FIELD

The present disclosure generally relates to graphitic compositions, coatings and materials. The present disclosure also relates to coating compositions comprising a conducting polymer and a metal source. The present disclosure also relates to coated substrates, materials and/or composites, which comprise a graphitic material and a metal source. The present disclosure also relates to methods, processes and uses of the compositions, coatings, coated substrates, materials, or composites for various applications.

BACKGROUND

Graphene and graphitic materials constitute a two-dimensional (2D) sheet of sp ² -hybridized carbon atoms having many unique properties of commercial value. Production methods for preparing such materials is still considerably limited.

Despite the success and promise of graphene and graphitic materials, it is yet to be widely used in commercial applications. There are significant difficulties in producing graphene and graphitic materials, and particularly with the commercial scalability of the processes being used. This has limited the availability of graphene and graphitic materials for various commercial applications.

There is a need for providing graphitic materials, and methods for preparing graphitic materials, which are commercially scalable and processable for preparing various coated substrates, materials and composites for use in various and particular applications. SUMMARY

The present inventors have identified compositions having good functionality and processability, which can be cost-effectively prepared from a conducting polymer and/or a graphitic material formed from a conducting polymer, and which may include a metal source. The conducting polymer may be selected to be soluble in an organic solvent to provide versatility in application of the composition. The present inventors have also surprisingly found that heating a conducting polymer, which may be coated on a substrate, to a predetermined temperature can produce a functional graphitised coating (e.g. graphitised coated substrate) suitable for various and particular applications. At least according to some embodiments or examples as described herein, various graphitised coatings can be provided for various applications in catalysis, printed electronics, conductive coatings, anti-corrosive coatings, composites, and energy storage devices, for example.

In one aspect, there is provided a coated substrate comprising a substrate at least partially coated with a graphitised coating, wherein the graphitised coating comprises one or more layers of a graphitic material formed by heating a coating composition present on the substrate, and wherein the coating composition comprises a conducting polymer.

In one embodiment, the coating composition further comprises a metal source, and wherein the coating composition forms a graphitised coating comprising the metal source. In one example, the metal source is a compound, complex or salt comprising a metal, metal oxide or combinations thereof. In another example, the metal source is a metal, metal oxide, or a precursor for forming a metal and/or metal oxide.

In another embodiment, the surface of the graphitised coating comprises one or more layers of the graphitic material, and wherein the metal source is interspersed on the surface of the graphitic material as individual particles. In another embodiment, the individual particles of the metal source are less than 500 nm. The individual particles may be in a range of about 1 to 500 nm in diameter. The individual particles of the metal source may be in the form of nanospheres. The individual particles may comprise or consist of a metal and/or metal oxide.

In another embodiment, the coated substrate comprises a metal, metal alloy, cermet or metal oxide that is coated with the coating composition. The coated substrate may be a scaffold, such as a static mixer, a material, such as a fibre or particle, or a composite.

In another aspect there is provided a composition comprising or consisting of a conducting polymer, a metal source, optionally one or more solvents, and optionally one or more additives. In one embodiment, the conducting polymer is selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, and poly(3,4-ethylenedioxythiophene).

In another embodiment, the metal source comprises a metal or metal oxide wherein the metal is selected from at least one of iron, cerium, cobalt, copper, zinc, nickel, palladium, platinum, gold, silver, ruthenium, iridium, rhodium, titanium vanadium, zirconium, niobium, tantalum, and chromium, or complexes thereof. The metal source may be interspersed in the coating composition.

In another embodiment, the coating composition is a liquid formulation comprising a conducting polymer, a metal source, and one or more solvents (e.g.

organic solvents). The metal source may be a precursor compound, complex or salt comprising a metal in the liquid formulation for forming metal or metal oxide particles in the graphitised coating on heating. The metal source may be soluble in the liquid formulation or present as a slurry.

In another aspect there is provided a method of preparing a coated substrate comprising a step of at least partially coating a substrate with a composition according to any embodiments or examples as described herein.

In another embodiment, the method comprises or consists the following steps of: (i) heating the coated substrate to a predetermined temperature to initiate formation of a graphitised substrate; and (ii) cooling the graphitised substrate. The predetermined temperature for step (i) may be between about 600 °C to about 1200 °C.

In another embodiment, the coated substrate may have a content of heteroatom, and wherein the heteroatom may be selected from one or more of nitrogen, oxygen, sulphur, or combinations thereof. The coated substrate may comprise a content of one or more of graphitic nitrogen, pyridinic nitrogen and pyrrolic nitrogen.

In another embodiment, the coated substrate may be selected from a printed or flexible electronic device, a medical device, an electrode, a sensor, a fabric, fibre or textile, a composite, an infrastructure component, pipe or conduit, and a carbon supported catalyst.

In another aspect there is provided a use of a coated substrate or coating composition, according to any one of the following applications: pintable electronic device, conductive coating, paint or ink ingredient, anti-corrosion coating or corrosion inhibitor, coating system layer, automobile or aerospace component, energy storage device component, a resin or polymer additive, and a catalyst for chemical reactions.

Other embodiments and examples of the composition, substrate, processes, uses, applications and methods of the present disclosure will become apparent from the following detailed description, the accompanying drawings and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Some embodiments of the present disclosure are described and illustrated herein, by way of example only, with reference to the accompanying Figures in which:

Figure 1 - is a scanning electron microscopy images showing the presence of palladium nanospheres formed on a graphitised substrate according to one example of the present disclosure.

DETAILED DESCRIPTION

The present disclosure describes the following various non-limiting examples, which relate to investigations undertaken to identify coating compositions for adhering to substrate to produce stable and effective coatings for use in various applications.

The present inventors have identified a coating composition having good functionality, which can be cost-effectively prepared from a conducting polymer and/or a graphitic material formed from a conducting polymer, and which may include a metal source.

The conducting polymer may be selected to be soluble in an organic solvent to provide versatility in application of the coating composition. The present inventors have also surprisingly found that heating a conducting polymer coated substrate to a

predetermined temperature can produce a functional graphitised substrate suitable for specialty applications, such as to provide a surface comprising a metal source that is effective for catalysis, printed electronics, conductive coatings, anti-corrosive coatings, composites, and energy storage devices. Substrates having a graphitised coating prepared by at least some of the embodiments or examples as described herein may be further modified to allow further versatility in its particular application. In at least some examples as described herein, the present coating compositions, coated substrates, carbon materials and processes for preparing the coated substrates, provide commercially processable, cost-effective and industrially scalable processes. In at least some examples as described herein, the surface of the coated substrates can provide a configuration or association between the graphitic material and the metal source to enable an effective surface for applications such as catalysis (e.g. catalytic reactions that require a carbon support, such as photocatalysis), printed electronics (e.g. inks, sensors, flexible electronics), conductive coatings (e.g. textiles, aerospace coatings, marine coatings), anti-corrosive coatings (e.g. aerospace coatings, marine coatings), composites (e.g. performance/engineering polymers, rubber, concrete), and energy storage devices (e.g. supercapacitors, fuel cells, batteries).

General Terms

Throughout this disclosure, unless specifically stated otherwise or the context requires otherwise, reference to a single step, composition of matter, group of steps or group of compositions of matter shall be taken to encompass one and a plurality (i.e. one or more) of those steps, compositions of matter, groups of steps or groups of compositions of matter. Thus, as used herein, the singular forms "a", "an" and "the" include plural aspects unless the context clearly dictates otherwise. For example, reference to "a" includes a single as well as two or more; reference to "an" includes a single as well as two or more; reference to "the" includes a single as well as two or more and so forth.

Those skilled in the art will appreciate that the disclosure herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features.

Each example of the present disclosure described herein is to be applied mutatis mutandis to each and every other example unless specifically stated otherwise. The present disclosure is not to be limited in scope by the specific examples described herein, which are intended for the purpose of exemplification only. Functionally- equivalent products, compositions and methods are clearly within the scope of the disclosure as described herein.

The term "and/or", e.g., "X and/or Y" shall be understood to mean either "X and Y" or "X or Y" and shall be taken to provide explicit support for both meanings or for either meaning.

Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

The term "consists of', or variations such as "consisting of, refers to the inclusion of any stated element, integer or step, or group of elements, integers or steps, that are recited in context with this term, and excludes any other element, integer or step, or group of elements, integers or steps, that are not recited in context with this term.

Unless otherwise indicated, the terms "first," "second," etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to a “second” item does not require or preclude the existence of lower-numbered item (e.g., a“first” item) and/or a higher-numbered item (e.g., a“third” item).

As used herein, the phrase“at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the list may be needed. The item may be a particular object, thing, or category. In other words,“at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required. For example,“at least one of item A, item B, and item C” may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C. In some cases,“at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.

Reference herein to“example,”“one example,”“another example,” or similar language means that one or more feature, structure, element, component or characteristic described in connection with the example is included in at least one embodiment or implementation. Thus, the phrases“in one example,”“as one example,” and similar language throughout the present disclosure may, but do not necessarily, refer to the same example. Further, the subject matter characterizing any one example may, but does not necessarily, include the subject matter characterizing any other example.

It will be clearly understood that, although a number of prior art publications are referred to herein, this reference does not constitute an admission that any of these documents forms part of the common general knowledge in the art, in Australia or in any other country.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the present

specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Coating Composition

The present disclosure provides a coating composition comprising or consisting of a conducting polymer and one or more solvents, and which may include a metal source. The coating composition may optionally comprise one or more solvents, and optionally one or more additives. At least according to some embodiments or examples, the metal source may be interspersed with a conducting polymer. The present inventors have identified a coating composition having good functionality, which can be cost-effectively prepared from a conducting polymer which may include a metal source. The conducting polymer may be selected to be soluble in an organic solvent to provide versatility in application of the coating composition. The present inventors have also surprisingly found that heating a conducting polymer coated scaffold to a predetermined temperature can produce a functional graphitised scaffold suitable for specialty applications, for example to provide a catalytic surface comprising a metal source that is effective for heterogeneous reactions. It will be appreciated that in the example of the functional graphitised catalytic coated scaffold, there can be provided a metal source (e.g. catalyst) interspersed with a heteroatom containing carbon material (e.g. graphitic material) that can provide enhanced chemical, electrical, and/or functional properties for the development of an effective catalytic system. The association of the graphitic material and metal source, being in the form of a catalyst material on the surface of the scaffold, has been found to provide an effective surface for heterogeneous reactions, for example, that can be effective for use on static mixers for operational performance in continuous flow processes.

In another example, the coating composition comprises or consists of a conducting polymer, one or more solvents and a metal source (e.g. catalyst material). It will be appreciated that heating the conducting polymer to a predetermined temperature provides the graphitic material as described herein. It will also be appreciated that heating the coating composition comprising or consisting of a conducting polymer, and one or more solvents and a metal source (e.g. catalyst material) can provide metal nanospheres interspersed with the graphitic material.

Further details and embodiments of the coating composition are described as follows and may be applied to various other embodiments or examples as described herein including processes and applications.

In one embodiment, the coating composition comprises a plurality of reactive sites provided by the conducting polymer and the metal source (e.g. catalyst material) for promoting a reaction between two or more reactants.

The coating composition may be provided as a coating composition for application to a substrate surface. The coating composition may therefore be provided as a coating for which the coating composition comprises or consists of a conducting polymer, and one or more solvents and a metal source. The coating composition or coating thereof may be provided as a partial coating or a complete layer on the substrate. The catalytic composition or coating thereof may be provided on one or both sides or surfaces of the substrate. For example, the coating composition may be deposited on the substrate by dip coating, spray coating or spin coating. It will be appreciated that other coating methods may be applicable such as brush coating, painting, slurry spraying, spray pyrolysis, sputtering, chemical or physical vapour deposition techniques, electroplating, screen printing, or tape casting.

Liquid Formulation

At least according to some embodiments or examples, the coating composition may be a liquid formulation comprising a conducting polymer, and one or more solvents and optionally a metal source. The metal source if present, may be dissolved in the solvent or provided as a slurry. It will be appreciated that the liquid formulation may assist in preparing a coated substrate comprising the coating composition. The conducting polymer may be selected to be soluble in an organic solvent to provide versatility in application of the coating composition. The coating composition may therefore be fluidic and flowable for versatile application. For example the coating composition may enable ease of application to the surface of a substrate. A coated substrate may therefore comprise a conducting polymer and a metal source. In one embodiment, the metal source is a catalyst material that is effective for heterogeneous reactions, for example hydrogenations. In other words, the coating composition may be used in coating complex substrates to form graphitic catalyst coatings for

heterogeneous reactions such as static mixer for continuous flow process. Coating the substrate with a liquid formulation can provide a wet film or coating on the substrate comprising or consisting of, in at least one example, the conducting polymer, metal source, one or more solvents, and optionally one or more additives. Drying of the wet film or coating can remove the one or more solvents to provide a dry film or coating comprising the conducting polymer and metal source. Heating of the dry film or coating according to any embodiments or examples as described herein can then provide a solid coating comprising or consisting of the conducting polymer and the metal source on a substrate. The substrate with the solid coating may be further heated at a predetermined temperature to provide a solid phase conversion of the solid coating into a graphitised coating comprising solid metal and/or metal oxide particles dispersed within or on the graphitised coating present on the substrate.

In another example, the coating composition is a suspension comprising or consisting of a conducting polymer, a metal source in the form of solid particles (e.g. metal particles), one or more solvents, and optionally one or more additives. For example, there may be provided a liquid formulation comprising or consisting of a conducting polymer, a plurality of metal particles and one or more solvents, and optionally one or more additives. The metal particles may be selected to provide catalytic activity. The solvent may be one or more organic solvents as described herein.

In some embodiments or examples, the coating composition may be a liquid formulation. The liquid formulation may comprise one or more solvents, such as one or more organic solvents. The liquid formulation may be a solution comprising the conducting polymer. The liquid formulation may be a suspension comprising the conducting polymer. In one example, there is provided a liquid formulation (e.g.

solution) comprising or consisting of a conducting polymer, a metal source, and optionally one or more organic solvents.

In some embodiments or examples, the coating composition may be a liquid formulation, and the metal source is soluble in the liquid formulation.

In some embodiments or examples, the coating composition may be a liquid formulation comprising or consisting of: an organic solvent, a conducting polymer soluble in the organic solvent, a metal source soluble in the organic solvent or present as a suspension in the organic solvent, and optionally one or more additives.

The liquid formulation of the coating composition, which may be provided on a substrate, may comprise or consist of the conducting polymer (e.g._PANI) and the metal source (e.g. metal or metal oxide) in a solvent (e.g. toluene). This may be provided by mixing PANI in a solvent along with a powdered metal, metal oxide or metal salt, for example. Once applied to a substrate, the liquid formulation can be dried (e.g. in an oven at about 90°C) to afford a substrate that is coated with a solid coating. The substrate with the solid coating can then be heated at a predetermined temperature to form a graphitised coating on the substrate according to any of the embodiments or examples as described herein. It will be appreciated that the heating is provided below any pyrolytic temperature of the conducting polymer such that the conversion of the solid conducting polymer into the graphitic material occurs in the solid phase (e.g. a solid conducting polymer is directly converted by heating into a solid graphitic material). In another embodiment or example, the coating composition may be a liquid formulation comprising or consisting of: one or more organic solvents, a conducting polymer of polyaniline sulfonate salt, a metal source comprising at least one of a metal compound, metal oxide, or complex, and optionally one or more additives one or more organic solvents;

In another embodiment or example, the coating composition may be a liquid formulation comprising or consisting of: one or more organic solvents, a conducting polymer of poly aniline dinonylnapthalenesulfonate salt, a metal source comprising at least one of a metal compound, metal oxide, or complex, and optionally one or more additives.

In another embodiment or example, the composition is a coating composition. The metal source may be a precursor compound, complex or salt comprising a metal that is soluble in the liquid formulation for forming metal or metal oxide particles in the graphitised coating on heating.

The metal source may be provided according to any examples or embodiments thereof as described herein. In some embodiments or examples, the metal source may be in the form of individual particles interspersed on the surface of the graphitic material as individual particles. The metal source may comprise or consist of a one or more metal complex, compound, oxide, or salt, or a combination thereof. The metal source may be soluble in a solvent such one or more organic solvents. The metal source may be provided for any of the above aspects, embodiments, or examples, according to any of the embodiments or examples thereof as described herein.

In other examples, the metal source may be a metal complex, compound, oxide, or salt. The metal source may comprise or consist of a noble metal, transition metal or rare-earth metal (e.g. lanthanides), or an oxide, or combination thereof. In some embodiments or examples, the metal or oxide thereof may independently be selected from the group comprising or consisting of iron, cerium, cobalt, copper, zinc, nickel, palladium, platinum, gold, silver, ruthenium, iridium, rhodium, titanium vanadium, zirconium, niobium, tantalum, and chromium. In some embodiments or examples, the metal may independently be selected from the group consisting palladium, platinum, ruthenium, and rhodium. In one embodiment or example, the metal may independently be selected from the group consisting of palladium, titanium and platinum. In another embodiment or example, the metal may independently be selected from the group consisting of palladium and platinum. In yet another embodiment or example, the metal may be palladium. In one embodiment or example, the metal or metal oxide thereof may independently be selected from the group consisting of copper, manganese, zirconium, titanium, zinc and silver. In another embodiment or example, the metal or metal oxide may independently be selected from the group consisting of copper, zirconium, titanium, zinc and silver.

It will be appreciated that reference to metal complex or metal compound refers to a metal in the form of a coordination compound or coordination complex and contains ions or molecules (e.g. ligands) linked to a metal (e.g. transition metal). For example, a metal organic framework (MOF). In another example, the metal complex or compound may be copper acetyl acetonate, copper stearate, copper acetate, zirconium acetyl acetonate, manganese acetyl acetonate, silver acetyl acetonate, silver carbonate, silver stearate, silver powder.

It will be appreciated that reference to metal salt refers to a metal comprising both anions and cations. For example a NCb anion is the counterion for a Pd metal cation. Some example counterions that may be used are NCb , Cl , S0 ₄ ² . For example, the metal salt may be selected from palladium nitrate.

Further examples of the metal source are described below that can also apply to any of the above embodiments or examples.

Graphitised Coating

A graphitised coating is prepared by heating a conducting polymer, to a predetermined temperature. The present process comprises or consists of applying a coating composition onto a substrate, drying the coated substrate to form a solid coating on the substrate and heating the solid coating to a predetermined temperature to from a graphitised coating on the surface of the substrate (e.g. liquid dried to provide a solid coating that undergoes solid conversion to form graphitic material without the conducting polymer or metal source forming a gaseous phase). In another example, a liquid formulation may be provided on the surface of the substrate and continually heated according at least some embodiments or examples to form a graphitised coating (e.g. liquid dried to provide a solid coating that undergoes solid conversion to form graphitic material in a single step without the conducting polymer or metal source forming a gaseous phase). The liquid formulation may be provided according to any embodiments or examples as described herein.

It will be appreciated that when the coating composition comprises a metal source the process allows the formation of a graphitised coating comprising a graphitic material and a metal source. For example, the coating composition further comprises a metal source, and wherein heating the coating composition forms a graphitised coating comprising the metal source. In one example, the metal source is a metal compound, metal oxide or metal complex. In another example, the metal source is a metal, metal oxide, or a precursor for forming a metal and/or metal oxide. The inventors have found that when the coating composition comprises a metal source that is a catalyst material, the catalyst material is at least according to some embodiments or examples in the form of individual particles interspersed on the surface of the graphitic material as individual particles, and may enable an effective surface for heterogeneous reactions, such as hydrogenation reactions performed under a continuous flow process. The coating composition at least according to some embodiments or examples described herein may be dried to form a solid coating or dried coating. The process can then enable the heating of the solid coating or dried coating at a predetermined temperature of between about 800 °C and 1200 °C to unexpectedly form a graphitised coating comprising solid metal in the form of particles on the surface on the graphitised coating.

One example to obtain a graphitic coated substrate is to provide a liquid coating composition comprising the conducting polymer (e.g. PANI) and a metal source (e.g. metal or metal oxide) in a solvent (e.g. toluene). The PANI can be provided in the solvent along with powdered metal, metal oxide or metal salt, to form a liquid formulation that can be applied to a substrate. The substrate coated with the liquid coating can then be dried (e.g. in an oven at about 90°C) to afford a substrate that is coated with a solid coating. The substrate with the solid coating can then be heated at a predetermined temperature to form a graphitised coating according to any embodiments or examples as described herein. The graphitised substrate may also be cooled. For example, the heating step can comprise or consist of heating the coated substrate to form a solid coating and heating the solid coating at a predetermined temperature to provide a solid phase conversion of the solid coating into the graphitised coated substrate. The heating of the coated substrate provides a solid phase conversion of the conducting polymer to the graphitic material, for example the conducting polymer is converted to the graphitic material by heating without introducing any vapour phase process (e.g. a solid conducting polymer is directly converted by heating into a solid graphitic material). It will be appreciated that the graphitised coated substrate with the graphitised coating comprises solid particles of metal and/or metal oxide dispersed throughout the graphitised matrix.

In one embodiment or example, the method of preparing the graphitic material comprises or consists of the steps of: (i) heating a conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, to a predetermined temperature to initiate formation of a graphitic material; and (ii) optionally cooling the graphitic material. In a further embodiment or example, the method of preparing the graphitic material further comprises a step of (i)(a) pre-heating the conducting polymer to a predetermined temperature to produce a stabilised conducting polymer, and (i)(b) heating the stabilised conducting polymer to a predetermined temperature to initiate formation of a graphitic material.

In another embodiment or example, there is provided a method of preparing a graphitic material comprising or consisting of the steps of: (i) heating the solid conducting polymer material to a temperature above about 550°C to initiate formation of a graphitic material; and (ii) cooling the graphitic material. The cooling step may provide a controlled cooling of the graphitic material, for example by a forced or convection cooling. The cooling step may comprise removal of the heating and allowing the graphitic material to cool by exposure to a lower temperature

environment. The cooling step may also be provided according to any one of the embodiments as described below in relation to cooling.

For example, the method of preparing a graphitic material comprises or consists of the steps of: (i)(a) optionally pre-heating the conducting polymer to a predetermined temperature to produce a stabilised conducting polymer; (i)(b) heating the conducting polymer to a predetermined temperature to initiate formation of a graphitic material; and (ii) optionally cooling the graphitic material.

In one embodiment or example, the method of preparing the graphitic material comprises or consists of the steps of: (i) heating a conducting polymer and metal source to a predetermined temperature to initiate formation of a graphitic material; and (ii) optionally cooling the graphitic material. In a further embodiment or example, the method of preparing the graphitic material further comprises a step of (i)(a) pre-heating the conducting polymer to a predetermined temperature to produce a stabilised conducting polymer, and (i)(b) heating the stabilised conducting polymer and metal source to a predetermined temperature to initiate formation of a graphitic material comprising the metal source.

In another embodiment or example, there is provided a method of preparing a graphitic material comprising or consisting of the steps of: (i) heating the solid conducting polymer material and solid metal source to a temperature above about 550°C to initiate formation of a graphitic material; and (ii) cooling the graphitic material.

In another embodiment or example, the method of preparing the graphitised coating comprises or consists of the steps of: (i) heating a conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, to a predetermined temperature to initiate formation of a graphitised coating; and (ii) optionally cooling the graphitised coating.

In another embodiment or example, there is provided a method of preparing a graphitised coating comprising or consisting of the steps of: (i) heating the solid conducting polymer material to a temperature above about 550°C to initiate formation of a graphitised coating; and (ii) cooling the graphitised coating. The cooling step may provide a controlled cooling of the graphitised coating, for example by a forced or convection cooling. The cooling step may comprise removal of the heating and allowing the graphitised coating to cool by exposure to a lower temperature

environment. The cooling step may also be provided according to any one of the embodiments as described below in relation to cooling. In one embodiment or example, the method of preparing the graphitised coating comprises or consists of the steps of: (i) heating a conducting polymer and metal source to a predetermined temperature to initiate formation of a graphitised coating; and (ii) optionally cooling the graphitised coating.

In another embodiment or example, there is provided a method of preparing a graphitised coating comprising or consisting of the steps of: (i) heating the solid conducting polymer material and solid metal source to a temperature above about 550°C to initiate formation of a graphitised coating; and (ii) cooling the graphitised coating.

For example, the method of preparing a graphitic material comprises or consists of the steps of: (i)(a) optionally pre-heating the conducting polymer to a predetermined temperature to produce a stabilised conducting polymer; (i)(b) heating the conducting polymer and metal source to a predetermined temperature to initiate formation of a graphitic material; and (ii) optionally cooling the graphitic material.

For step (i) the predetermined temperature may be between about 200°C to about 2200 °C. The predetermined temperature for step (i) may be in a range from between about 300 °C and 2000 °C, about 400 °C and 1800 °C, about 500 °C and 1600 °C, or about 600 °C and 1000 °C. In an example, the predetermined temperature for step (i) may be in a range from between about 600 °C and 1200 °C. For example the predetermined temperature for step (i) may be in a range from between about 800 °C and 1200 °C. The predetermined temperature for step (i) may be at least 200 °C, at least 300 °C, at least 400 °C, at least 500 °C, at least 600 °C, at least 700 °C, at least 800 °C, at least 900 °C, at least 1000 °C, at least 1500 °C, or at least 1800 °C. The

predetermined temperature for step (i) may be less than about 2200 °C, less than about 2000 °C, less than about 1800 °C, less than about 1500 °C, less than about 1000 °C, less than about 900 °C, less than about 800 °C, or less than about 700 °C. For example, the temperature required to form the graphitic material from the conducting material may be less than 2200 °C. The predetermined temperature for step (i) may be provided in a range between any two of these previously described upper and/or lower values. The predetermined temperature may allow for a more controlled production of the graphitic material. For step (i)(a) the predetermined temperature may be in a range between about 200 °C and about 600 °C. The predetermined temperature for step (i)(a) may be in a range from between about 250 °C and 550 °C, about 300 °C and 500 °C, or about 350 °C and 450 °C. The predetermined temperature for step (i)(a) may be at least 200 °C, at least 300 °C, at least 400 °C, or at least 500 °C. The predetermined temperature for step (i)(a) may be less than about 600 °C, less than about 550 °C, less than about 500 °C, less than about 450 °C, less than about 400 °C, or less than about 350 °C. The predetermined temperature for step (i)(a) may be provided in a range between any two of these previously described upper and/or lower values.

For step (i)(b) the predetermined temperature may be in a range between about 600 °C to about 2200 °C. The predetermined temperature for step (i)(b) may be in a range from between about 650 °C and 2000 °C, about 700 °C and 1800 °C, about 750 °C and 1600 °C, or about 800 °C and 1000 °C. The predetermined temperature for step (i)(b) may be in a range from between about 650 °C and 900 °C. In an example, the predetermined temperature for step (i)(b) may be in a range from between about 600 °C and 1200 °C. For example the predetermined temperature for step (i)(b) may be in a range from between about 800 °C and 1200 °C. The predetermined temperature for step (i)(b) may be at least 600 °C, at least 700 °C, at least 800 °C, at least 900 °C, at least 1000 °C, at least 1500 °C, at least 1800 °C, or at least 2000 °C. The

predetermined temperature for step (i)(b) may be less than about 2200 °C, less than about 2000 °C, less than about 1800 °C, less than about 1500 °C, less than about 1000 °C, less than about 900 °C, less than about 800 °C, or less than about 700 °C. The predetermined temperature for step (i)(b) may be provided in a range between any two of these previously described upper and/or lower values.

At least according to some embodiments or examples as described herein, the conducting polymer may be maintained at the predetermined temperature in step (i)(a) for about 30 to about 180 minutes. The conducting polymer may be maintained at the predetermined temperature in step (i)(a) for about 35 and 170 minutes, about 40 and 160 minutes, about 42 and 140 minutes, about 45 and 120 minutes, about 48 and 100 minutes, about 50 and 80 minutes, or about 55 and 70 minutes. The conducting polymer may be maintained at the initial predetermined temperature for step (i)(a) for at least 60 minutes, at least 70 minutes, at least 80 minutes, at least 90 minutes, at least 100 minutes, at least 110 minutes, at least 120 minutes, at least 130 minutes, at least 140 minutes, at least 150 minutes, at least 160 minutes, or at least 170 minutes. The conducting polymer may be maintained at the predetermined initial temperature for step (i)(a) for less than 180 minutes, less than 170 minutes, less than 160 minutes, less than 150 minutes, less than 140 minutes, less than 130 minutes, less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, or less than 70 minutes. The predetermined temperature for step (i)(a) may be provided in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples as described herein, the conducting polymer may be maintained at the predetermined temperature in step (i)(a) for about 0 to about 240 minutes. The conducting polymer may be maintained at the

predetermined temperature in step (i)(a) for about 5 and 220 minutes, about 10 and 200 minutes, about 15 and 180 minutes, about 20 and 150 minutes, about 25 and 100 minutes, or about 30 and 60 minutes. The conducting polymer may be maintained at the initial predetermined temperature for step (i)(a) for at least 1 minute, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 35 minutes, at least 40 minutes, at least 45 minutes, at least 50 minutes, or at least 55 minutes. The conducting polymer may be maintained at the predetermined initial temperature for step (i)(a) for less than 200 minutes, less than 180 minutes, less than 160 minutes, less than 140 minutes, less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, less than 80 minutes, less than 70 minutes, or less than 60 minutes. The predetermined temperature for step (i)(a) may be provided in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples, the conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for about 30 to about 180 minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for about 35 and 180 minutes, about 40 and 160 minutes, about 42 and 140 minutes, about 45 and 120 minutes, about 48 and 100 minutes, about 50 and 80 minutes, or about 55 and 70 minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for at least 60 minutes, at least 70 minutes, at least 80 minutes, at least 90 minutes, at least 100 minutes, at least 110 minutes, at least 120 minutes, at least 130 minutes, at least 140 minutes, at least 150 minutes, at least 160 minutes, or at least 170 minutes. The conducting polymer may be maintained at the predetermined temperature for step (i) or step (i)(b) for less than 180 minutes, less than 170 minutes, less than 160 minutes, less than 150 minutes, less than 140 minutes, less than 130 minutes, less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, or less than 70 minutes. The predetermined temperature for step (i) or step (i)(b) may be provided in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples, the conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for about 0 to about 240 minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for about 5 and 220 minutes, about 10 and 200 minutes, about 15 and 180 minutes, about 20 and 150 minutes, about 25 and 100 minutes, or about 30 and 60 minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for at least 1 minute, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 35 minutes, at least 40 minutes, at least 45 minutes, at least 50 minutes, or at least 55 minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be maintained at the predetermined temperature for step (i) or step (i)(b) for less than 200 minutes, less than 180 minutes, less than 160 minutes, less than 140 minutes, less than 120 minutes, less than 110 minutes, less than 100 minutes, less than 90 minutes, less than 80 minutes, less than 70 minutes, or less than 60 minutes. The predetermined temperature for step (i) or step (i)(b) may be provided in a range between any two of these previously described upper and/or lower values.

At least according to some embodiments or examples as described herein, the conducting polymer may be pre-heated to the predetermined temperature for step (i)(a) at a rate of about 2 °C/minute to about 15 °C/minute, about 4 °C/minute to about 12 °C/minute, or about 6 °C/minute to about 10 °C/minute. The conducting polymer may be pre-heated to the predetermined temperature for step (i)(a) at a rate of less than about 15 °C/minute, less than about 12 °C/minute, less than about 10 °C/minute, less than about 8 °C/minute, less than 6 °C/minute, or less than 4 °C/minute. The conducting polymer may be pre-heated to the predetermined temperature for step (i)(a) at a rate of at least about 4 °C/ minutes, at least about 6 °C/minutes, at least about 8 °C/minutes, at least about 10 °C/minutes, or at least about 12 °C/minutes. The conducting polymer may be pre-heated to the predetermined temperature step (i)(a) at a rate that may be provided in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples as described herein, the conducting polymer may be pre-heated to the predetermined temperature for step (i)(a) at a rate of about 1 °C/minute to about 50 °C/minute, about 10 °C/minute to about 40 °C/minute, or about 15 °C/minute to about 30 °C/minute. The conducting polymer may be pre- heated to the predetermined temperature for step (i)(a) at a rate of less than about 40 °C/minute, less than about 35 °C/minute, less than about 30 °C/minute, less than about 25 °C/minute, less than 20 °C/minute, or less than 15 °C/minute. The conducting polymer may be pre-heated to the predetermined temperature for step (i)(a) at a rate of at least about 1 °C/ minutes, at least about 5 °C/minute, at least about 10 °C/minute, at least about 15 °C/minute, or at least about 20 °C/minute. The conducting polymer may be pre-heated to the predetermined temperature step (i)(a) at a rate that may be provided in a range between any two of these previously described upper and/or lower values.

In another embodiment or example, the conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of about 2 °C to about 15 °C/minute, about 4 °C/minute to about 12 °C/minute, or about 6

°C/minute to about 10 °C/minute. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of less than about 15 °C/minute, less than about 12 °C/minute, less than about 10 °C/minute, less than about 8 °C/minute, less than 6 °C/minute, or less than 4 °C/minute. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, can be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of at least about 4 °C/ minutes, at least about 6 °C/minutes, at least about 8 °C/minutes, at least about 10 °C/minutes, or at least about 12 °C/minutes. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature step (i) or step (i)(b) at a rate that may be provided in a range between any two of these previously described upper and/or lower values.

In yet another embodiment or example, the conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of about 1 °C/minute to about 50 °C/minute, about 10 °C/minute to about 40 °C/minute, or about 15 °C/minute to about 30 °C/minute. The conducting polymer, or a coating

composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of less than about 40 °C/minute, less than about 35 °C/minute, less than about 30 °C/minute, less than about 25 °C/minute, less than 20 °C/minute, or less than 15 °C/minute. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, can be heated to the predetermined temperature for step (i) or step (i)(b) at a rate of at least about 1 °C/ minute, at least about 5 °C/minute, at least about 10 °C/minute, at least about 15 °C/minute, or at least about 20 °C/minute. The conducting polymer, or a coating composition according to any embodiments or examples thereof as defined herein, may be heated to the predetermined temperature step (i) or step (i)(b) at a rate that may be provided in a range between any two of these previously described upper and/or lower values.

In another embodiment or example, the graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate of about 1 °C/minute to about 100 °C/minute, about 2 °C/minute to about 100 °C/minute, about 50 °C/minute to about 80°C/minute, about 25 °C to about 50 °C/minute, about 25 °C to about 40 °C/minute, about 15 °C to about 25 °C/minute, or about 5 °C to about 15 °C/minute. The graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate of less than about 100 °C/minute, of less than about 80 °C/minute, less than about 60 °C/minute, less than about 40 °C/minute, less than about 20 °C/minute, less than about 10 °C/minute, or less than about 5 °C/minute. The graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate of at least about at least about 1 °C/minute, 5 °C/minute, at least about 10 °C/minute, at least about 20

°C/minute, at least about 40 °C/minute, at least about 60 °C/minute, or at least about 80 °C/minute. The graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate at a rate that may be provided in a range between any two of these previously described upper and/or lower values. The rate of cooling may influence the nanostructure of the graphitic material. In another embodiment or example, the graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate of about 10 °C/minute to about l00°C/minute. In yet another embodiment or example, cooling the graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) at a controlled rate may be, for example, cooling the graphitic material formed to ambient temperature at a rate of 1 °C/minute to 100 °C/minute, 50 °C/minute to 100 °C/minute, 25 °C/minute to 50 °C/minute, 25 °C/minute to 40 °C/minute, 15 °C/minute to 25 °C/minute, or 5

°C/minute to l5°C/minute. In one example, cooling the graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (ii) to ambient temperature may be at a rate of less than 5 °C/minute. In another example, cooling the graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (ii) to ambient temperature may be at a rate of up to 18 °C/minute or at a rate of up to 25 °C /minute. The graphitic material, or a graphitised coating according to any embodiments or examples thereof as defined herein, formed in step (i) or step (i)(b) can be cooled in step (ii) to ambient temperature at a rate at a rate that may be provided in a range between any two of these previously described upper and/or lower values.

Conducting Polymer

Conducting polymers are polymers with conjugated chain structures. It will be appreciated that a conducting polymer refers to any organic polymer or organic copolymer that is capable of conducting electricity, and may for example include a polymer that is a semi-conductor. It will be appreciated that a conducting polymer may require further processing to provide desired conductance properties. An example of a conducting polymer is polyaniline. It will be appreciated that the terms "conducting polymer" or "polymer" can include one or more "copolymers", and the term

"monomer" can include one or more comonomers.

The conducting polymer may have a linear backbone. The conducting polymer may be selected from the group consisting of a polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, and polype- ethyl enedioxy thiophene). In at least some examples, the conducting polymers can be selected to provide for further improved processability. In at least some examples, polyaniline polymers provide improved conductivity. It will be appreciated that the conducting polymer includes any salts thereof, such as those formed by reaction with an acid, for example a protonic acid. The conducting polymer can comprise, or be a reaction product of, an unsubstituted or substituted monocyclic, bicyclic, or tricyclic hetaryl monomer comprising at least one annular heteroatom selected from nitrogen and sulphur. The conducting polymer can comprise, or be a reaction product of, an unsubstituted or substituted monocyclic, bicyclic, or tricyclic aryl monomer comprising at least one exocyclic heteroatom selected from nitrogen and sulphur. For example, the conducting polymer can comprise, or be a reaction product of, an unsubstituted or substituted monocyclic aryl monomer comprising at least one exocyclic heteroatom selected from nitrogen and sulphur. In an example, the conducting polymer comprises or consists of a polymerised monocyclic monomer having a single aromatic ring. In another example, the polymerised monocyclic monomer having a single aromatic ring comprises at least one exocyclic heteroatom selected from nitrogen and sulphur. It will be appreciated that the reaction products can involve reaction with a protonic acid and free radical initiator. To achieve an increased conductivity in conducting polymers, a counter ion may be introduced by protonation and / or redox reaction.

In another example, the conducting polymer comprises, or is a reaction product of, an unsubstituted or substituted monocyclic, bicyclic, or tricyclic hetaryl monomer and/or an unsubstituted or substituted monocyclic aryl monomer. The hetaryl monomer may comprise at least one annular heteroatom selected from nitrogen and sulphur. The aryl or hetaryl monomer may comprise at least one exocyclic heteroatom selected from nitrogen and sulphur. In another example, the conducting polymer comprises, or is a reaction product of, an unsubstituted or substituted monocyclic hetaryl or aryl monomer.

Polypyrrole and polyazepine are examples of conducting polymers prepared from a reaction product of a monocyclic hetaryl comprising at least one heteroatom selected from nitrogen. Polyindole is an example of a conducting polymer prepared from a reaction product of a bicyclic hetaryl comprising at least one heteroatom selected from nitrogen. Polycarbazole is an example of a conducting polymer prepared from a reaction product of a tricyclic hetaryl comprising at least one heteroatom selected from nitrogen. A polyarylamine, such as polyaniline, is an example of a conducting polymer prepared from a reaction product of a monocyclic aryl monomer comprising at least one exocyclic heteroatom selected from nitrogen. Polythiophene is an example of a conducting polymer prepared from a reaction product of a monocyclic hetaryl comprising at least one heteroatom selected from sulphur. Poly(3,4- ethylenedioxythiophene) is an example of a conducting polymer prepared from a reaction product of a bicyclic hetaryl comprising at least one heteroatom selected from sulphur. Polyphenylene sulfide is an example of a conducting polymer prepared from a reaction product of a monocyclic aryl monomer comprising at least one exocyclic heteroatom selected from sulphur.

In one example, the conducting polymer is a polyarylamine, for example polyaniline. The polyarylamine may comprise, or be a reaction product of, an unsubstituted or substituted monocyclic, bicyclic, or tricyclic hetaryl monomer and/or an unsubstituted or substituted monocyclic aryl monomer. The hetaryl monomer may comprise at least one annular heteroatom selected from nitrogen and sulphur. The aryl monomer may comprise at least one exocyclic heteroatom selected from nitrogen and sulphur. In another example, the polyarylamine comprises, or is a reaction product of, an unsubstituted or substituted monocyclic hetaryl or aryl monomer.

The conducting polymer may be a base or salt, for example a polyaniline emeraldine salt. The conducting polymer salt may be selected from a phosphorus or sulphur containing salt. In one example the conducting polymer salt is a sulfonate salt. The salt may be a dinonylnapthalenesulfonate (DNNSA), methanesulfonate (MSA), camphorsulfonate (CSA), p-toluenesufonate (TSA), dodecyl benzene sulfonate

(DBS A), dinonylnapthalene sulfonate (DNNSA), or combinations thereof. In one example, the conducting polymer salt is a dinonylnapthalene sulfonate salt (DNNSA).

In another example, the conducting polymer salt is an organic solvent soluble conducting polymer salt. The organic solvent soluble conducting polymer salt may be provided wherein at least 0.1. 0.5, 1, 5, 10, 25, or 50 g of the conducting polymer salt is soluble in 100 mL of an organic solvent (e.g. toluene), when measured at standard room temperature and pressure.

In another example the conducting polymer salt is a phosphorus containing salt. The conducting polymer salt may be a phosphonate salt or a phosphonate salt. In some embodiments or examples, the phosphonate salt may be derived from phosphonic acids such as phenylphosphinic acid, styrilphosphonic acid, 2-chloroethyl-phosphonic acid, n-decylphosphonic acid, n-benzylphosphonic acid, n-butylphosphonic acid, aminotris(methylene phosphonic acid). In some embodiments or examples, the phosphonate salt may be derived from diesters of phosphoric acid (e.g. (2- methylpropyl) hydrogen phosphate (DiBHP), bis(2-ethylhexyl) hydrogen phosphate (DiOHP) and its non-branched analogue, and bis(n-octyl) hydrogen phosphate

(DnOHP)). In some embodiments or examples, the phosphonate salt may be a phenylphosphonate, styrilphosphonate, 2-chloroethyl-phosphonate, n- decylphosphonate, «-benzyl phosphonate, «-butyl phosphonate, aminotris(methylene phosphonate, (2-methylpropyl) hydrogen phosphonate, bis(2-ethylhexyl) hydrogen phosphonate, and bis(n-octyl) hydrogen phosphonate, or combinations thereof.

The polyaniline base or salt may be further processed into a polyaniline emeraldine base or salt. At least according to some embodiments or examples as described herein, may be a polyaniline emeraldine base or polyaniline emeraldine salt. The polyaniline salt may be polyaniline hydrochloric acid. The polyaniline salt may be a polyaniline sulfonate sa/t. The polyaniline salt can be a sulfonate, for example where the acid is dinonylnapthalenesulfonic acid (DNNSA) In an embodiment or example, the polyaniline salt can be a sulfonate where the sulfonic acid may be methanesulfonic acid (MSA), camphorsulfonic acid (CSA), p-toluenesufonic acid (TSA), dodecyl benzene sulfonic acid (DBS A), dinonylnapthalene sulfonic acid (DNNSA), or combinations thereof. The conducting polymer may be polyaniline methanesulfonate salt (PANI-MSA). The conducting polymer may be polyaniline camphorsulfonate salt (PANI-CSA). The conducting polymer may be polyaniline p-toluenesufonate salt

(PANI-TSA). The conducting polymer may be polyaniline dodecyl benzene sulfonate salt (PANI-DBSA). The conducting polymer may be polyaniline dinonylnapthalene sulfonate salt (PANI-DNNSA). Polyaniline

An aniline monomer can be polymerised to form polyaniline. Polyaniline can be in three potential oxidation states: leucoemeraldine (white), emeraldine (green), and pernigraniline (blue/violet). The repeat unit of Formula 1 below provides x as half a degree of polymerization.

Formula 1

Leucoemeraldine is a fully reduced state (e.g. n = 1, m = 0). Pemigraniline is a fully oxidized state with imine links instead of amine links (n = 0, m = 1). The polyaniline can be in one of these three states or a mixture thereof. The emeraldine form of polyaniline (n = m = 0.5), is referred to as emeraldine base (EB), if neutral, although when protonated is called emeraldine salt (ES), with the imine nitrogens protonated by an acid. Protonation facilitates delocalising the otherwise trapped diiminoquinone-diaminobenzene state. Emeraldine base is the preferred form of polyaniline because of its typical high stability at room temperature and on protonation to provide the emeraldine salt form, has high electrical conductivity.

Polyphenylene Sulfide

The conducting polymer may be a polyphenylene sulfide. Polyphenylene sulfide is an organic polymer comprising of aromatic rings linked with sulphide moieties. The repeat unit of Formula 2 below provides one example of a repeating unit of polyphenylene sulfide.

Formula 2

Polyphenylene sulfide can be converted to the semiconducting form by oxidation or use of various dopants. Polyphenylene sulfide also offers high temperature resistance, chemical resistance, flowability, dimensional stability and electrical characteristics. Polypyrrole

A pyrrole monomer can be polymerised to form polypyrrole. Polypyrrole is a conducting polymer. The repeat unit of Formula 3 below provides one example of a repeating unit of polypyrrole.

Formula 3

Polypyrrole in its oxidized form is a good electrical conductor. Higher conductivities can be achieved by doping polypyrrole with large anions, such as tosylate.

Polycarbazole

A carbazole monomer can be polymerised to form polycarbazole. Polycarbazole is an electrically conducting polymer in its oxidised state. The repeat unit of Formula 4 below provides one example of a repeating unit of polycarbazole.

Formula 4

When the nitrogen of the polycarbazoles is oxidised prior to the backbone, which can create a high localised charge and good electrical conducting properties.

Polyindole

An indole monomer can be polymerised to form polyindole. Polyindole is a conductive polymer containing a benzene ring linked with a pyrrolitic ring. The repeat unit of Formula 5 below provides one example of a repeating unit of polyindole.

Formula 5

Polyazepine

An azepine monomer can be polymerised to form polyazepine. The repeat unit of Formula 6 below provides one example of a repeating unit of polyazepine.

Formula 6 Polythiophene

A thiophene monomer can be polymerised to form polythiophene. Polythiophene becomes conductive when oxidised. The repeat unit of Formula 7 below provides one example of a repeating unit of polythiophene.

Formula 7

The electrical conductivity of polythiophene results from the delocalisation of electrons along the polythiophene backbone. Polythiophene also has good optical properties which respond to various environmental stimuli, and include colour shifts in response to changes in solvent, temperature and applied potential. Both colour changes and conductivity changes are induced by the twisting of the polymer backbone, disrupting conjugation. Poly(3,4-ethylenedioxy)thiophene

A 3,4-ethylenedioxythiophene monomer can be polymerised to form poly(3,4- ethylenedioxythiophene). Poly(3,4-ethylenedioxythiophene) is a transparent conducting polymer, which can be employed in liquid crystal displays (LCDs) and solar cells. The repeat unit of Formula 8 below provides one example of a repeating unit of poly(3,4-ethylenedioxythiophene).

Formula 8

Poly(3,4-ethylenedioxythiophene) has good optical transparent properties in its conducting state, high stability and a moderate band gap and low redox potential.

Poly(3,4-propylenedioxy)thiophene

A 3,4-propylenedioxythiophene monomer can be polymerised to form poly(3,4- propylenedioxy thiophene). Poly(3,4-propylenedioxythiophene) is a transparent conducting polymer with applications in electrochromic devices. The repeat unit of Formula 9 below provides one example of a repeating unit of poly(3,4- propy 1 enedi oxy thi ophene) .

Formula 9 Poly(3,4-propylenedioxythiophene) has excellent optical and electrochromic properties as well as good processability and solubility.

In some embodiments or examples, each individual polymerised chain of the conducting polymer, or any salt thereof, may be independently comprised of individual monomer units of between about 100 to 1500. The number of individual monomer units may be at least about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200. The number of individual monomer units may be less than about 1500, 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, or 500. The number of individual monomer units may be between about 300 to 1400, 500 to 1300, 600 to 1200, or 700 to 1100. The number of individual monomer units in an individual polymerised chain may be in a range provided by any lower and/or upper limit as previously described.

The conducting polymer or salt thereof may have a number average molecular weight of at least 10,000. For example, number average molecular weight may be at least about 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, or 80,000. The number average molecular weight may be in a range of about 10,000 to 120,000, 20,000 to 115,000, 30,000 to 110,000, 40,000 to 105,000, 50,000 to 100,000, or 60,000 to 100,000. The number average molecular weight may be less than about 120,000, 110,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, or 40,000. The number average molecular weight may be in a range provided by any lower and/or upper limit as previously described.

It will be appreciated that the conducting polymer described herein, such as polyaniline, may allow versatility in application of the end product graphitic material. For example, a polyaniline sulfonate salt is particularly suitable for providing controlled production of graphitic material. It will be appreciated that the process for producing graphitic material as described in the present disclosure can provide a cost- effective scalable process for obtaining graphitic material having advantageous properties of functionality and dispersibility.

It will be appreciated that the conducting polymer of the present invention may be provided in a high purity. In an embodiment or example, the purity of conducting polymer may be in a range from about (by weight %) 70 to 99, about 75 to 98, about 80 to 97, about 85 to 96, about 90 to 95. The purity of conducting polymer may be at least (by weight %) 70, 75, 80, 85, 90, 95, or 99. The purity of the conducting polymer may be less than about (by weight %) 99, 98, 97, 96, 95, 90, 85, 80, 75. The purity of conducting polymer may be in a range provided by any lower and/or upper limit as previously described. It will be appreciated that the conducting polymer may be dissolved or dispersed in an organic solvent for coating on a substrate. In other words the conducting polymer and at least according to some embodiments or examples is present in a solid phase and is capable of being dissolved or dispersed in an organic solvent such that the conducting polymer can be applied or coated onto a scaffold or substrate and then heated to form a scaffold or substrate coated with the graphitic material.

In an embodiment or example, the coated substrate comprising the conducting polymer may have residual organic solvent, for example in an amount of less than (by weight %) 8, 7, 6, 5, 4, 3, 2, or 1. The amount of residual organic solvent may be (by weight %) at least 1, 2, 3, 4, 5, 6, 7, or 8. The amount of residual organic solvent may be in a range provided by any lower and/or upper limit as previously described. In an embodiment or example, the conducting polymer may have residual monomer in an amount of less than (by weight %) 5, 4, 3, 2, 1, or 0.5.

At least according to some embodiments or examples, the ratio of sulphur to nitrogen (S/N ratio) when present for the conducting polymer may be in a range of about 0.1 to 0.5, 0.15 to 0.45, or 0.2 to 0.4. The S/N ratio may be less than 0.5, 0.45, 0.4, 0.35, 0.3, or 0.25. The S/N ratio may be at least 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5. The S/N ratio may be in a range provided by any lower and/or upper limit as previously described. For example, the S/N ratio for polyaniline sulphonate salt may be in a range of about 0.1 to 0.5, 0.15 to 0.45, or 0.2 to 0.4. The S/N ratio for polyaniline sulphonate salt may be less than 0.5, 0.45, 0.4, 0.35, 0.3, or 0.25. The S/N ratio for polyaniline sulphonate salt may be at least 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5. The S/N ratio for polyaniline sulphonate salt may be in a range provided by any lower and/or upper limit as previously described.

Metal Source

It will be appreciated that a metal source may be selected and varied based on a particular reaction or application required. For example the metal source may be a catalyst material and selected to provide for heterogeneous catalysis reactions in a continuous flow reactor environment. The metal source may be a metal or metal oxide. The metal source may be a metal compound including metal salts and metal complexes.

At least according to some embodiments or examples, the metal source may comprise at least one metal or metal oxide wherein the metal is selected from iron, cerium, cobalt, copper, zinc, nickel, palladium, platinum, gold, silver, ruthenium, iridium, rhodium, titanium vanadium, zirconium, niobium, tantalum, and chromium, or complexes thereof. The metal source may include alloys of the metals. In another example, the metal may be selected from palladium, platinum, ruthenium, rhodium, or any oxide, complexes, or combinations thereof. In one example the metal may be selected from palladium or a palladium complex thereof, such as palladium and/or any oxides and/or any alloys thereof.

In one embodiment or example, the metal or metal oxide thereof may

independently be selected from the group consisting of copper, manganese, zirconium, titanium, zinc and silver. In another embodiment or example, the metal may

independently be selected from the group consisting of copper, zirconium, titanium, zinc and silver.

At least according to some embodiments or examples, the metal source may be in the form of nanoparticles. The metal source may have an average particle size from about 1 nm to about 500 nm. In one embodiment, the metal source may have an average particle size selected from about 5 nm to about 300 nm. In some embodiments, the metal source may have an average particle size of at least about 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 150 nm, 200 nm, or 250 nm. In some embodiments, the metal source may have an average particle size of less than about 500 nm, 400 nm, 300 nm, 200 nm, 150 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm or 10 nm. The metal source may have an average particle size range selected from any two of the above upper and/or lower values.

In another example, the coating composition is a suspension comprising metal source in the form of solid particles (e.g. metal particles) and one or more solvents. For example, there may be provided a liquid formulation comprising or consisting of a plurality of metal particles and one or more solvents, and optionally one or more additives. The liquid carriers may be provided by one or more organic solvents as described herein. In some embodiments or examples, the metal source may be interspersed in the coating composition. For example, the metal particles may comprises an organic soluble metal complex, metal compound or metal salt, or combination thereof. In one example, the metal particles may be catalytic metal particles. It has been surprisingly found that when a metal compound, metal salt or metal complex, used in the liquid formulations is heated together with a conducting polymer, a graphitised coating comprising metal particles interspersed in the surface coating is obtained.

At least according to some embodiments or examples, the metal source may be in the form of individual particles interspersed on the surface of the graphitic material as individual particles. The metal source may comprise or consist a one or more metal complex, compound, oxide, or salt, or a combination thereof. The metal complex, compound, oxide, or salt, or a combination thereof, may provide a precursor for forming interspersed particles, such as interspersed nanoparticles or nanospheres. The metal complex, compound, oxide, or salt, or a combination thereof, may provide an organic solvent soluble precursor for forming interspersed particles. For example, the metal complex, compound, oxide, or salt, or a combination thereof, may be heated along with a conducting polymer to form interspersed metal nanoparticles on the graphitic material.

The metal source may comprise a noble metal, transition metal or rare-earth metal (e.g. lanthanides), or a combination thereof.

In some embodiments or examples, the metal may independently be selected from the group comprising or consisting of iron, cerium, cobalt, copper, zinc, nickel, palladium, platinum, gold, silver, ruthenium, iridium, rhodium, titanium vanadium, zirconium, niobium, tantalum, and chromium. In other embodiments or examples, the metal or metal oxide thereof may independently be selected from the group consisting of copper, manganese, zirconium, titanium, zinc and silver. In another embodiment or example, the metal may independently be selected from the group consisting of copper, zirconium, titanium, zinc and silver. In some embodiments, the metal may independently be selected from the group consisting palladium, platinum, ruthenium, and rhodium. In one embodiment or example, the metal may independently be selected from the group consisting of palladium, titanium and platinum. In another embodiment or example, the metal may independently be selected from the group consisting of palladium and platinum. In yet another embodiment or example, the metal may be palladium.

It will be appreciated that reference to metal complex or metal compound refers to a metal in the form of a coordination compound or coordination complex and contains ions or molecules (e.g. ligands) linked to a metal (e.g. transition metal). For example, a metal organic framework (MOF). In another example, the metal complex or compound may be copper acetyl acetonate, copper stearate, copper acetate, zirconium acetyl acetonate, manganese acetyl acetonate, silver acetyl acetonate, silver carbonate, silver stearate, silver powder.

It will be appreciated that reference to metal salt refers to a metal comprising both anions and cations. For example a NCb anion is the counterion for a Pd metal cation. Some example counterions that may be used are NO3 , Cl , S0 ₄ ² . For example, the metal salt may be selected from palladium nitrate.

At least according to some embodiments or examples, the metal source may be provided in the coating composition in an amount of from about 1 wt % to about 20 wt % of the total mass of the coating composition. In some embodiments, the metal source may be provided in the coating composition in an amount of from about 2 wt % to about 10 wt %, for example of from about 4 wt % to about 8 wt % of the total mass of the catalytic coating composition. In some embodiments, the metal source may be provided in the coating composition in an amount of less than about 20 wt %, less than about 15 wt %, less than about 10 wt %, or less than about 6 wt % of the total mass of the coating composition. In some embodiments, the metal source may be provided in the coating composition in an amount of at least about 1 wt %, at least about 2 wt %, at least about 3 wt %, or at least about 4 wt % of the total mass of the coating

composition. The metal source may be provided in the coating composition in an amount selected from any two of the above upper and/or lower values. In some embodiments or examples, the metal source may be provided by one or more organic soluble metal compounds, such as one or more metal salts and/or metal oxides. The organic soluble metal salts and metal oxides may be precursors to, or may facilitate formation of, metal particles on the surface of the graphitised coating or graphitic material thereof. The organic soluble metal salts and metal oxides may decompose upon heating to form the catalytically active metal particles on the surface of the graphitic material. The organic soluble metal salts can be selected from lead nitrate, lead dibenzylideneacetone, ruthenium acetylacetonate, copper acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, zirconium acetylacetonate, silver carbonate, silver acetate, silver (powder), silver stearate, copper stearate, or combinations thereof. The metal oxides can be selected from titanium oxide, zinc oxide, copper oxide, ruthenium oxide, manganese oxide, or combinations thereof. The metal oxides may be provided as dispersions in an organic solvent prior to coating on a substrate and drying and/or heating to form the graphitised coating.

Additives

Other compounds or additives may also be included in the coating compositions to achieve additional advantages or impart various further properties to the

composition. Additional additives, such as binders, may facilitate coating of the catalyst composition to a substrate. In one example, the binders are polymeric binders. Polymeric binders can be thermoplastics or thermosets and may be elastomers. Binders may also comprise monomers that can be polymerized before, during, or after the application of the coating composition to the substrate. Polymeric binders may be cross-linked or otherwise cured after the ink has been applied to the substrate.

Other compounds or additives may include dispersion aids (including surfactants, emulsifiers, and wetting aids), adhesion promoters, thickening agents (including clays), defoamers and anti-foamers, biocides, fillers, flow enhancers, stabilizers, cross-linking and curing agents, and combinations thereof.

For example, suitable additives may comprise or consist of one or more of:

(a) rheology modifiers such as hydroxypropyl methyl cellulose (e.g. Methocell 311), modified urea (e.g. Byk 411, 410), cellulose acetate butyrates (e.g. Eastman CAB-551-0.01, CAB-381-0.5, CAB-381-20), and polyhydroxycarboxylic acid amides (e.g. Byk 405);

(b) wetting agents such as fluorochemical surfactants (e.g. 3M Fluorad);

(c) surfactants such as fatty acid derivatives (e.g. AkzoNobel, Bermadol SPS 2543), quaternary ammonium salts, ionic and non-ionic surfactants;

(d) dispersants such as non-ionic surfactants based on primary alcohols (e.g. Merpol 4481, DuPont) and alkylphenol -formaldehyde-bisulfide condensates (e.g. Clariants 1494);

(e) anti-foaming agents;

(f) levelling agents such as fluorocarbon-modified polymers (e.g. EFKA 3777);

(g) pigments, such as those used in aerospace paint compositions, which may include organic phthalocyanine, quinaridone, diketopyrrolopyrrole (DPP), and diarylide derivatives and inorganic oxide pigments (for example to enhance visibility of the reactivation treatment and where it has been applied)

(h) dyes including organic and inorganic dyes such as fluorescents (Royale Pigment and Chemicals) (e.g. to enhance visibility of the reactivation treatment and where it has been applied), fluorescein, and phthalocyanines;

(i) anti-corrosion additives such as phosphate esters (e.g. ADD APT, Anticor C6), alkylammonium salt of (2-benzothiazolythio) succinic acid (e.g. BASF, Irgacor 153), triazine dithiols, and thiadiazoles.

The additives may be selected from rheology modifiers, wetting agents, surfactants, dispersants, anti-foaming agents, levelling agents, colorants and anti corrosion agents. Anti-foaming agents may be obtained commercially from, for example, BYK and include BYK-05, BYK-354, and BYK-392. The colorant may be a UV fluorescent dye. The additives may be selected from colorants and anti-corrosion agents. The additives may be selected from dyes and anti-corrosion agents. The additives may be selected from UV fluorescent dyes and anti-corrosion agents. The additives may be UV fluorescent dyes. The additives may be anti-corrosion agents.

The optional additives may be colorants such as dyes. Dyes may be organic, soluble in the surrounding medium, and black or chromatic substances (see Rompp Coatings and Printing Inks, page 221, keyword "colorant"). The optional additives may for example be selected from those as described in the book "Coating Additives" by Johan Bielemann, Wiley-VCH, Weinheim, New York, 1998. The dyes may include organic and inorganic dyes. The dyes may be organic dyes, such as azo dyes (e.g. monoazo such as arylamide yellow PY73, diazo such as diarylide yellows, azo condensation compounds, azo salts such as barium red, azo metal complexes such as nickel azo yellow PG10, benzimidazone). The dyes may be fluorescents (e.g. Royale Pigment and chemicals, to enhance visibility of the coating and where it has been applied), fluorescein, phthalocyanines, porphyrins. The colorants such as fluorescent dyes could for example be used with UV goggles to look for fluorescence after spraying to insure coverage. It will be appreciated that dyes may be organic soluble for improved compatibility or miscibility with the solvents. Peak absorption may be below about 295 nm, for example, which is the natural cut-on for sunlight. Further examples of fluorescent dyes may include acridine dyes, cyanine dyes, fluorine dyes, oxazine dyes, phenanthridine dyes, and rhodamine dyes.

The optional additives may be colorants such as pigments. Pigments may be in powder or flake-form and can provide colorants which, unlike dyes may be insoluble in the surrounding medium (see. Rompp Lacke und Druckfarben, Georg Thieme Verlag Stuttgart / New York 1998, page 451, keyword "pigments"). Pigments are typically composed of solid particles less than about 1 pm in size to enable them to refract light, for example within light wavelengths of between about 0.4 and about 0.7 pm. In one aspect, pigments have solid particles between about 200 nm and about 1000 nm, such as between about 500 nm and about 1000 nm. The pigments may be selected from organic and inorganic pigments including color pigments, effect pigments, magnetically shielding, electrically conductive, anticorrosion, fluorescent and phosphorescent pigments. Further examples of suitable pigments may, for example, be as described in German Patent Application DE-A-2006053776 or EP-AO 692 007. Organic pigments may include polycyclic pigments (e.g. phthalocyanide such as copper phthalocyanine, anthraquinones such as dibrom anthanthrone, quinacridones such as quinacridone red PV19, dioxazines such as di oxazine violet PV23, perylene, thionindigo such as tetrachloro), nitro pigments, nitroso pigments, quinoline pigments, and azine pigments. The pigments may be inorganic. The inorganic pigments may be selected from carbon black (e.g. black), titanium dioxide (e.g. white), iron oxides (e.g. yellows, reds, browns, blacks), zinc chromates (e.g. yellows), azurites (e.g. blues), chromium oxides (e.g. greens and blues), cadmium sulphoxides (e.g. greens, yellows, reds), lithopones (e.g. whites). Examples of pigments used in aerospace paint compositions may include organic phthalocyanine, quinaridone, diketopyrrolopyrrole (DPP), and diarylide derivatives and inorganic oxide pigments (for example to enhance visibility of the reactivation treatment and where it has been applied).

The anti-corrosion additives may for example facilitate prevention or reduction in corrosion of metal substrates (e.g. metal or metal alloy). Examples of anti-corrosion agents include metal salts including rare earth metals, such as salts of zinc, molybdate, and barium (e.g. phosphates, chromates, molybdates, or metaborate of the rare earth metals).

The additive(s) are usually present in an amount of less than about 10% based on the total weight of the composition or formulation. For example, the total amount of all additives combined, if present, may be provided in an amount of less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, or 0.05%. The additives may be provided in an amount of greater than about 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%. The total amount of all additive(s), if present, may be provided in an amount (based on the total weight of the formulation or the components thereof) of a range between any two of the above values, for example between about 0.01% and about 10%, between about 0.05% and 5 %, between about 0.1% and about 3%, or between about 0.5% and about 2%.

Solvents

The solvent may be selected to provide a fluidic carrier for the coating composition. The solvent may be an organic solvent. In an example, the organic solvent is a non-aqueous organic solvent. The organic solvents can be selected from various water immiscible solvents. The solvent can be selected from water miscible solvents.

The organic solvents can be selected from the group comprising aromatics, chlorinated aromatics, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, esters, alcohols, and ketones. It will be appreciated that the alcohols are water immiscible alcohols having at least a medium alkyl chain or aryl group. The water immiscible alcohols can be n-butanol or larger alkyl chain alcohols.

It will be appreciated that the ketones are water immiscible ketones having at least medium chain ketones such as methyl ethyl ketone or ketones with larger alkyl chains.

The organic solvent can be selected from the group comprising aromatics, halogenated aromatics, halogenated aliphatic hydrocarbons, aliphatic hydrocarbons, glycols, ethers, glycol ethers, esters, alcohols, ketones, or combinations thereof.

In another example, the organic solvent is a non-aqueous organic solvent selected from toluene, xylene and mesitylene. In another example, the organic solvent is a non-aqueous organic solvent selected from an aromatic hydrocarbon, for example, toluene and xylene. In another example, the organic solvent is a cyclic amide, for example, «-methyl -2-pyrrol i done.

The organic solvent can also be selected to dissolve an acid dopant (i.e. protonic acid), for example a protonic acid of DNNSA can be provided in the organic solvent such as glycol ethers (e.g. 2-butoxyethanol), hydrocarbons (e.g. heptane), or aromatic hydrocarbons (e.g. toluene or xylene).

Following the reaction process, the organic solvents (e.g. same water immiscible solvents) can be used to dilute the product in order to give the desired final

concentration and properties.

Suitable exemplary liquid solvents include aromatics, such as xylene, toluene or alkylnaphthalenes; chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as butanol, isobutanol, or glycol and also their ethers and esters, such as 2-butoxy ethanol; ketones, such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.

In some examples, solvents may contain less than about 800 ppm of water, for example less than about 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, or 100 ppm water. Anhydrous forms of the solvents are preferred. The solvent(s) may be present in an amount (based on the total weight of the formulation or the components thereof) of less than about 99%, 98%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40%. The solvents may be present in an amount (based on the total weight of the reactivation formulation or the components thereof) of greater than about 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. The solvent may be present in an amount of a range between any two of those values, for example between about 90 and 99%, between about 50% and 70%, or between about 35% and 60%.

The solvents may contain incidental impurities, for example in an amount (wt % of the total formulation) is less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001%. Graphitised Coated Substrates and Graphitised Metal Coated Substrates

It will be appreciated that the coated substrates, at least according to some embodiments or examples as herein described, may be processed by heating to convert any conducting polymer present in the coating into a graphitic material. A coated substrate, such as a coated static mixer and coated electrode, may comprise a graphitic material and optionally a metal source. Coated substrates are also referred to herein as graphitised coated substrates, graphitised metal coated substrates, graphitised catalytic coated substrates and graphitised catalytic coated static mixers, respectively. The graphitised coated substrates, graphitised catalytic coated substrates and graphitised catalytic coated static mixers may also be referred to as graphitised catalytic scaffolds, graphitised catalytic scaffolds and graphitised catalytic static mixers, or as graphitised scaffolds and graphitised static mixers, respectively. A coating composition according to any embodiments or examples thereof may be used to prepare a coated substrate.

The surface of the coated scaffold may comprise one or more layers of the graphitic material. The metal source when present, is embedded within or interspersed on the surface of the graphitic material as individual portions. The individual portions may be in the form of particles or nanospheres, for example palladium nanospheres (see Figure 1). The individual portions, particles or nanospheres, may be separated from each other when present on the surface of the graphitic material or substrate, for example provided as independently spaced apart portions, particles or nanospheres.

In relation to the metal source, in one example the individual portions, particles or nanospheres, may be in a range of about 1 to 500 nm in diameter. For example, the diameter of the individual nanospheres of the metal source may be provided with diameters (in nm) in a range of about 5 to 400, 10 to 350, 25 to 300, or 500 to 250. The diameter of the individual portions, particles or nanospheres of the metal source may be provided with diameters (in nm) of at least about 1, 5, 10, 25, 50, 75, 100, or 150. The diameter of the individual portions, particles or nanospheres of the metal source may be provided with diameters (in nm) of less than about 500, 450, 400, 350, 300, or 250. The diameter of the individual portions, particles or nanospheres of the metal source may be provided with diameters (in nm) in a range between any two of the previous upper and/or lower values. In one example, the density or number of nanospheres on the surface of the graphitic material may be (in nanospheres per pm) at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95. The density or number of nanospheres on the surface of the graphitic material may be (in nanospheres per pm) less than 150, 125, 100, 75, 50, or 25. The density or number of nanospheres on the surface of the graphitic material may be (in nanospheres per pm) provided in a range between any two of the previous upper and/or lower values, for example 1 to 150, 5 to 50, or 25 to 100

In one example, the coated substrate structure may comprise or be formed from a metal, metal alloy, cermet and metal oxide. In one example the substrate comprises or is formed from titanium, aluminium, stainless steel, and an alloy thereof. In another example, the coated substrate structure may be a scaffold (e.g. a static mixer, electrode), material (e.g. a fibre or particle), or a composite. In one example, the substrate is a scaffold and is formed by additive manufacturing. In another example, the substrate may be a scaffold (e.g. a static mixer). It will be appreciated that a static mixer may be configured to enhance chaotic (e.g. transverse) mixing and/or heat transfer.

Properties of a graphitised substrate and graphitised metal substrate

The inventors found that the graphitised coated substrate described herein demonstrated unexpected enhanced properties. It is believed that the enhanced properties of the graphitised substrate are related to the structural changes and morphologies obtained from the formation of graphitised substrate formed by heating the conducting polymer and metal source. The structural changes and morphologies can be analysed through conductivity, thermogravimetric analysis, x-ray photoelectron spectroscopy, Raman spectroscopy, and scanning electron microscopy. X-ray fluorescence (XRF) may be used to analyse structural changes and morphology of the graphitic material, i.e. to determine the composition of any trace elements present in the graphitic material. Elemental microanalysis may also be used to obtain bulk elemental content. It will be appreciated that x-ray photoelectron spectroscopy (XPS) may provide information relating to the surface elemental composition of the graphitised substrate. The XPS may also provide information relating to the particular chemical species present on the surface of the graphitised substrate. The present disclosure provides a graphitised substrate that may comprise or consist of a heteroatom, including for example, nitrogen, oxygen, sulphur, or combinations thereof. In an embodiment or example, the content of nitrogen may be in an amount of about 0.2 % to about 20 %. The content of oxygen may be in an amount of about 0 % to about 20 %. The content of sulphur may be in an amount of about 0 % to about 20 %.

In some embodiments or examples, the content of nitrogen may be in a range selected from between about 0.5 % and 15 %, about 1.0 % and 12 %, about 2.0% and 10%, about 3.0 % and 8.0 %, or about 5 % and 7.5 %. For example, the content of nitrogen may be in the range of about 3.0 % and 6.0 %. The content of nitrogen may be less than about, 20 %, less than about 19 %, less than about 18 %, less than about 17 %, less than about 16 %, less than about 15 %, less than about 14 %, less than about 13 %, less than about 12 %, less than about 11 %, less than about 10 %, less than about 9.5 %, less than about 9.0 %, less than about 8.5 %, less than about 8.0 %, less than about 7.5 %, less than about 7.0 %, less than about 6.5 %, or less than about 6.0 %. The content of nitrogen may be at least about 0.5 %, at least about 1.0 %, at least about 1.5 %, at least about 2.0 % at least about 2.5 %, at least about 3.0 %, at least about 3.5 %, at least about 4.0 %, at least about 4.5 %, at least about 5.0 %, at least about 5.5 %, at least about 6.0 %, at least about 6.5 %, at least about 7.0 %, at least about 7.5 %, at least about 8.0%, at least about 8.5 %, at least about 9.0 %, at least about at least about 9.5 %, at least about 10 %, at least about 11 %, at least about 12 %, at least about 13 %, at least about 14 %, at least about 15 %, at least about 16 %, at least about 17 %, at least about 18 %, or at least about 19 %. The content of nitrogen may be in a range provided by any lower and/or upper limit as previously described.

In some embodiments or examples, the content of oxygen may be in a range selected from between about 0.4 % and 18 %, about 0.6 % and 12 %, about 0.8 % and 8.0 %, or about 1.0% and 6.0%. For example, the content of oxygen may be in a range of about 1.0 % and 10 %. In an example, the content of oxygen may be in a range of about 1.0 % and 2.0 %. The content of oxygen may be less than about 20 %, less than about 18 %, less than about 16 %, less than about 14 %, less than about 12 %, less than about 10 %, less than about 9.0 %, less than about 8.0 %, less than about 7.0 %, less than about 6.0%, less than about 4.0%, less than about 2.0 %, or less than about 1.0 %. The content of oxygen may be at least about 0.4 %, at least about 0.6 %, at least about 0.8 %, at least about 1.0 %, at least about 2.0%, at least about 3.0%, at least about 4.0%, at least about 6.0 %, at least about 8.0 %, at least about 10 %, at least about 12 %, at least about 14 %, at least about 16 %, or at least about 18 %.. The content of oxygen may be in a range provided by any lower and/or upper limit as previously described.

In some embodiments or examples, the content of sulphur may be in a range selected from between about 0.01 % and 18 %, about 0.02 % and 12 %, about 0.03 % and 8.0 %, about 0.04 % and 2.0 %, about 0.05 % and 0.6 %, about 0.06 % and 0.4 %, or about 0.07 % and 0.2 %. For example, the content of sulphur may be in a range of between about 0.01 % and 1.0 %. In an example, the content of sulphur may be in a range of between about 0 % and 5.0 %. In another example, the content of sulphur may be in a range of between about 0 % and 0.2 %. The content of sulphur may be less than about 18 %, less than about 15 %, less than about 12 %, less than about 10 %, less than about 8.0%, less than about 6.0 %, less than about 4.0 %, less than about 2.0 %, or less than about 1.5 %, less than about 1.0%, less than about 0.5%, less than about 0.1%, less than about 0.05%, less than about 0.01%, less than about 0.005%, or less than about 0.001%. In one example, the content of sulphur is less than about 2.0 %. In another example, the content of sulphur may be less than about 0.2 %. The content of sulphur may be at least 0.02 %, at least about 0.04 %, at least about 0.06 %, at least about 0.08 %, at least about 1.0 % at least about 2.0 %, at least about 3.0 %, at least about 4.0 %, at least about 6.0 %, at least about 8.0 %, at least about 10 %, at least about 12 %, at least about 14 %, at least about 16 %, or at least about 18 %. The content of sulphur may be in a range provided by any lower and/or upper limit as previously described.

It will be appreciated that trace materials may be present in the conducting polymer or graphitic material. The trace materials as described herein may be trace materials present in the conducting polymer or graphitic material in trace amounts. It will be appreciated that the content of any trace materials if present, may be less than (in ppm) 50,000, 20,000, 10,000, 5000, 2000, 1000, 500, 200, 100, 50, 10, 5, or 1. For example, the trace materials may be present in a concentration of less than 150 ppm. In one example, the content of trace materials in the conducting polymer or graphitic material is less than about 50 ppm. For example, the trace materials may be metals, halides, silicon, phosphorus, sulphur, arsenic, selenium, or combinations thereof, present in the conducting polymer or graphitic material. It will be appreciated that any reference to“trace” materials, such as“trace metals” present in graphitic material relate to the trace metal content in the graphitic material, and does not relate to the metal source or any precursors thereof that form interspersed particles on the surface of the graphitic material. The trace metals may be iron, sodium, magnesium, aluminium, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, germanium, molybdenum, or combinations thereof. For example, the content of trace metals, if present, in the conducting polymer or graphitic material may be less than (in ppm) 200, 150, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 or 1. The trace halides may be fluoride, chloride, bromide, iodide, or combinations thereof. The trace halides may be chloride, bromide, iodide, or combinations thereof. For example, the content of trace halides, if present, in the conducting polymer or graphitic material may be less than (in ppm) 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1.

In one example, the content of trace silicon, if present, in the conducting polymer or graphitic material may be less than (in ppm) 100, 50, 20, 15, 10, 5, 2, or 1. In another example, the content of trace sulphur, if present, in the conducting polymer may be less than (in ppm) 50,000, 20,000, 10,000, 5000, 2000, 1000, 500, 200, 100, 50, 10, 5, or 1. In another example, the content of trace sulphur, if present, in the graphitic material may be less than (in ppm) 2000, 1800, 1600, 1400, 1200, 1000, 500, 100, 50, 20, 10, 5, or 1.

The heteroaryl or heteroatom content may be controlled by the process parameters as described herein for the preparation of graphitised substrate, for example, the conducting polymer starting material and / or the predetermined temperature.

In some embodiments or examples, the heteroatom content may be controlled by heating the coated substrate to a temperature of between about 350 °C to about 2200 °C. The temperature may be at least about 350 °C, at least about 450 °C, at least about 550 °C, at least about 650 °C, at least about 750 °C, at least about 850 °C, at least about 950 °C, at least about 1200 °C, at least about 1500 °C, or at least about 1800 °C. The temperature may be less than about 2200 °C, less than about 1800 °C, less than about 1500 °C, less than about l200°C, or less than about l000°C. In an example, the heteroatom content may be controlled by heating the graphitic material to a temperature of between about 600 °C to about 1200 °C. In another example, the heteroatom content may be controlled by heating the graphitic material to a temperature of between about 800 °C to about 1200 °C. The temperature may be in a range provided by any lower and/or upper limit as previously described.

The nitrogen heteroatom content can comprise one or more of three primary N-bonding configurations, namely graphitic nitrogen, pyridinic nitrogen and pyrrolic nitrogen. In an embodiment, the nitrogen in the graphitic material may be pyridinic nitrogen, pyrrolic nitrogen, graphitic nitrogen, or combinations thereof. Pyridinic nitrogen refers to nitrogen atoms that bond with two carbon atoms at the edges or defects of graphene and which contributes one p electron to the p system of graphene. Pyrrolic nitrogen refers to nitrogen atoms that contribute two p electrons to the p system of graphene. Graphitic nitrogen refers to nitrogen atoms that substitute for carbon atoms in the graphene matrix.

At least according to some embodiments or examples as described herein, the content of graphitic nitrogen may be in a range between about 0 % to about 50 % (% of total nitrogen content of the graphitic material). In some embodiments or examples, the content of graphitic nitrogen may be in a range between about 5 % and 65 %. In another embodiment or example, the content of graphitic nitrogen may be in a range between about 30 % and 60 %. In an embodiment or example, the content of graphitic nitrogen may be selected from a range of between about 1 % and 60 %, about 2 % and 49 %, about 10 % and 48 %, about 20 % and 47 %, about 25 % and 46 %, or about 30 % and 45 %. The content of graphitic nitrogen may be less than about 65 %, less than about 60%, less than about 50 %, less than about 45 %, less than about 40 %, or less than about 35 %. The content of graphitic nitrogen may be at least about 10 %, at least about 20 %, at least about 30 %, or greater than about 35 %. The content of graphitic nitrogen may be in a range provided by any lower and/or upper limit as previously described. The inventors have surprisingly found that at least according to some embodiments or examples of the process as described herein that a nitrogen content in the graphitic material can be provided that predominantly consists of graphitic nitrogen, pyridinic nitrogen and pyrrolic nitrogen.

The graphitised substrate may be subjected to Raman spectroscopy. Raman analysis provides characteristic peaks depending of specific types of carbon present.

At least according to some embodiments or examples, the graphitised substrate comprises a G band, a 2D band, and optionally a D band. In some embodiments or examples, the graphitised scaffold comprises a G band, a 2D band, and a D band which occur around 1560, 2700, and 1360 cm ¹ respectively. The D band, present at 1360 cm ¹ is referred to as a structural disorder spectrum peak, its intensity reflects the situation in disordered crystal structures. The frequency band at 1580 cm ¹ , designated the G band, refers to monocrystalline graphite specific, graphite lattice CC bond stretching vibration of the inner surface. The degree of graphitisation is used to characterise the complete structure of the sp ² hybridized bond structure. This indicates that in the Raman spectrum, there is a certain correlation between the relative disorder of the graphitic material at 1360 cm ¹ material and the degree of graphitisation at 1580 cm ¹ . It will be appreciated that the more crystalline graphitic materials exhibit the 2D peak around 2700 cm ¹ . At least according to some embodiments or examples of the process as described herein, the degree of order of carbon structures within the graphitic material can be gradually increased with increasing temperature.

In some embodiments or examples, the graphitic material may be in the form of a single layer. In another embodiment, the graphitic material may be in the form of two or more layers, such as stacked sheets. The graphitic material may comprise between about 2 to 100 layers, about 5 to 50 layers, about 10 to 25 layers, or about 15 to 20 layers. The graphitic material may comprise less than 100 layers, 80 layers, 60 layers, 40 layers, 20 layers, 10 layers, 5 layers, or less than 4 layers. The graphitic material may comprise at least about 2 layers, at least about 5 layers, at least about 10 layers, at least about 20 layers, at least about 40 layers, at least about 60 layers, or at least about 80 layers. The graphitic material may comprise layers in a range provided by any lower and/or upper limit as previously described.

It will be understood that the present disclosure provides a graphitic material that has an inherent content of heteroatoms provided by the heteroaryl groups in the conducting polymer. The inherent content of heteroatom is derived from heating the conducting polymer (e.g. polyaniline salt). During the heating process, the

predetermined temperature initiates the formation of graphitic material through the carbonisation of the conducting polymer network. In an embodiment, the carbonisation of the conducting polymer, e.g. polyaniline sulfonate salt, enables the formation of a graphitic material containing inherent heteroatomic species. Advantageously, formation of the graphitic material from heating the conducting polymer, e.g.

polyaniline sulfonate salt, at least according to some embodiments or examples as described herein, can improve charge transfer efficiency due to improved conductivity of the graphitic material, and can further enhance dispersibility.

It has been surprisingly found that the present disclosure provides a graphitic material having excellent conductivity. At least according to some embodiments or examples, the graphitic material may have a conductivity in a range selected from between about 0.5 S/cm and 1000 S/cm, about 2 S/cm and 800 S/cm, about 5 S/cm and 600 S/cm, about 10 S/cm and 400 S/cm, or about 20 S/cm and 200 S/cm. The conductivity of the graphitic material may be at least about 0.5 S/cm, at least about 2 S/cm, at least about 5 S/cm, at least about 10 S/cm, at least about 20 S/cm, at least about 30 S/cm, at least about 50 S/cm, at least about 100 S/cm, at least about 200 S/cm, at least about 500 S/cm, or at least about 800 S/cm. The conductivity of the graphitic material may be less than about 800 S/cm, less than about 500 S/cm, less than about 200 S/cm, less than about 100 S/cm, less than about 50 S/cm, less than about 20 S/cm, less than about 10 S/cm, or less than about 5 S/cm. The conductivity of the graphitic material may be may be in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples, the graphitised film or coating or \ coated substrate may have a conductivity in a range selected from between about 1 S/cm and 1000 S/cm, about 5 S/cm and 800 S/cm, about 10 S/cm and 600 S/cm, about 20 S/cm and 400 S/cm, or about 50 S/cm and 200 S/cm. The conductivity of the graphitised film or coating or coated substrate may be at least about 1 S/cm, at least about 5 S/cm, at least about 15 S/cm, at least about 30 S/cm, at least about 40 S/cm, at least about 50 S/cm, at least about 100 S/cm, at least about 200 S/cm, at least about 300 S/cm, at least about 400 S/cm, at least about 500 S/cm, at least about 600 S/cm, at least about 700 S/cm, or at least about 800 S/cm. The conductivity of the graphitised film or coating or coated substrate may be less than about 800 S/cm, less than about 700 S/cm, less than about 600 S/cm, less than about 500 S/cm, less than about 400 S/cm, less than about 300 S/cm, less than about 200 S/cm, or less than about 100 S/cm. The conductivity of the graphitised film or coating or coated substrate may be may be in a range between any two of these previously described upper and/or lower values.

It will be appreciated that other properties may be used to define the properties of the graphitic material, for example, surface area, density and porosity. The surface area and pore size of the graphitic material can be measured using the Brunauer- Emmett-Teller (BET) method and determined by degassing the samples at 250°C for 16 hours prior to analysis. The BET surface areas were determined from the adsorption and desorption isotherms of nitrogen at -l96°C using a Quantachrome Autosorb- 1 volumetric adsorption system. The packed or particle density of the graphitic material can also be measured. It will also be appreciated that these properties can be controlled and dictated by various factors, such as the conducting polymer, which can allow for versatility in its application. Without wishing to be bound by theory, properties such as surface area, pore density and porosity can vary by orders of magnitude depending on their degree of stacking, crumpling, pillaring, and their heteroatom and defect content.

In some embodiments or examples, the surface area of the graphitic material may be in a range of about 0.5 m ² /g to 750 m ² /g, about 1.0 m ² /g to 500 m ² /g, about 1.5 m ² /g to 250 m ² /g, about 2.0 m ² /g to 100 m ² /g, or about 2.5 m ² /g to 50 m ² /g. The surface area of the graphitic material may be at least about 0.5 m ² /g, at least about 1.5 m ² /g, at least about 2.0 m ² /g, at least about 2.5 m ² /g, at least about 5.0 m ² /g, at least about 10 m ² /g, at least about 50 m ² /g, at least about 100 m ² /g, at least about 200 m ² /g, at least 300 m ² /g, at least 400 m ² /g, at least 500 m ² /g, at least 600 m ² /g, or at least 700 m ² /g. The surface area of the graphitic material may be less than about 750 m ² /g , less than about 500 m ² /g, less than about 400 m ² /g, less than about 250 m ² /g, less than about 200 m ² /g, less than about 150 m ² /g, less than about 100 m ² /g, less than about 50 m ² /g, less than about 25 m ² /g, less than about 10 m ² /g, less than about 5 m ² /g, or less than about 2 m ² /g. The surface area of the graphitic material may be may be in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples, the total pore volume of the graphitic material may be in a range of about 0.2 cm ³ /g to 10 cm ³ /g, about 0.3 cm ³ /g to 8 cm ³ /g, about 0.4 cm ³ /g to 7 cm ³ /g, about 0.5 cm ³ /g to 6 cm ³ /g, about 0.7 cm ³ /g to 5 cm ³ /g, about 0.8 cm ³ /g to 4 cm ³ /g, 0.9 cm ³ /g to 3 cm ³ /g, or about 1.0 cm ³ /g to 2.0 cm ³ /g. The total pore volume of the graphitic material may be at least about 0.2 cm ³ /g, at least about 0.5 cm ³ /g, at least about 1.0 cm ³ /g, at least about 2.0 cm ³ /g, at least about 4 cm ³ /g, at least about 6 cm ³ /g, or at least about 8 cm ³ /g. The total pore volume of the graphitic material may be less than about 9 cm ³ /g, less than about 7 cm ³ /g, less than about 5 cm ³ /g, less than about 3 cm ³ /g, less than about 1.5 cm ³ /g, or less than about 0.4 cm ³ /g. The total pore volume of the graphitic material may be may be in a range between any two of these previously described upper and/or lower values.

In some embodiments or examples, pore size of the graphitic material may be in a range of about 0.5 nm to 500 nm, about 1.0 nm to 100 nm, about 1.5 nm to 50 nm, about 2.0 nm to 25 nm, about 2.5 nm to 15 nm, or about 3.0 nm to 10 nm. The pore size of the graphitic material may be at least about 0.5 nm, at least about 1.0 nm, at least about 2.0 nm, at least about 5.0 nm, at least about 10 nm, at least about 25 nm, at least about 50 nm, at least about 100 nm, at least about 200 nm, or at least about 400 nm. The pore size of the graphitic material may be less than about 500 nm, less than about 300 nm, less than about 200 nm, less than about 150 nm, less than about 80 nm, less than about 40 nm, less than about 30 nm, less than about 20 nm, less than about 15 nm, less than about 10 nm, less than about 8 nm, less than about 4 nm, or less than about 2 nm. The pore size of the graphitic material may be may be in a range between any two of these previously described upper and/or lower values. Environment

At least according to some embodiments or examples as described herein, the method of preparing the graphitised substrate from the conducting polymer and the metal source via a heating process may be carried out in a controlled environment. For example, the controlled environment may be a furnace. It will be appreciated that other heating methods may be used whereby the method is carried out in a controlled environment. For example, the heating method may be selected from any one of flash pyrolysis, flash vacuum pyrolysis, laser pyrolysis, or microwave pyrolysis.

In some embodiments or examples, the controlled environment may be air or inert gas. The inert gas may be selected from any one of nitrogen, helium or argon.

The inert gas may be selected from nitrogen or argon. In a preferred embodiment, the inert gas is nitrogen. In some embodiments or examples, the controlled environment may be at atmospheric pressure or vacuum. In some embodiments or examples the controlled environment may also be used to provide a cooling step according to any embodiment or example thereof as described herein.

In some embodiments or examples, the inert gas flow rate may be in a range between about 0.5 L/min to about 30 L/min. The inert gas flow rate may be in a range from between about 1 L/min and 20 L/min, about 1.5 L/min and 15 L/min, or about 2 L/min and 10 L/min. The inert gas flow rate may be less than about 30 L/min, less than about 25 L/min, less than about 20 L/min, less than about 15 L/min, less than about 10 L/min, or less than about 5 L/min. The inert gas flow rate may be at least about 0.5 L/min, at least about 1 L/min, at least about 1.5 L/min, at least about 2 L/min, at least about 2.5 L/min, at least about 3 L/min, at least about 3.5 L/min, at least about 4 L/min, at least about 5 L/min, or at least about 10 L/min. The inert gas flow rate may be provided in a range between any two of these previously described upper and/or lower values. At least according to some embodiments or examples, the inert gas flow rates can provide further advantages in facilitating higher N and/or O content, and/or lower S content, in the graphitic material.

In another example, the oxygen level in the controlled environment (by volume %) may be maintained below about 2%, for example below about 1%, 0.1%, 0.01%, or 0.001%. Applications

The coating compositions or coated substrates according to various embodiments or examples as described herein may be used in particular applications. Some of the applications, methods, or uses, include catalysis (e.g. catalytic reactions including as carbon supported catalysts, photocatalysis, or other catalytic reactions such as heterogeneous catalysis), printed electronics (e.g. inks, sensors, flexible electronics), conductive coatings (e.g. textiles, aerospace coatings, marine coatings), anti-corrosive coatings (e.g. aerospace coatings, marine coatings), composites (e.g. performance and engineering polymers, coated fibres, polymer compositions, rubber, concrete etc.), and energy storage devices (e.g. electrodes, coated electrodes, supercapacitors, fuel cells, batteries). The coating compositions may be used as an additive or ingredient in other compositions, or used as a layer in combination with other layers in a coating system (e.g. as an intervening layer, such as on a conversion coated metal substrate optionally comprising other post-coating layers). Further details of the applications are provided as follows.

Printable electronics

Printed electronics may include portable electronics, signage, lighting, product identification, flexible electronic devices (such as those that can be rolled or bent), photovoltaic devices, medical and diagnostic devices, antennas (including RFID antennas), displays, sensors, thin-film batteries, electrodes, for example.

The coating compositions or coated substrates according to at least some embodiments or examples as described herein, for example graphitised substrates, may be provided in or used for preparing printable electronics. In one example, there is provided a process or method of preparing a printed electronic device, comprising applying a layer of an electrically conductive ink to a portion of a surface of the substrate, wherein the electrically conductive ink comprises a coating composition according to any of the embodiments or examples as described herein, and optionally an additive. The additive may be a binder, for example, or other additive as described herein. The electrically conductive ink may be applied to the substrate using any suitable method, including, but not limited to, by syringe, spray coating, electrospray deposition, ink-jet printing, spin coating, thermal transfer (including laser transfer) methods, screen printing, rotary screen printing. Conductive coatings

The coating compositions or coated substrates according to at least some embodiments or examples as described herein, for example graphitised coated substrates, may be used in or provided as conductive coatings. In one example, there is provided a process or method of preparing a conductive coating or conductive coated substrate, comprising at least partially coating a substrate with a coating composition (e.g. graphitised coating), according to any examples as described herein.

In some examples, the conductive coatings may include a variety of smart textile applications, such as sensors, data transmission lines, or heated fabrics. For example, fibres for use in textile may be coated with a coating composition according to any examples as described herein to form a coated substrate that is a coated fibre. The coated fibres may be used in preparing fabrics and textiles. In another example, prepared fabrics and textiles may be coated with a coating composition according to any examples as described herein.

In other examples, the conductive coatings may be applied to automobile, aerospace and marine technologies, such as conductive paints. The conductive paints may be useful in dissipating lightning strike occurrences, for example. Conductive coatings (e.g. paints) may comprising a coating composition according to any embodiments or examples thereof as described herein. The coating compositions may be mixed with resins, polymers, and/or various additives in forming further coating compositions for particular applications.

The conductive coating may be applied to the substrate using any suitable method, including, but not limited to, spray coating, electrospray deposition, spin coating, dip coating. Anti-corrosive coatings

The coating compositions or coated substrates according to at least some embodiments or examples as described herein, may be used as corrosion inhibitors or as anti-corrosive coatings. The anticorrosive coatings may be used in the automobile,, aerospace, marine, and oil and gas industry for example. The coating compositions or coated substrates may be used in, or for coating, or preparing, various structural components, infrastructure, pipes and conduits, for example. The coating compositions may be used together with other coatings, such as conversion coated metal substrates. The coatings may be provided as intervening and/or post-coating layers in a coating system.

Composites

The coating compositions or coated substrates according to at least some embodiments or examples as described herein, may be used in preparing composites. For example, the coating compositions may be used as an additive or ingredient in other compositions, such as mixed or blended into resins or polymer compositions that are used in preparing composites. The coating compositions may be used in coating fibres that are used in composites. The coating compositions may be used to coat a composite material or component. In other examples, the coating compositions may be used in preparing particular performance or engineering based polymers, rubbers, and/or concretes.

Energy storage devices

The coating compositions or coated substrates according to at least some embodiments or examples as described herein, may be used as or in preparing electrodes (e.g. carbon electrode to replace AC or CC electrodes), coated electrodes, or various layers or interconnecting components/structures. The coating composition or coated substrate may be used in an energy storage device including primary and/or secondary batteries, supercapacitors, fuel cells. Catalytic Processes

The coated substrates, for example graphitised scaffolds or graphitised static mixers, according to any examples as herein described, may be suitable for use in catalysis. In one example, the coated substrates may be suitable for heterogeneous reactions, such as hydrogenation reactions. In another example, the coated substrates may be suitable for photocatalytic reactions. The coated substrates may be used as carbon supported catalysts (e.g. photocatalysis or hydrogenations). In one example, there is provided a process or method of preparing a product by a heterogeneous reaction comprising one or more graphitised static mixers according to any examples as described herein. In another example, there is provided a use of one or more graphitised static mixers according to any examples as described herein in a heterogeneous reaction, system, method or process. In one example, the heterogeneous reaction is a hydrogenation reaction.

In one example, there is provided a continuous flow process for a heterogeneous reaction comprising one or more graphitised static mixers according to any examples as described herein. In one example, the heterogeneous reaction is a hydrogenation reaction.

In one example, there is provided a continuous flow chemical reactor for use in reaction of one or more fluidic reactants, the reactor comprising one or more graphitised scaffolds according to any examples as described herein. The graphitised scaffold may be a graphitised static mixer.

A continuous flow reaction system (also referred to as a continuous flow chemical reaction system) can comprise one or more chamber sections in fluidic communication with each other. One or more chamber sections can comprise a static mixer or coated scaffold according to any examples thereof as described herein. The static mixer (also referred to herein as a“static mixer element”) may be configured for inserting into a continuous flow chemical reaction system, and may be referred to as a “static mixer insert”. It will be appreciated that the static mixer, or reactor thereof, may comprise one or more reactant inlets for supply of one or more fluidic reactants to a chamber section, and one or more outlets in fluid communication with the static mixer for receiving an output stream comprising a product or products of the reaction. The static mixers can provide an integral element as part of a chemical reactor chamber. The static mixer element for a continuous flow chemical reaction system chamber may be configured to define a plurality of passages for dispersing and mixing one or more fluidic reactants during flow and reaction thereof through the mixer. A substantial part of the surface of the scaffold may comprise the coating composition comprising the conducting polymer and the metal source, wherein the metal source is a catalyst material, as described herein. It will be appreciated that the coated scaffold, such as the graphitised static mixer, can provide the surface of the scaffold with catalytically reactive sites. It will be appreciated that the catalytically reactive sites comprise the catalytic material, for example as portions, particles or nanospheres in the surface of the graphitic material present in the scaffold or surface of the static mixer.

It will be appreciated that the coated scaffold describe herein may be at least partially coated with the coating composition and may be used in a continuous flow chemical reactor for synthesising a reaction product, for example a hydrogen insertion or hydrogenation reaction. A range of products may be obtained from the process, for example products obtained from a hydrogen insertion or hydrogenation reaction. The process may cover production of a range of inorganic and organic compounds, and for example may involve the following types of reactions and products:

• Hydrogenation or hydrogen insertion with a nitrogen species or compound comprising nitrogen, for example reaction of a hydrogen species and a nitrogen species to form ammonia;

• CO2 hydrogenation to produce products such as methanol, formic acid, dimethyl carbonate and carbon monoxide;

• Alkene hydrogenation, for example hexene to hexane or benzene to cyclohexane; and

• Alkyne hydrogenation, for example alkyne to alkene and/or alkane, or nitriles to amines.

It will be appreciated that various parameters and conditions used in the process, such as temperatures, concentration/amounts of materials and reactants, may be selected depending on a range of variables of the process including the product to be synthesised, chemical reaction or mechanisms involved, reactant source, selection of catalyst(s) on the coated scaffold, or type of substrate or reactor being used and materials and configuration thereof.

In some embodiments or examples, there is provided:

1. A coated scaffold comprising at least a partially coated scaffold with a graphitised coating, wherein the surface of the coated scaffold comprises one or more layers of a graphitic material, wherein the graphitised coating may be formed by heating a coating composition comprising a conducting polymer.

2. The coated scaffold as defined herein, wherein the coating composition further comprises a catalyst material, wherein heating the coating composition forms a graphitised catalytic coating.

3. The coated scaffold as defined herein, wherein the surface of the coated scaffold comprises one or more layers of the graphitic material, and wherein the catalyst material may be interspersed on the surface of the graphitic material as individual particles.

4. The coated scaffold as defined herein, wherein the individual particles of the catalyst material may be in a range of about 1 to 500 nm in diameter.

5. The coated scaffold as defined herein, wherein the individual particles of the catalyst material may be in the form of nanospheres.

6. The coated scaffold as defined herein, wherein the pre-coated scaffold structure comprises a metal, metal alloy, cermet or metal oxide.

7. The coated scaffold as defined herein, wherein the scaffold is a static mixer.

8. A catalytic coating composition comprising of a conducting polymer or a graphitic material of the conducting polymer, a catalyst material, optionally one or more fluidic carriers, and optionally one or more additives.

9. The catalytic coating composition as defined herein, wherein the conducting polymer is selected from the group consisting of polyarylamine, polyarylthiol, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, and poly(3,4- ethy 1 enedi oxy thi ophene) .

10. The catalytic coating composition as defined herein, wherein the conducting polymer is polyarylamine. 11. The catalytic coating composition as defined herein, wherein the conducting polymer is a polyaniline base or polyaniline salt.

12. The catalytic coating composition as defined herein, wherein the polyaniline salt is a poly aniline sulfonate salt.

13. The catalytic coating composition as defined herein, wherein the polyaniline sulfonate salt is selected from the group consisting of polyaniline methanesulfonic acid, polyaniline camphorsulfonic acid, polyaniline p-toluenesufonic acid, polyaniline dodecyl benzene sulfonic acid, or polyaniline dinonylnapthalenesulfonate, and combinations thereof.

14. The catalytic coating composition as defined herein, wherein the polyaniline sulfonate salt is a polyaniline dinonylnapthalenesulfonate salt.

15. The catalytic coating composition as defined herein, wherein the catalytic material comprises a metal selected from at least one of iron, cerium, cobalt, copper, zinc, nickel, palladium, platinum, gold, silver, ruthenium, iridium, rhodium, titanium vanadium, zirconium, niobium, tantalum, and chromium, or complexes thereof.

16. The catalytic coating composition as defined herein, wherein the metal is selected from palladium, platinum, ruthenium, or rhodium, or complexes thereof.

17. The catalytic coating composition as defined herein, wherein the catalyst material is interspersed in the catalytic coating composition.

18. The catalytic coating composition as defined herein, wherein the graphitic material is prepared by heating a conducting polymer to a predetermined temperature.

19. The catalytic coating composition as defined herein, wherein the composition is a liquid formulation, and the conducting polymer is a fluid and/or the fluidic carrier comprises a liquid.

20. The catalytic coating composition as defined herein, wherein the catalytic coating composition is a solid composition comprising a plurality of particles of the graphitic material and the catalyst material.

21. A method of preparing a coated scaffold comprising a step of at least partially coating a scaffold with a catalytic coating composition as defined herein.

22. The method as defined herein, wherein the composition comprises a conducting polymer. 23. The method as defined herein, wherein the method comprises or consists the following steps:

(i) heating the coated scaffold to a predetermined temperature to initiate formation of a graphitised scaffold; and

(ii) optionally cooling the graphitised scaffold.

24. The method as defined herein, wherein the predetermined temperature for step (i) is between about 200 °C to about 2200 °C.

25. The method as defined herein, wherein the predetermined temperature for step (i) is at least 600 °C.

26. The method as defined herein, wherein the heating process of step (i) comprises (i)(a) pre-heating the coated scaffold to predetermined temperature to stabilise the coated scaffold, and (i)(b) heating the stabilised coated scaffold to a predetermined temperature to initiate formation of graphitised scaffold.

27. The method as defined herein, wherein the predetermined temperature of step (i)(a) is between about 200 °C to about 600 °C.

28. The method as defined herein, wherein the predetermined temperature of step (i) or step (i)(b) is between about 600 °C to about 2200 °C.

29. The method as defined herein, wherein the predetermined temperature of step (i) or step (i)(b) is between about 650 °C to about 900 °C.

30. The method as defined herein, wherein the coated scaffold is maintained at the predetermined temperature of step (i)(a) for about 30 to about 180 minutes.

31. The method as defined herein, wherein the coated scaffold is maintained at the predetermined temperature of step (i) or step (i)(b) for about 30 to about 180 minutes.

32. The method as defined herein, wherein the coated scaffold formed in step (i) or step (i)(b) is cooled in step (ii) to ambient temperature at a rate of about 2 °C to about 100 °C/minute.

33. The method as defined herein, wherein the method is carried out in a controlled environment.

34. The method as defined herein, wherein the controlled environment is air or inert gas. 35. The method as defined herein, wherein the controlled environment is at atmospheric pressure or vacuum.

36. The method as defined herein, wherein the coated scaffold has a content of heteroatom, and wherein the heteroatom is selected from one or more of nitrogen, oxygen, sulphur, or combinations thereof.

37. The method as defined herein, wherein the content of heteroatom is selected from nitrogen in an amount of about 0.2 % to about 20 %, oxygen in an amount of about 0 % to about 20 %, and sulphur in an amount of about 0 % to about 20 %.

38. The method as defined herein, wherein the content of heteroatom is controlled by heating the coated scaffold to a temperature of between about 350 °C to about 2200 °C.

39. The method as defined herein, wherein the coated scaffold comprises a G band, a 2D band, and optionally a D band.

40. The method as defined herein, wherein the coated scaffold comprises a content of one or more of graphitic nitrogen, pyridinic nitrogen and pyrrolic nitrogen.

41. The method as defined herein, wherein the coated scaffold comprises a content of graphitic nitrogen in a range between about 0.2 % to 50 %.

42. The method as defined herein, wherein the coated scaffold has a conductivity of at least 30 S/cm.

43. The method as defined herein, wherein the coated scaffold comprises nanospheres.

44. A continuous flow chemical reactor for use in reaction of one or more fluidic reactants, the reactor comprising one or more graphitised scaffolds as defined herein.

45. The continuous flow chemical reactor as defined herein, wherein the graphitised scaffold is a graphitised static mixer.

46. A continuous flow process for a heterogeneous reaction comprising one or more graphitised scaffolds as defined herein, the graphitised scaffolds being provided as one or more graphitised static mixers.

47. The continuous flow process as defined herein, wherein the heterogeneous reaction is a hydrogenation reaction. EXAMPLES

The present disclosure is further described by the following examples. It is to be understood that the following description is for the purpose of describing particular examples only and is not intended to be limiting with respect to the above description.

Example 1 - General process for the preparation of a coating composition

A conducting polymer (e.g. a polyaniline salt) or a graphitic material was dissolved or dispersed in an organic solvent (e.g. toluene or N-Methyl-2-Pyrrolidone). A metal source (e.g. Pd precursor) was added to the solution and sonicated for 30 minutes at 40 °C to form a catalytic coating composition. The catalytic coating composition was stirred for 24 hours to achieve a solution without any visible sediment.

Example la

According to the general process described above, polyaniline-DNNSA was dissolved in an organic solvent. Palladium nitrate dihydrate (Pd(NCb)2 2H ₂ 0) was used as Pd precursor. Typically, Pd(NCb)2 2H ₂ 0 (2.14 g) was added to PANI-DNNSA solution (15.0 g, 32 wt%) in order to give an expected elemental Pd content of 5 wt%. Example 2 - General process for the preparation of a coated substrate

A substrate (e.g. a scaffold) was dip or spin coated in the coating composition via immersion for 20 seconds. The excess solution was allowed to drain from the scaffold aided by pressurised air, optionally in order to ensure that the fluidic paths of the scaffold remained open. The coated scaffold was then placed in a convection over overnight until a constant mass was reached. A uniform thin film or coating was formed on the surface of the scaffold.

Example 2a

According to the general process described above, a 3D printed 316 stainless steel static mixer was then dip coated in the PANI-DNNSA/Pd(N0 ₃ ) ₂ catalytic coating composition solution via immersion for 20 seconds and dried according to the general process described above.

Example 2b

According to the general process described above, a stainless steel plate was then dip coated in the PANI-DNNSA/Pd(N03)2 catalytic coating composition solution via immersion for 20 seconds and dried according to the general process described above.

Example 3 - General process for preparation of a graphitised substrate

The coated substrate was transferred to a horizontal tube furnace and held at room temperature for 30 minutes to purge the system with N2 _(g). The coated scaffold was then optionally stabilised at 280 °C (ramp at 5 °C/min, hold for 1 h). After this time the temperature raised to 800 °C (ramp at 5 °C/min, hold for 1 h) while continuing to flush with a stream of N2 _(g).

The furnace was then allowed to cool to < 200 °C and the coated substrate removed.

Example 3a

The coated 3D printed 316 stainless steel static mixers were heated and cooled according to the general heating and cooling process described above to form graphitised static mixers.

Example 3b

The coated stainless steel static plate was heated and cooled according to the general heating and cooling process described above to form a graphitised plate.

Example 4 - General process for the preparation of coating composition powders and particles

A conducting polymer (e.g. a polyaniline salt) or a graphitic material was dissolved or dispersed in an organic solvent (e.g. toluene or N-Methyl-2-Pyrrolidone). A metal source (e.g. Pd precursor) was added to the solution and sonicated for 30 minutes at 40 °C to form a coating composition. The coating composition was stirred for 24 hours to achieve a solution without any visible sediment.

The solution was transferred to a crucible followed by drying and calcination.

Example 4a

According to the general process described above, polyaniline-DNNSA was dissolved in an organic solvent. Palladium nitrate dihydrate (Pd(NCb)2 2H ₂ 0) was used as Pd precursor. Typically, Pd(NCb)2 2H ₂ 0 (2.14 g) was added to PANI-DNNSA solution (15.0 g, 32 wt%) in order to give an expected elemental Pd content of 5 wt%.

The solution was then dried according to the process described above.

Example 5a - General process for preparation of conducting polymer metal/metal oxide coatings

Metal oxide or metal salt or metal particles (1 wt%) was added to 35 wt% of a conducting polymer (e.g. a polyaniline salt) in a solution of solvent (e.g. toluene solution). The mixture was stirred manually for approximately 1 minute then sonicated for 30 to 60 minutes. The resulting viscous solution was applied to a substrate (e.g. quartz, nickel foam) using a known method as descried herein (e.g. hand-casted, spin- coated, dip-coated). The wet coating thickness varied from 50 to 150 microns. The coating on the substrate was then dried in an oven at 90°C for approximately 12 hours to form a coated substrate.

Example 5b - General process for the preparation of conducting polymer metal/metal oxide powders

Metal oxide or metal salt or metal particles (1 wt%) was added to 50 wt% of a conducting polymer (e.g. a polyaniline salt) in a solution of solvent (e.g. toluene solution). The mixture was stirred manually for approximately 1 minute then sonicated for 30 to 60 minutes, and then transferred to a round bottom flask. Additional toluene was used to aid the transition. Toluene from the mixture was removed by rotary evaporator at 40°C for 30 to 45 minutes under vacuum. Acetone (50x by weight) was added to the conducting polymer metal/metal oxide sample. The mixture was stirred for 30 to 60 minutes, allowing solid precipitated out of solution completely. The precipitate was filtered and washed with acetone until the washing solution become clear. The dark solid conducting polymer metal/metal oxide powder was dried in an oven at 90°C for approximately 12 hours to form a powder.

Example 5c - General process for the preparation of graphitic metal/metal oxide coatings and powders

The coated substrate as described in Example 5a or the powder as described in

Example 5b were inserted into the middle of a horizontal quartz tube furnace. When powder sample was used, a quartz combust boat was used as sample container. The furnace was purged with in-house nitrogen gas for 10 minutes, then heated up to 800 or 1000 or 1060 or l200°C, respectively, under continuing nitrogen gas flow at a heating rate of l5°C/min. Once the target temperature was reached, the furnace was held at the target temperature for 5 min, then allowed to cool down to ambient temperature under the nitrogen flow. The graphitic metal/metal oxide coated substrate or powder was removed from the furnace and stored in a desiccator. The following table provides a list of graphitic metal/metal oxide coated substrate or powder prepared according to the general processes described above in Examples 5a, 5b and 5c.