°C for about 3 h. Among these treatments, nitrogen gas was introduced at temperatures at about 350 and greater. Samples were observed using SEM at each temperature interval and the same samples were then treated at a higher temperature.

[0162] Example 11: Non-modified AOA-S1 green fibres from toluene (Example I) as shown in Figure 12. The fibre morphology had no change below about 150 °C in air, once the oven temperature reached about 200 °C, the fibres began to fuse and crosslink within about 2 h. With the further increase in temperature, the inter-fibre crosslinking increased.

[0163] Example 12: Non-modified AOA-S1 green fibres from xylene (Example II), as shown in Figure 13. Similar to Example 11, the fibre morphology had no change below about 150 °C in air, once the oven temperature reached about 200 °C, the fibres began to fuse and crosslink within about 2 h. With further increase in temperature up to about 300 °C, the maximum inter-fibre crosslinking was reached. With a further increase in temperature, the fibre appeared stable as seen from about 300 °C to about 400 °C; the network structure had no obvious change as viewed under an electron microscope.

[0164] Example 13: Non-modified but purified AOA-S1 (maltenes-free S1) green fibres from xylene (Example III), as shown in Figure 14. The thermal stability of the purified (maltenes- free) S1 green fibres is improved with the removal of maltenes fractions (about 22 wt% maltenes in the as-received S1 original sample). Each individual AOA-green fibres in this example was able to withstand the thermal treatment up to about 300 °C for over about 7 h without the appearance of fibre fusing and inter-crosslinking, which was unlike Examples 11 and 12 (without removal of maltenes from raw asphaltene S1), whereby the fibres began to fuse with each other at a temperature as low as about 200 °C within a short time period of about 2 h. Once the temperature reached about 350 °C, inter-fibre fusing and crosslinking were observed and fibre shrinkage was observed at about 400 °C.

[0165] Example 14: Chemically modified AOA-S1 green fibres with commercial PAN additive (CF-13, 14 and 16, Examples 2 to 4 above), were smaller in diameter than the non-modified AOA-S1 green fibres, and these fibres withstand a temperature of about 300 °C in air for over about 7 h without any crosslinking, as shown in Figure 5. The fibres did not appear to change their morphology at about 400 °C for about 3 h under a nitrogen atmosphere.

[0166] Example 15: Chemically modified AOA-S1 green fibres without commercial PAN additive (CF-22, Example 8 above) from xylene, as shown in Figure 7, had similar diameter sizes as the unmodified AOA-S1 green fibres. Unlike the unmodified AOA-S1 green fibres that fuse and crosslink at a temperature as low as about 200 °C within about 2 h treatment as described in Examples 11 and 12 above, the modified AOA-S1 green fibres could withstand a temperature at about 300 °C for about 2 h, and no fibre-fusing was observed as shown in Figure 15. An additional 5 h treatment at about 300 °C did not change the fibre morphology and did not cause any fibre fusing and cross-linking. With the oxidative stabilization treatment, the thermal treated fibres appeared to become strong and less brittle, as observed under an electron microscope. vi) Elemental Analysis

[0167] As-received S1 was purified to provide AOA S1-pent and the separated fraction percentages were summarized in Table 2 through the collective weight of each fraction.

[0168] Table 2. Separation results from the as-received asphaltene sample (S1)

Contents Weight (%)

Purified asphaltene 77.0

Maltenes 22.1

Solid residue 0.9 [0169] Figure 1(a) showed the result of elemental analysis of the asphaltene samples. When S1 was compared with S1-T/W and S1-Pent, weight percent of the nitrogen decreased from about 2.3 to about 1.1 wt%. The sulfur amount increased from about 7.8 to about 8.3 wt%. The elemental composition may vary depending on the source of asphaltenes and the process of separation. For example, sulfur in asphaltenes isolated from low-temperature coal tar can be as low as 0.38% (by difference). S1 -fiber (Tol), S1 -fibre (Xyl) and S1-pent (xyl) in Figure 1(a) were AOA green fibres spun from S1 -toluene, S1 -xylene and S1 -pent-xylene solutions, respectively. Most of the elemental compositions were consistent with those of their corresponding precursors S1 and S1-pent. The current electrospinning process did not change the elemental compositions of asphaltene before and after spinning; no volatile fraction was removed during the fibre passing through the electrical field.

[0170] Figure 1(b) showed the comparison of the elemental analyses of chemically modified S1 green fibres (CF-13) with commercial PAN additive and CF-20 and CF-21 without commercial PAN additive from a pyridine/DMF solvent system and CF-22 without commercial PAN additive from a xylene/DMF solvent system. In comparison with their precursor S1, the CF-13 fibre sample had an increase of nitrogen contentfrom the commercial PAN additive and a low percentage of sulphur. However, CF-20, 21 and 22 fibre samples did not have significant changes in their elemental compositions without the commercial PAN additive. vii) FTIR

[0171] ln-situ PAN was prepared in CF-23 (Example 10) through in-situ polymerization of acrylonitrile monomer without the addition of asphaltenes at the same conditions as those applied in Examples 1 to 9 with the pyridine/DMF solvent system. This example showed the formation of in-situ PAN as shown in the FTIR spectrum in Figure 1(c), whereby the peaks at 2245 cnr ¹ and 1450 cnr ¹ are the characteristic peaks of PAN in comparison with commercial PAN. AOA-S7 is a mixture of many chemical functionalities that have strong absorptions that overlap the absorption peaks of commercial PAN and/or in-situ PAN. As representative examples, the spectra of CF-21 (Example 9) and CF-22 (Example 8) were demonstrated in Figure 1 (c) and compared with the spectrum of S1. The increased intensities of peaks at 1686 and 1593 cnr ¹ of CF-21 and CF-22 were comparable with that of S1 , indicating the formation of C=0 and C=N bonds through in-situ polymerization, where a bathochromic shift (from 1686 to 1671 cnr ¹ for CF-21 and to 1655 cnr ¹ for CF-22) was also observed, indicating the formation of ester derivatives. viii) Electrospinning of Chemically Modified Asphaltene (S1) with Commercial PAN Additive [0172] The chemically modified asphaltene S1 composite slurry/solution with commercial PAN additive (CF-14, Example 3 above) demonstrated an adaptive viscosity and homogeneity visually as shown in Figure 2. Further qualitative assessment of its mechanical strength was conducted by drop-casting a thin layer of the modified asphaltene composite slurry/solution (Example 3) on a glass slide. For comparison, a thin layer of unmodified S1 , S1-T/W and S1-Pent asphaltene solutions were each drop-cast on a glass slide. After solvents were evaporated, the resulting thin films, as shown in Figure 3, behaved differently amongst the samples tested. All of the unmodified asphaltenes samples of the as-received S1, and purified S1-T/Wand S1-Pent asphaltenes, cracked but stayed on the glass slides as seen in the optical microscopic images in the first row in Figure 3, while the thin film prepared from the modified S1 asphaltene composite slurry/solution, self-peeled off the glass slide and twisted during dry-up process shown in the second row in Figure 3. Unlike the unmodified asphaltenes, magnification of the twisted thin film surface showed a smooth and crack-free surface morphology. This observation showed that the mechanical properties, such as strength, of the modified S1 asphaltene composite, was improved over the unmodified asphaltene samples.

[0173] The modified S1 asphaltene composite with commercial PAN additive (Example 3) was concentrated in the pyridine/DMF solvent system to about 30 to about 35 wt%, and visually, a similar slurry, as shown in Figure 2, was obtained and electrospun with the spinning conditions: the electric field at about 60 kV/m, the feeding rate at about 3 pL/min, and the drum collector speed at about 520 rpm. The resulting fibres shown in Figure 4(a) were very long but have, under nagnification, small size in diameters in comparison with the unmodified S1 fibres. Moreover, unlike the unmodified S1 fibres (either from toluene solution of S1, xylene solution of S1 or xylene solution of S1 -pent) that were very brittle under a electron microscopic focus shown in Figure 4(b), the fibres shown in Figure 4 (a) were not easily fractured, and there was barely any break sections of fibres shown under any arbitrary focus and any arbitrary focusing duration, indicating stronger fibres than unmodified fibres .

[0174] The small modified AOA green fibres contained several beads/particles in different sizes. These bead/particles have higher thermal stability than S1 and different surface morphologies from S1 droplets as demonstrated in Figure 6. With additional experiements in CF-20, 21 and 22 (Examples 7 to 9), there were no such beads in the resulting fibres from those experiments, comfirming that these beads/particles were from the commercial PAN additive. These beads can be potentially digested into fibres by further tuning the slurry formations and spinning conditions under tension with additional stretching.

[0175] While the present application has been described with reference to examples, it is to be understood that the scope of the claims should not be limited by the embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

[0176] All publications, patents and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Where a term in the present application is found to be defined differently in a document incorporated herein by reference, the definition provided herein is to serve as the definition for the term.